1 Processing for Properties

Han E. H. Meijer

Centre for Polymers and Composites (CPC), Eindhoven Polymer Laboratories,

Eindhoven University of Technology, Eindhoven, The Netherlands

List of Symbols and Abbreviations 4

1.1 Introduction 7
1.2 Modeling Aspects 9
1.2.1 Introduction 9
1.2.2 Injection Molding 10
1.2.3 Dimensional Stability 11
1.2.4 Density and Stress Distributions 12
1.2.5 Choice of the Constitutive Equation 17
1.2.6 Deformation History 21
1.2.7 Discussion 28
1.3 Structure Development During Flow 30
1.3.1 Introduction *. 30
1.3.2 Chaotic Distributive Mixing 33
1.3.3 Dispersive Mixing 36
1.3.4 Two-Zone Models 37
1.3.5 Phase Separation 40
1.3.6 Crystallization 45
1.3.7 Liquid Crystalline Polymers 47
1.3.8 Discussion 49
1.4 Reactive Processing 49
1.4.1 Introduction 49
1.4.2 Thermoplasts in Reactive Solvents 50
1.4.3 In Situ Characterization 52
1.4.4 Discussion 54
1.5 Processing for Ultimate Properties 55
1.5.1 Introduction 55
1.5.2 Ultimate Modulus and Strength 56
1.5.3 Ultimate Toughness 60
1.5.4 Discussion 64
1.6 Extruder Modeling 64
1.6.1 Introduction 64
1.6.2 Single Screws 65
1.6.3 Twin Screws 66
1.6.4 Discussion 68
1.7 Concluding Remarks 69
1.8 References 70
4 1 Processing for Properties

List of Symbols and Abbreviations

Ca capillary number
d membrane thickness
D diffusion constant
De Deborah number
Dlc critical thickness/interparticle distance
G gas
G' shear modulus
h mold thickness
H characteristic geometric dimension; channel depth
J flux
L liquid
Mc molecular weight between crosslinks
Me molecular weight between entanglement points
N
i first normal stress difference
P viscosity ratio, pressure
P permeability
R drop radius
S solubility
t time
T temperature
Tc crystallization temperature
td delay time
T
&
glass transition temperature
Tm melting temperature
Teff effective temperature
Tpol polymerization temperature
V process velocity
v
v piston velocity
x> y> z Cartesian coordinates
a selectivity or separation parameter
8 gap height
7 shear rate
dimensionless parameter in PTT model
viscosity of continuous phase
Vd viscosity of dispersed phase
X fluid relaxation time
dimensionless parameter in PTT model
p density
a stress
T shear stress
ABS acrylonitrile-butadiene-styrene
BA butvlmethacrvlate
 List of Symbols and Abbreviations

BMC bulk molding compounds

B.R Berghmans point
CA cellulose acetate
CIPS chemically induced phase separation
CTM cavity transfer mixer
DIPS diffusion-induced phase separation
DR draw ratio
DSC differential scanning calorimetry
EtOH ethanol
FDM finite difference method
FEM finite element method
FIB flow-induced birefringence
GAIM gas-assisted injection molding
GMC glassfiber (mats) reinforced compounds
GPC gel permeation chromatography
HDPE high density polyethylene
HIPS high impact polystyrene
HPF high performance fibers
HPPE high performance polyethylene
IPN interpenetrating network
LDA laser Doppler anemometry
LDPE low density polyethylene
MD machine direction
MeOH methanol
MFI melt flow index
MMA methylmethacrylate
MMIM multi-material injection molding
NMP ^-methyl pyrrolidone
PAR polyarylate
PC polycarbonate
PEI polyetherimide
PES polyethersulfone
PETP poly(ethylene terephthalate)
PH polyhydroxyether
PIB polyisobutene
PMMA poly(methylmethacrylate)
PP polypropylene
PPE poly(phenylene-ether)
PS polystyrene
PSF polysulfone
PTT Phan-Thien Tanner
PUR polyurethane
REX reactive extrusion
RIM reaction injection molding
RMP reactor modified polymers
6 1 Processing for Properties

ROA rheo-optical analyzer

RRIM reinforced reaction injection molding
RTM resin transfer molding
SAXS small angle X-ray scattering
SBR styrene-butadiene rubber
SRIM structural reaction injection molding
S solid
St styrene
STP standard temperature and pressure
SUPG streamline upwind method
TCE trichloroethylene
TD transverse direction
TIPS temperature-induced phase separation
UHMWPE ultrahigh molecular weight polyethylene
WAXS wide angle X-ray scattering

1.1 Introduction
Given their intrinsically anisotropic
nature [with strong intramolecular covalent
bonds in the backbone, weak intermolecu-
lar interactions of secondary van der Waals
and/or hydrogen bonds, and the physical
network (entanglement) forces] polymers
can be considered as the prime example of
materials where neither the chemical struc-
ture nor the design solely determines the
product's properties. As a consequence, in
polymer technology the complete "chain of
knowledge" is explored, from pure synthe-
sis (organic chemistry), via catalysis, reac-
tor technology (chemical engineering) and
polymer design or the development of new
polymeric systems (polymer chemistry and
physics), to the final shaping process and
product design (mechanical engineering).
In the processing of polymers, the topic of
this Volume, the whole, complex, deforma-
tion-temperature history proves to be rele-
vant and, as a consequence, this research
area is based on (relatively advanced) com-
putational methods on the one hand and rhe-
ology on the other.
Most important for polymers is their ease
of processability via automated mass pro-
duction technologies. The prime example
thereof is the injection molding process,
where processability is exploited through
freedom in .materials choice and product
design. Apart from related processes, e.g.,
(reinforced or structural) reactive molding,
transfer molding, and pressing, the contin-
uous processing techniques e.g., profile
extrusion, film casting, film blowing, and
blow molding, find extensive applications.
Processes like these have attracted a great
deal of attention, resulting in optimization
processes with respect to controlled produc-
tion and in the prediction of the influence of
process parameters on the consistency and
quality of the production process. This con-
1.1 Introduction
trol results partly from (a large number of)
experiments, yielding practical expertise,
and partly from mathematical modeling
(Chap. 2 of this Volume).
The trends in modeling nowadays are
such that attention is focused on the predic-
tion of product properties, given the mate-
rial and production process selected, the
processing conditions, and the final product
design. Purely because of its great practical
importance, the injection molding process
has been chosen as the, given its complex-
ity, not so much obvious, but certainly the
most relevant process to be modeled. Sub-
stantial progress has been made in the last
few years in predicting, e.g., the accuracy
and dimensional stability, in the short and
the long term, of injection molded products.
Polymers are rarely used in their virgin
form. Mostly additives are used, from sta-
bilizers and antioxidants, color pigments,
and reinforcing agents, such as fillers and
fibers, to dispersed rubber inclusions in
order to obtain improved impact properties.
Mixing in the molten state is, consequently,
inherently part of polymer processing. The
resulting morphology strongly determines
the final properties (Chaps. 3 and 12 of this
Volume), and interfacial design proves to be
relevant for the final application (Chaps. 8
and 15 of this Volume). Reactions often
occur during processing and the macromol-
ecules forming the continuous phase, the
compatibilizers at the interfaces, or the dis-
persed phase itself, are made in situ
(Chaps. 6, 7, 8, and 9 of this Volume). Crys-
tallizable polymers form heterogeneous
structures upon crystallization and the
temperature-deformation history strongly
influences the resulting microstructure
(Chaps. 4 and 5 of this Volume).
While the mechanical (and thermal) prop-
erties of polymeric materials, with modulus
values of typically 3 GPa and strength val-
ues of 0.05 GPa, are generally far inferior
8 1 Processing for Properties
to those of competitive structural materials,
like metals and ceramics, processing tech-
niques have been developed to explore the
maximum theoretical values of polymers if
they are loaded not by their weak secondary
bonds, but by their strong covalent bonds.
Exceptional values for the modulus and
strength of 150 and 4 GPa are now realized
and, given their low density, the specific val-
ues for polymers are by far superior to those
of the more classical structural materials. A
prerequisite for obtaining these rather spec-
tacular mechanical properties is full align-
ment of the chains, in order to be able to load
the covalent bonds. The shape of the prod-
uct is, necessarily, a fiber, and some of the
properties are lost again if 2- or 3-dimen-
sional structures have to be made using
fiber-reinforced composites. Basically, two
different techniques are available to orient
the chains. The first starting with complete-
ly stiff molecules that, consequently, have
to be spun from solutions to orient them in
a dry, wet, or air-gap spinning operation, and
second, a method based on flexible mole-
cules that are stretched in the solid state
(Chaps. 11 and 16 of this Volume). Thermo-
tropic polymers can be regarded as interme-
diates between these extremes, and process-
ability is introduced by generating flexibil-
ity in the molecular structure, either by alter-
nating stiff and flexible segments ("spac-
ers") in the main chain or by adding flex-
ibility, or alternatively rigidity, to the poly-
mer side chains. These examples already
reveal the great potential of polymers, given
the enormous flexibility in adjusting their
basic structure, via chemistry, or alterna-
tively by changing their morphology via
physical or chemo-physical processes such
as (reactive) blending or by introducing
orientation.
For the group of functional polymers,
special processing techniques have been
developed, e.g., spin-coating, and different
light-controlled in situ polymerization pro-
cesses combined with selective dissolution
methods (see Chap. 13 of this Volume). An
area of great importance is that of the intrin-
sic conductive polymers which, being con-
jugated, without exception can be regarded
as intractable from a processing point of
view. However, new developments are also
promising here, and interesting results have
already been obtained (Chap. 14 of this Vol-
ume). Similar arguments hold for polymers
(and their processing techniques) that are
being developed for their optical properties.
Apart from specific applications, e.g., the
development of graded index optical fibers,
the bulk properties are also investigated, and
by controlling the microstructure, optical
clarity can sometimes be combined with
obtaining the intrinsic ultimate toughness of
the polymers. For this purpose, specific pro-
cessing routes have been developed, based
on systems where reactive diluents are used
to help processability and where, after
molding or shaping, the reactive solvents
are polymerized and thus converted into
nonsolvents. The concomitant phase separ-
ation is often accompanied by phase inver-
sion, and yields specific morphologies that
cannot be realized by more conventional
processing techniques (see Chap. 10 of this
Volume).
In this introductory chapter, we will
review some of these developments, focus-
ing on how processing enhances the
product's properties. The content of this
chapter more or less follows that of Vol. 18
of this Series. It starts with a summary of
what has been obtained to date with
advanced modeling (Sec. 1.2). Attention is
then given to structure development during
flow. Apart from the classical fluid-fluid
mixing, the TIPS, DIPS (Sec. 1.3) and CIPS
(Sec. 1.4) processes (temperature, diffu-
sion, and chemically induced phase separa-
tion processes, respectively) will be dealt

with in somewhat more detail and some
remarks on crystallization during process-
ing are made. That processing can be used
to attain the ultimate properties in terms
of stiffness and strength on the one hand
and toughness on the other is clearly illus-
trated (Sec. 1.5). Finally, a short review
on extruder modeling is given (Sec. 1.6)
and some concluding remarks are made
(Sec. 1.7).
1.2 Modeling Aspects
1.2.1 Introduction
The recent development of powerful and
relatively cheap computer hardware, in the
form of easily accessable workstations,
which can eventually be combined via a
high capacity ethernet to form complex net-
works, has evoked an explosive develop-
ment of user-friendly computer software.
The consequences of these developments in
the area of modeling polymer processes
have been substantial. Classically, process-
ing handbooks were mainly based on qual-
itative reasoning and the solution of, bas-
cially one-dimensional, differential equa-
tions, see, e.g., the textbooks of McKelvey
(1962), Middleman (1968, 1977), Tadmor
and Klein (1971), Bernhardt (1974), Zia-
bicki (1976), Funt (1976), Janssen (1978),
Tadmor and Gogos (1979), Fenner (1970,
1979), Potente (1981), Rauwendaal (1986),
and Macosko (1989). Nowadays, the com-
bination of 3D continuum mechanics and
computational mechanics in the analysis of
polymer processes is attempted, see, e.g.,
the textbook on transport phenomena by
Bird et al. (1960) and those on polymer pro-
cessing by Petrie (1979), Pearson (1985),
Pearson and Richardson (1983), Tucker
(1989), Thomson et al. (1989), Isayev
(1987, 1990), White (1990 a, b), and Agas-
1.2 Modeling Aspects
sant (1991), based on the 3D-material
description in rheological textbooks by, e.g.,
Lodge (1964), Ferry (1980), Astarita and
Marrucci (1974), Schowalter (1978), Jane-
schitz-Kriegl (1983), Crochet et al. (1984),
Tanner (1985), Doi and Edward (1986), Bird
et al. (1987), Larson (1988), Joseph (1990),
and Macosko (1994).
As a result, present research is no longer
so much aimed at the description of the pro-
cess under consideration, but merely at the
prediction of product properties resulting
from the total preparation (e.g., compound-
ing) and final shaping processes. In this
respect, textbooks publications lag behind
and most of this work is published in theses
and in the open literature, where the combi-
nation of advanced rheology and computa-
tional methods in the analysis of polymer
processes is attempted. Interestingly, in
most cases the necessary assumptions made
to enable careful analysis of the production
process are less severe than the uncertain-
ties in the input data, specifically in the con-
stitutive equations. This holds not only for
the (rheological) constitutive equation for
the Cauchy stress tensor, which is the sub-
ject of the rheological textbooks mentioned
earlier, but also for those for the density, the
(anisotropic) heat conduction, nucleation-
induced crystallization, and the kinetics of
reactions and phase separation. In summary,
those equations that describe the structure
development in anisotropic, heterogeneous
systems. As a consequence, a lot of basic
research is devoted to a detailed study of the
distinct processes that occur on a local scale.
Implementation of these, generally micro-
scopic, events in the macroscopic flow
equations is not a straightforward task.
Local processes could influence the contin-
uum processes and vice versa. Generally,
extra assumptions are needed, specifically
on their possible mutual interactions. More-
over, polymer physics then becomes invol-
10 1 Processing for Properties
ved in the research area of polymer process-
ing analysis and this not only makes the
research necessarily multi-disciplinary, but
also complicates the whole issue consider-
ably. This holds especially for the rheology
and the microrheology. Constitutive equa-
tions proposed for the description of poly-
mer solutions and melts have been without
exception tested only in weak, rotational,
simple shear flows. It is known, however,
that their descriptions of a material's behav-
ior in strong, irrotational extension flows
differ considerably (Walters, 1992; Hudson
and Jones, 1993). Up to now, there has been
no real possibility of testing the materials in
these flows, although many attempts to
design new equipment for the analysis of
stretching flows have recently been under-
taken. Examples include the Rheostrain, as
developed by Vinogradov et al. (1970),
Franck and Meissner (1984), and Munstedt
(1975, 1979); a revival of the Rheotens, as
promoted by Wagner (1994,1996); the Rhe-
ometrics extensional rheometer, as devel-
oped by Meissner (1969, 1971, 1992),
Meissner et al. (1981, 1982), Meissner and
Hostettler (1992), and Li et al. (1990), all
for polymer melts; while for polymer solu-
tions we find the opposed tube device, as
developed by Keller et al. (1987), Fuller
etal. (1987), Mikkelsen et al. (1988),
Schunk et al. (1990), and Schunk and Scriv-
en (1990), and the constant strain rate test
device, as investigated by McKinley (1995)
and Van Nieuwkoop and Muller von Czer-
nicki (1997). Only the future can show
whether these new apparatuses will function
properly. For the time being, in polymer pro-
cessing, where typically complex flows pre-
vail, which combine shear and elongational
flow, researchers have to live with a multi-
tude of constitutive equations, which should
be tested in real practice. Nevertheless,
some attempts have been made to test rhe-
ological equations in (generally 2D, isother-
mal) complex flow, using the so-called
hybrid experimental numerical technique
[see, e.g., Hendriks et al. (1990), Oomens et
al. (1993), Baaijens (1994c), and Baaijens
etal. (1994, 1995)].
1.2.2 Injection Molding
As an example of what can be obtained
nowadays, we will focus for a start on the
prediction of the properties of injection
molded products. Given the relevance of
this process for daily practice, over the years
a lot of attention has been paid by different
research groups all over the world to the
modeling of injection molding [and related
processes such as RIM (reaction injection
molding), RRIM or SRIM (reinforced or
structural RIM), RTM (Resin transfer mold-
ing), and pressing]. See, e.g., Hieber and
Shen (1980), Hieber et al. (1983), and Chi-
ang etal. (1991a, b), who developed C-
flow; Boshouwers and van der Werf (1988),
who developed Inject-3; the CEMEF code
originating from Agassant's group (see,
e.g., Chap. 2 of this Volume); Polyflow as
developed by Crochet's group [see, e.g.,
Crochet and Legat (1992), Fan and Crochet
(1995)], based on which the code Poly mold
for injection molding was derived; Kenne-
dy (1993) who developed Moldflow in its
new release; Dupret and Vanderschuren
(1988) and Couniot etal. (1993), who
improved the Louvain-la-Neuve code; Pap-
athanasiou and Kamal (1993) and Nguyen
and Kamal (1993), who developed their vis-
coelastic code; and finally, the VIp code, as
developed by our group, Sitters (1988),
Douven (1991), Vos etal. (1991), Peters
et al. (1994), Douven et al. (1995), Caspers
(1995), and Zoetelief (1995).
All modern modeling is based on the so-
called 2.5D approach, originally developed
at Cornell University by Hieber and Shen.
In this approach the temperature and veloc-

ity fields are solved in full 3D and the pres-
sure equation in 2D, applying the lubrifica-
tion approximation (Hieber and Shen, 1980;
Hieber et al., 1983). A combined FEM/
FDM (finite element/finite difference meth-
od) is used, with the finite elements applied
in the midplane of the cavity and the finite
differences added at every nodal point in the
perpendicular direction. This elegant meth-
od combines the flexibility of the finite ele-
ments necessary to describe complex prod-
ucts, with the high resolution required in the
off-plane direction, given the large gra-
dients in temperature and velocity that are
present here, without yielding unrealistic
and thus unworkable computing times. Typ-
ically the influence of the process parame-
ters was obtained from these analyses.
Examples include the prediction of the posi-
tion of the flow front, thus predicting air
inclusions and yielding opportunities to
optimize the position and number of the
gates. Furthermore, the pressure and veloc-
ity field resulted, thus allowing for an eval-
uation of the machine size and clamping
force to be used. Finally the temperature
profiles were computed, thus yielding pre-
dictions for possible local hot spots, and
more importantly, the cooling time and thus
the process cycle time. These analyses could
even be performed for products that have
relatively complex shapes.
Accordingly, different groups developed
similar codes, adding, for example, the pos-
sibility to analyze reactive molding, to pro-
cess crystallizable materials, to predict fiber
orientation, to simulate gas injection, etc.
(Hayes, 1991; Liang et al., 1993; Saiuet al.,
1992; Cintra and Tucker, 1994; Turng and
Wang, 1991; Turng et al., 1993). The VIp
code was developed as an extension of the
above research in the direction of the pre-
diction of product properties. Since these
properties generally depend on the complete
thermo-mechanical deformation history of
1.2 Modeling Aspects 11
every material element during flow, it
proved to be of utmost importance to follow
every individual "particle" during process-
ing. This particle tracking required the solu-
tion of an extra equation, the equation of
conservation of identity. This is a pure con-
vection equation which is extremely diffi-
cult to solve accurately, and the results were
experimentally checked by using tracers in
the form of multicolors. In this way, multi-
material injection molding, where different
materials are sequentially or simultaneous-
ly injected into the mold, could also be ana-
lyzed (Vos et al., 1991; Peters et al., 1994).
Moreover, product properties, e.g., accura-
cy and dimensional stability (Sec. 1.2.3),
prove to depend on the total density distri-
bution on the one hand and the flow, tem-
perature, and pressure-induced frozen-in
stresses on the other (Sec. 1.2.4). The first
requires a temperature and time history
dependent constitutive equation for the den-
sity, e.g., the KAHR model (Kovacs et al.,
1979), while the latter requires the temper-
ature, time, and deformation history depen-
dent constitutive equation for the stress ten-
sor (Sec. 1.2.6). Different viscoelastic con-
stitutive equations, of both the integral and
differential type, were used. The problem is
as mentioned, to find the correct material
parameters for these equations (Sec. 1.2.5).
Nevertheless, the first results look promis-
ing. This can be illustrated by the compari-
son of predicted experimentally determined
values for different relevant quantities,
using a simple strip only.
1.2.3 Dimensional Stability
In Fig. 1-1 the change with time of three
important dimensions of this elementary
strip are shown, yielding its dimensional
(in)stability. The comparison of theory and
experiment is amazing especially if it is real-
ized that these changes in dimension depend
12 1 Processing for Properties

0.03

0.02

0.01

.E -0.01
CO

-0.03 - 10T

-0.04 41
110
-0.05 Geometry of the test strip, with P3 and P4
the position of two pressure transducers
-0.06
10 10 10 10'
time [s]
Figure 1-1. Measured (symbols) and predicted (lines) strain due to recovery of the length (x, - ) , and width at
75 (O, -) and 110 (+, -) mm from the gate. Storage temperature 343 K (Caspers, 1995).

on the combined action of a multitude of determined values. Simulation with the

parameters, e.g., the density distribution and
the frozen-in thermal (and pressure-indu-
ced) stresses, which yield short-time warp-
age, and the frozen-in flow-induced stress-
es, which represent the molecular orienta-
tion and determine the long term stability.
The only manipulation that has been applied
to the above calculations is that the storage
temperature was taken as 4 C higher (74 C)
than in the experiments (70 C). The calcu-
lated results proved to be extremely depen-
dent on this temperature, shifting the time
axis by one decade for a change of only 4 C.
Figure 1-2 shows the predicted and mea-
sured pressure profiles with time, at three
different locations on the strip. As usual, the
pressure at the gate is taken as the initial con-
dition. The predictions further downstream
differ markedly from the experimentally
code revealed that this is due to inaccuracy
in the data for the density, which controls
the whole process in the post-filling stage
where the discrepancy occurs, and not so
much to problems with the rheological con-
stitutive equation, wrong values for the ther-
mal boundary conditions, or the influence
of mold elasticity.
1.2.4 Density and Stress Distributions
Changes in density upon cooling directly
affect the short term dimensions of the
molded product and give rise to shrinkage.
Apart from long term effects, like physical
ageing (the slow but continuous tendency of
a material to increase its density by better
segmental packing), these changes in den-
sity can cause anisotropic shrinkage, given

x10
Figure 1-2. Measured (symbols) and predicted (lines) pressure distribution as a function of time, at the gate (x),
at P3 (O), and at P4 (+); for their position see Fig. 1-1 (Caspers, 1995).
the 3D density profiles that result from the
molding process. In Figs. 1-3 and 1-4, the
density distributions throughout the product
are given for several processing conditions.
The comparison between experimental val-
ues and predictions is clearly only qualita-
tive. More attention should be paid to the
experimental determination of the parame-
ters in the constitutive equation for the den-
sity. This is not straightforward, task, given
the severe conditions, with respect to high
pressures combined with extreme tempera-
ture gradients and fast cooling rates, that
occur in injection molding [see, e.g., Picca-
rolo (1992), Piccarolo et al. (1992), and
Brucatoetal. (1993)].
The second influence on short-term
changes in the dimensions of a product is
caused by the occurrence of thermal stress-
es. They also cause warpage of the product
1.2 Modeling Aspects 13
in the case of asymmetric cooling. The
development of temperature (and pressure)
induced enthalpic stresses during molding
is illustrated in Fig. 1-5. Typically for injec-
tion molding, as compared to pressureless
shaping processes (e.g., during the cooling
of metals and glasses), where similar fro-
zen-in stresses develop due to inhomogene-
ous cooling, is the occurrence of tensile
stresses on the outside of the product. These
stresses were first computed (see Fig. 1-5)
using linearized forms of the different vis-
coelastic constitutive equations (which is
allowed, given the small deformations in
this stress build up) and subsequently
experimentally determined (see Fig. 1-6).
The last is difficult, since by whatever tech-
nique is used to determine the thermal
stresses (e.g., birefringence, or, more gen-
erally applicable, layer removal), it is
14 1 Processing for Properties

2.5
"xN
X
2 _
s/ X
/
o \\
1.5 X X
& x x ^ ^ ; x
/ o
o X
x
1 x x x X x /
\
Q> / \
o /
0.5
O o o /
[kg/nf ]

o o o o o
0?i + +

Q_
-0.5 +
G '
+ + +
+ + +
-1 + + + +

J1
-1.5 - -

-2
H

-2.5 i i i I I 1 I

-0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1

2z/h M

Figure 1-3. Measured (symbols) and predicted (lines) reduced density distributions across the normalized thick-
ness at 8 (x), 28 (O), and 107 (+) mm from the gate (Caspers, 1995).

always extremely difficult to measure accu- ingly good, given the problems mentioned
rately close to the walls. In Fig. 1-6 the com- above.
parison is made and found to be satisfacto- The flow-induced stresses can be calcu-
ry. lated to a good approximation in a decou-
Finally, the most difficult to determine pled way, and thus eventually in a post-pro-
stresses are the frozen-in flow-induced cessing operation, with the kinematics of the
stresses, since they depend directly on the process and the temperature history used as
quality of the constitutive equation used, input data for the calculation of the stress-
combined with an accurate temperature his- es, using a viscoelastic constitutive equation
tory prediction. Moreover, uncertainties (Baaijens and Douven, 1990; Baaijens,
arise given the still unsolved problems that 1991; Douven et al., 1995). The kinematics
can occur while passing the glass transition can, in their turn, be calculated with a his-
region [see, e.g., Wimberger Friedl (1991)]. tory-independent, generalized Newtonian
They give rise to the anisotropic shrinkage rheological constitutive equation. This pos-
found in the long term, especially if the sibility, which is based on the overruling
product is stored at relatively high temper- effect of the boundary and the initial condi-
atures (see Fig. 1-1). The development of tions on the kinematics of the flow, which
these orientational entropic stresses during are given in terms of prescribed velocities
the process is depicted in Fig. 1-7, while a rather than prescribed stresses, speeds up
quantitative comparison is made in Fig. the calculations of these stresses consider-
1-8. The quality of the prediction is strik- ably (with a reduction of the computation
 1.2 Modeling Aspects 15
2.5

1.5
x
1 ox
ox
0.5
X X X X

0<
o o o
-0.5

-1

-1.5

-2

-2.5 _l !_
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8
2z/h [-]

-1 -0.8 -0.6 -0.4 -0.2 0.2 0.4 0.6 0.8 1

Figure 1-4. As Fig. 1-3, for two different holding pressure profiles (a) decreasing from 80MPa to 20MPa for a
holding time of 10s, and (b) increasing from 20 to 80 MPa (Caspers, 1995).
16 1 Processing for Properties

3.7s

7.7s

5.7s /=8.7s

Figure 1-5. Development with time, during injection, holding, and cooling of the temperature and pressure
induced stress profiles (O"n) over the thickness and length of the injected strip (Baaijens, 1991).

- : visco-elastic
--: viscous elastic
o : measured
-10
-0.8 -0.6 -0.4 -0.2 0.2
time of 90%). Similar decoupled calcula-
tion methods are applied for the determina-
tion of fiber orientation in these kind of
flows (Cintra and Tucker, 1994).
1.2.5 Choice of the Constitutive Equation
A major problem encountered in the cal-
culation of flow-induced stresses is the
proper choice of the viscoelastic, history
dependent, rheological constitutive equa-
tion. In the above results, the compressible
Leonov model was used. If we fit the rheo-
logical data with a KBKZ type of integral
model, more specifically with a Wagner
model, then the predictions of these stress-
es differ from the experimental by some-
thing like 100%. This can be reduced to a
difference of 20 % if a slight change in the
nonlinear damping function, which hardly
changes the quality of the fit of the rheolog-
ical data in shear, is incorporated (Baaijens
andDouven, 1990; Baaijens, 1991; Douven
et al., 1995). Similar arguments were found
in the modeling of the film blowing process
1.2 Modeling Aspects 17
Figure 1-6. Measured
(symbols) and predicted
[viscoelastic (), viscous-
elastic (-)] residual stress
profiles over the thickness
of the strip (Zoetelief et al.,
1996).
0.4 0.6 0.8
(Tas, 1994). Here, an amazing number of
film properties, e.g., the modulus, yield
stress, tensile strength, elongation to break,
and tear resistance, could be related to the
stress acting on the frost line, see Figs. 1-9
and 1-10.
In calculating the stress at the frost line,
not only does the flow inside the die have to
be incorporated, but also a correct choice of
the constitutive equation proved to be of
utmost importance. A Phan-Thien Tanner
(PTT) type model gave much better results
then the KBKZ type model (see Fig. 1-11).
This is not so much to do with the difference
between the integral or the differential con-
stitutive equations, although the numerical
analysts generally prefer the latter, but rath-
er with the difference in their description of
the nonlinear behavior, especially in elon-
gational flows.
These facts have motivated a number of
research groups to use more complex flows
to determine the parameters in constitutive
equations, via the use of field information
rather than boundary information [see, e.g.,
18 1 Processing for Properties

'end of filling stage, t = 0.67 s f = 3.21s

end of compression stage f = 4.7s

N1 (MPa)
Gate freeze-off
0.1

0.08

0.06

0.04
End of filling
0.02

0.5 1 1.5

2.7s
Figure 1-7. Development with time, during injection, holding, and cooling of flow-induced stress profiles (first
normal stress difference iV,) over the thickness and length of the injection-molded strip. The bottom right figure
gives the Nx history at x = 8 mm, at a distance of 0.35 mm from the midplane, indicating its growth during injec-
tion (et, X(T)i), the fast decay due to relaxation after the flow stopped, and the steep rise when Tg is approached
(si, A(r)T) upon further cooling of the product, with e the deformation rate and X(T), the temperature-depen-
dent relaxation time. For an explanation see Sec. 1.5.2 (Baaijens, 1991).
 1.2 Modeling Aspects 19

x10

Figure 1-8. Measured

(symbols) and predicted
(lines) residual birefrin-
gence across half the
thickness at 25 (x), 41
(O),60(+),andll0(*)
mm from the gate (Cas-
pers, 1995).
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

E modulus MD

Figure 1-9. Film mod-

ulus in machine direction
(MD) and transverse
direction (TD) versus (a)
the macroscopic draw
ratio (VJ/VQ) and (b) the
stress acting at the frost
line, for three types of
low density polyethylene
(LDPE) of different melt
flow index (MFI): L0 (o),
LI (x), (both MFI 1), and
L8 (+) (MFI 8) (Tas,
1994).
0.2 0.4 0.6 0.8
Stress MD [MPa]
 1 Processing for Properties

b),5r

Figure 1-10. As Fig. 1-9, but for

the yield stress, the tensile strength
in the machine (MD) and the
transverse (TD) directions, the
elongation to break, and the tear
resistance (Tas, 1994).
10 20 30 0.2 0.4 0.6
DR[-1 Stress MD [MPa]

x10 PTT
4 6
Stress MD, exp. [MPa]
x10 Leonov
4 6
Stress MD, exp. [MPa]
Figure 1-11. Calculated versus measured stress at the frost line, using four different constitutive equations (Tas,
1994).
Brown and McKinley (1994), Baaijens
(1994c), and Baaijens et al. (1994, 1995).
The most promising method nowadays
seems to be the combined LDA (laser Dop-
pler anemometry) and FIB [flow-induced
birefringence, measured with the ROA
(rheo-optical analyzer)] measurements that
determine the kinematics and the stresses
[applying the (empirical) stress optical law]
in the flow. Typical flows used are the pla-
nar 4:1 or higher (up to 32:1) contraction
flows, and the flow around a centric or
eccentric cylinder placed in a rectangular
duct. Typical examples of model predictions
compared with experimental results are in
Figs. 1-12 to 1-15 using the discontinuous
Galerkin method [see, e.g., Fortin and For-
1.2 Modeling Aspects 21
Giesekus
x10
8 10
Stress MD, exp. [MPa]
x 10 x 10
Wagner
x10
8 4 6
Stress MD, exp. [MPa]
x10 x10
tin (1989), Guenette and Fortin (1995), and
Baaijens (1994 a, b)]. In these types of
flows, the Deborah number is defined as
De = VH/X, with V a characteristic process
velocity, Ha. characteristic geometry dimen-
sion and X the fluid relaxation time. The
Deborah number is used as the relevant scal-
ing parameter.
1.2.6 Deformation History
The last examples clearly show that once
the geometry becomes somewhat more
complex, such that the stresses start to deter-
mine the kinematics, the choice of constit-
utive equation used to determine those kin-
ematics becomes relevant. It should be real-
22 1 Processing for Properties
De = 0.55
-10 -8
Figure 1-12. Contraction flow (4:1) data: comparison of the measured (symbols) and predicted (lines: PTT-a
model) normal stress profile at the center line for a polymer solution, for two different values of the Deborah
number (De): (a) 0.55, (b) 0.77 (Baaijens, 1993).
ized that the prediction of the deformation
pattern is a rather sensitive criterion for the
quality of our modeling, since deformation
patterns consist of the integral with time of
the velocity profile. Classical rheological
techniques without exception use the veloc-
ity profile, differentiated in the direction of
the largest gradients, and subsequently inte-
grated in the direction of the smallest gra-
dients, if any, by measuring the stresses via
torques or pressure drops. As already stat-
ed, the deformation history of the material
elements is, moreover, of utmost relevance
for predicting product properties that
depend on the total temperature-deforma-
tion-time history. Thus, computationally,
special particle-tracking routines have been
developed to solve the equation of conser-
vation of identity equal to zero, | = 0, with
the dot the material derivative and being
typically the place and time of entering the
mold if we deal with injection molding. This
pure convection equation suffers from
numerical diffusion and dispersion. That is
why different strategies have been devel-
oped to solve it, e.g., the streamline upwind
N,(Pa)
De = 0.77
120r
methods (SUPG) (Brook and Hughes,
1982), the time discontinuous Galerkin least
squares methods, and the discontinuous
Galerkin methods (Johnson, 1987). The rel-
evance of solving this equation properly
originates from the consideration that all
convection-dominated problems show the
same numerical difficulties, i.e., for exam-
ple, high Reynolds number flows in hydro-
dynamics, high Peclet number flows in non-
isothermal situations, high Deborah number
flows (if viscoelasticity dominates), and
high Dahmkoller number flows in reactive
molding and extrusion.
If the deformation history has to be pre-
dicted with sufficient accuracy in injection
molding, or if MMIM (multi-material injec-
tion molding), or GAIM (gas-assisted injec-
tion molding) have to be analyzed, or if RIM
(reaction injection molding) is the topic of
research, in all cases it proves to be wise to
start the research with simplified geome-
tries. At CPC Eindhoven, the plunger-driv-
en flow was chosen as a representative
geometry, given its characteristic of well-
defined initial conditions, while maintain-
 Velocity Velocity

Normal stress difference Normal stress difference

o
Q.

o
CD
o

Figure 1-13. Measured (symbols) and predicted (lines: 4-mode PTT-a model with <*= e=0.1) velocity (top), first normal stress (middle), and shear
stress (bottom) profiles for the flow of a polymer solution (5 % PIB/C14) around a (a) centric and (b) eccentric cylinder, De= 1.87 (Baaijens, 1994c). CO
24 1 Processing for Properties

Figure 1-14. Measured (top) and predicted (bottom) birefringence patterns for the flow of an LDPE melt at
190C around (a) a centric and (b) an eccentric cylinder, PTT-a (=0.1 =0.1), De = 4A (Baaijens et al., 1995).

if<,
W'
V. Jtt
Figure 1-15. (a) Measured deformation pattern of a start-up flow around a cylinder for a PS melt at 175 C,
De = 24, predicted using a (b) Carreau Yasuda or a (c) PTT-a model (with =0.1 and =0.35) (Selen, 1995).

ing some difficulties encountered in mold-
ing processes via the presence of its foun-
tain flow at the top and reversed fountain
flow at the bottom plunger (Vos et al., 1991;
Spoelstra, 1992; Corbey, 1992; Peters et al.,
1994; Zoetelief, 1995). Some results com-
paring experimental and computed defor-
mation patterns are given in Figs. 1-16 to 1-
21.
Finally, an example is given of a splitting
flow, as currently occurs in injection mold-
ing and where the standard 2.5 D programs
show local difficulties. Since the pressure
equation is not solved in the direction
perpendicular to the streamlines (see
Sec. 1.2.2), the flow-splitting cannot be
described. Mostly, the properties of the in-
flowing material are simply copied to both
exits. This is physically wrong, since the
wrong materials' elements flow in the
wrong places. As a consequence, all histo-
ry dependent parameters, and even the con-
 1.2 Modeling Aspects 25

3 Experimental

*&.. -*;."
*/

--.*.,-, * . . .

0 mm 10 mm 20 mm 30 mm 40

b Calculated

0 mm 10 mm 20 mm 30 mm 40 mm

Figure 1-16. Measured (top) and predicted (bottom; only the results in half of the geometry are drawn) defor-
mation patterns at the midplane of the cylinder for a polystyrene (PS) melt in the two-plunger flow geometry at
473 K. The parameter is the total axial plunger displacement (Zoetelief, 1995).
26 1 Processing for Properties

ABS (T=473 K)

Experimental

0 mm 10 vim 20 mm 30 mm 40 mm

Calculated with 'dynamic' yield stress value

Calculated with 'static' yield stress value

Figure 1-17. As in Fig. 1-16, but for acrylonitrile-butadiene-styrene copolymer (ABS) with (a) experimental,
(b) calculations with a "dynamic" and (c) a "static" value for the yield stress (Zoetelief, 1995).
 1.2 Modeling Aspects 27

a PS (variation of T and vp) b ABS (variation of T and vp)

Experimental Experimental

443 473 503 K 43.2 mmls 443 K 473 K 503 K 43.2 mmls

Calculated Calculated

443K 473 K 503 K 43.2 mmls 443 K 473 K 503/< 43.2 mmls

Figure 1-18. Influence of temperature (at piston speed of 1 mm/s) and piston velocity (at a temperature of 473 K)
on the deformation pattern for (a) PS and (b) ABS; the remarkable difference in behavior of the two polymers
(both measured and predicted) is due to the differences in the temperature dependence of the Newtonian plateau,
i.e., the shear thinning transition, versus that of the yield stress (Zoetelief, 1995).

vected temperature, are wrongly predicted.
This problem becomes specifically obvious
if particle tracking is investigated. A solu-
tion is obtained by adapting local analyses
(see Fig. 1-22), or alternatively, by using the
same particle tracking technique to follow
flow fronts. This last, flexible method is eas-
ily extendable to full 3 D molding analyses
and basically replaces the transient filling
problem by a quasi-stationary one. This is
realized by taking the through flow of air
into account. The air in the mold is quasi-
stationary flowing and is, at time t-tx, at
the entrance replaced by a polymer melt.
The method tracks the air-polymer inter-
face. The polymer is assumed to stick at the
walls while, at the interface between the
mold and the air, a slip condition is adopt-
ed in order to allow for a replacement of air
by polymer melt and to prevent the presence
28 1 Processing for Properties

PS/ABS (T=473 K)

Experimental

PS

ABS

0 mm 10 mm 20 mm 30 mm 40 mm

Calculated

PS

Figure 1-19. As in Fig.

ABS 1-16, with PS layers placed
on top of the ABS (Zoete-
lief, 1995).
0 mm 10 mm 20 mm 30 mm 40 mm

of (extremely thin) air layers at these boun-
daries (Reijnierse, 1995). This method is
also capable of analyzing the GAIM (gas-
assisted injection molding) process by
tracking the second (polymer-gas) inter-
face, injected at t-t2 as well (Haagh, 1996)
(see Fig. 1-23).
Finally, the inverse problem is men-
tioned. If, in a specific product, another
material should be incorporated locally via
co-injection techniques, the inverse prob-
lem can illustrate where and when this mate-
rial should be injected into the mold (see
Fig. 1-24).
1.2.7 Discussion
Using the injection molding process (and
partly the film blowing process) as an exam-
ple, it has been illustrated that in the last
decade progress has been made in predicting
polymer product properties that result from
the complex temperature and deformation
history experienced during processing.
 1.2 Modeling Aspects 29

ABS/PS (T=473 K)

Experimental

ABS

PS

0 mm 10 mm 20 mm 30 mm 40 mm

Calculated

ABS

Figure 1-20. As in Fig.

PS 1-16, with ABS layers on
top of the PS (Zoetelief,
1995).
0 mm 10 mm 20 mm 30 mm 40 mm

Today attention is focused on the solution of
the full 3 D problem, using higher order
(spectral) elements. The reason is that in
most applications where a careful, detailed
analysis is a prerequisite for faster product
development, as in components for the elec-
tronic industry, the 2.5 D approach is no
longer valid, since generally not one "thin"
direction can be recognized. Interestingly,
the assumptions necessary to be able to
model transient, nonisothermal, viscoelastic
flows in complex geometries like those that
occur in injection molding, put less con-
straints on the validity of the predictions than
the uncertainties in the (material) input data.
Consequently, a lot of effort is nowadays
devoted to accurately measuring the constit-
utive behavior of polymers. The advantage
of this "back-to-basis" approach is evident,
since it is more straightforward to relate the
molecular structure of polymers to, e.g., their
rheology than all the way to the product's
properties. In the next section the heteroge-
neity of polymer systems is reviewed.
30 1 Processing for Properties

td

300

210

180

Figure 1-21. As in
Fig. 1-16, but for a reac-
tive, highly filled epoxy
120 with different delay times,
td, before movement of
the plunger starts, and dif-
ferent wall temperatures;
the stars * indicate the
occurrence of wall slip
due to progressive curing
80 90 100 110 115 120 130 (Spoelstra, 1992).

1.3 Structure Development ing], and TIPS, DIPS, or CIPS processes

During Flow
1.3.1 Introduction
Blending offers a versatile technique to
create new materials with specific, well-
tuned properties. Many different techniques
are applied to combine the properties of the
individual constituents in the final polymer
mixture, from RMP (reactor modified poly-
mers), via REX (reactive) extrusion blend-
(thermally, diffusion, and chemically
induced phase separation, respectively), to
MMIM (multi-material injection molding).
Without exception the properties of the final
product are determined by the resulting
morphology, and this is why the structure
development during flow is studied. For the
most simple case of mixing of two fluids,
two dimensionless numbers can be defined
that characterize the mixing behavior: the
capillary number Ca, which represents the
 1,0
0.9
0.8
0.7
0,8
0.5
0.4

0,3
0.2
.1
-1.0
0.0

a. (wrong) injection time label b, (wrong) gapwise injection position label

1 0 CO
0.8 CO

ruci
0.6
c
CD

Devellopment
-.8 D
c

- ing f r low
.,0

d. (correct) gapwise injection position label

c. (correct) injection time labei

Figure 1-22. Correctly predicted (c) and erroneous (a) injection time and wrong (b) and correct (d) gapwise injection position label distributions after a
flow splitting in injection molding (Zoetelief, 1995).
32 1 Processing for Properties

Figure 1-23. Simulation of the transient GAIM pro-

cess at different stages of injection in (a) a cylindrical
channel and (b) a planar flow around a corner. Injec-
tion time (material) labels and the air (light
blue)-polymer and polymer-gas (dark blue) interfac-
es are depicted, while in the flow around the corner
(bl) these interfaces are drawn explicitly (b2), com-
bined with the resulting velocity field throughout the
different phases (b3) (Haagh, 1996).

gate

1 v

0.5-

1 o-

-0.5-

b1

5~H b2

b3
Figure 1-24. Solution of the inverse problem. Fig-
ure l-24b illustrates where and when a second mate-
rial has to be injected in the linegate in order to fill a
specific area in the final product (see Fig. 1-24 a)
(Zoetelief, 1995).
 1.3 Structure Development During Flow
ratio of the shear stress applied (T= 7]cy) to
the capillary pressure (o/R), and the viscos-
ity ratio p
Ca = ^ (1-1)
G
(1-2)
rid
with r]c and r\d the viscosities of the contin-
uous and the dispersed phase, respectively,
7 the shear rate, R the local dispersed drop
radius, and crthe interfacial tension.
In general, at in the beginning of the mix-
ing process, the drop radius is large and the
effect of interfacial tension is by far over-
ruled by the shear stress applied. The drops
deform affinely with the matrix, provided
that the viscosity ratio is not too large if only
simple shear is available [see Janssen
(1993), Meijer and Janssen (1994), and
Chap. 3 of this Volume for further details].
As a consequence, only simple mixing
should be analyzed in these regions of the
flow, and the focus should be on obtaining
exponential rather than linear stretching of
the dispersed phase (Sec. 1.3.2). If the cap-
illary number approaches the value of one,
by a continuous decrease in the radius of the
deformed long slender threads which are
formed, Rayleigh distortions grow and the
threads disintegrate into lines of drops
(Sec. 1.3.3). In a real mixing process, a
quasi-stationary situation will result where
drop break up and drop coalescence equili-
brate, and simple models have been derived
for liquid-solid and liquid-liquid disper-
sions in elementary geometries (Sec. 1.3.4).
Of course blending is only one of the tech-
niques that can be used; other processes do
exist (Sec. 1.3.5). Finally, even in the seem-
ingly most obvious case of a one-component
fluid, structure development during flow
can occur if the liquid-solid transition is
met, e.g., in crystallizable polymers (Sec.
1.3.6).
33
1.3.2 Chaotic Distributive Mixing
Based on the elegant approach developed
by Ottino and co-workers [see, e.g., Ottino
(1989, 1990, 1991)] to study the basics of
mixing in simplified geometries, the impor-
tance of applying the bakers transformation,
even in continuous flows, has become evi-
dent. This transformation consists of three
elementary steps: stretching, folding, and
returning to the original position, and gener-
ates exponential rather than linear mixing if
repeated in (typically) time or spatially peri-
odic flows. No better procedure exists and,
without counteracting forces like the inter-
facial stresses, nanodimensions are easily
reached within a, e.g., 20-fold, repetition of
this procedure. All well-designed static mix-
ers (e.g., the Sulzer, Ross, Multiflux, and
Kenics mixers) apply the bakers transforma-
tion and they can, consequently, be consid-
ered as the most efficient mixers, at least for
pure distributive mixing. In our laboratory,
apart from the rectangular cavity, the peri-
odic curved cavity flow is analyzed as an
intermediate step towards more realistic
geometries as found in single and twin screw
extruders. At the moment, the cavity is only
slightly curved and the attention is focused
on particle tracking with the conservation of
mass of the dispersed blob, the influence of
its initial position, and the protocol followed
in the movements of the two opposed walls.
In these studies of (almost) 2D isothermal
prototype mixing flows, the left and right
wall are kept stationary, while the upper and
lower walls are sequentially moved in a
clockwise direction at a moderately low
speed over a fixed distance. A period is
defined as one loop in the protocol: if both
the upper wall and the lower wall have been
sequentially moved once. Periodic points
are points that return to their initial position
after one (order one) or more (order two,
etc.) periods. "Hyperbolic" points favor
34 1 Processing for Properties

mixing, since in their neighborhood effi-

cient stretching occurs due to the presence
of hyperbolic streamlines, while the accom-
panying "elliptical" points form islands and
are thus to be avoided. Of course, "parabol-
ic" periodic points also exist, e.g., when an
extra obstacle is added to the flow. Period-
ic points are the key to understanding expo-
nential, chaotic mixing. In both experiments
and simulations, a tracer blob is positioned
around one of these periodic points and its
deformation with time is followed. More
details of the experimental set-up and
results can be found in Chap. 3 of this Vol-
ft
ume. Interestingly, analytical solutions are
available for these kinds of flows (even if
an extra rotor is added in the midplane),
based on a large number (typically 30) of
intermediate steps to accelerate conver-
gence of the series expansions. In the final
result, only three terms of the expansions Figure 1-25. Results of modeling the periodic flow
have to be taken into account to obtain accu- in a curved cavity. The initial position of the blob,
rate results (Meleshko et al., 1991; Melesh- around a hyperbolic point of order one (), is indicat-
ed in green. The resulting deformed drop is given by
ko and Peters, 1996). Figure 1-25 shows a
the threads (red, partly covered by the blue line) after
typical line stretch obtained in this period- six and (blue) 12 periods. The bottom figure gives an
ic flow, if the original blob is located at a enlargement showing not only the extremely good
hyperbolic point of order one. Fig. 1-26 resolution obtained from these analytical solutions,
illustrates the effects of different initial blob but also some higher order periodic points (order 6),
positions and wall movement protocols. indicated with small squares, of the hyperbolic (filled
squares) and elliptic (open squares) type (Krasnopols-
Important in following the blob deforma- kayaetal., 1996, 1997).
tion is the necessity to nonuniformly distrib-
ute the points on the circumference of the 1-29, where all periodic points are shown,
original blob that are to be traced with time. combined with the different line stretching
The reason for this is obvious: during fold- of blobs placed at these points.
ing and stretching, two neighboring points Different measures for mixing can be
can, ultimately, be separated infinitely far defined: the statistical square density, the
from each other. This is the definition of intensity of segregation, and the entropy
(deterministic) chaos. An iterative proce- (Krasnopolskaya et al., 1996, 1997). They
dure is adopted which adds extra initial yield different results when applied to the
points between two points that tend to sep- periodic flow in the curved cavity. More
arate too far. The necessity of this is illus- importantly, they implicitly demonstrate the
trated in Fig. 1-27. problems of scale-up in mixing operations,
Also periodic points of higher order than since the absolute grid size chosen for the
one prove to be relevant for efficient mix- evaluation of the mixing quality clearly
ing. This is illustrated in Figs. 1-28 and determines the outcome (see Fig. 1-30).
 1.3 Structure Development During Flow 35

; . $ !

Figure 1-27. Influence of the distribution of the trac-

er points on the original blob circumference, (a) Non-
uniform distribution of 50000 points, (b) nonconnect-
ed, and (c) connected originally uniformly distribut-
ed, after 12 periods (Krasnopolskaya et al., 1996,
1997).

Figure 1-26. Influence of different wall motion pro-

tocols and initial blob positions on the final stretch- 2.5
ing. In Fig. 1-26 a a different protocol (half of the wall
displacement of Fig. 1-25) and a different initial posi-
tion (around an elliptical point of order one) were used
(results are shown after 20 periods, yielding the same
total wall displacement, and consequently the same
"money for mixing", as in Fig. 1-25). Figures l-26b
(original blob in a hyperbolic point of order one),
l-26c (central), and l-26d (four blobs with the same
total size as the big blob, arbitrarily placed) illustrate
the influence of the blob position (all results after 10
periods) (Krasnopolskaya et al., 1996, 1997).

-1.5 -1
Figure 1-28. Higher order periodic points in the curved
cavity flow. Order 1 (), order 2 (o), order 4 (+), and
order 6 () (Krasnopolskaya et al., 1996, 1997).
36 1 Processing for Properties
Figure 1-29. Resulting dimensionless line stretch S
after n periods of identical protocols of blobs with
initial size 0=5 mm positioned close to a hyperbolic
H(o) or elliptical E(o) periodic point of order (o). Fig-
ure 1-29 a: w = 9, E(2) surrounded by H(6), 5=1800.
Figure l-29b: n = 9.5, E(2), 5=1800. Figure 1-29c:
n=10, H(2), 5=1700. Figure 1-29d: w=12.5, H(l),
5 = 5600 (Krasnopolskaya et al., 1996, 1997).
Since the prerequisites for efficient mix-
ing are now well understood, at least in ele-
mentary geometries, attempts are nowadays
made to analyze real 3D mixers (including
those that are frequently used in the process
industry, e.g., stirred tanks, etc.) via flow
simulations using these basic concepts.
Thus periodicity is sought exclusively and
attempts are made to identify periodic
points. This is not a straightforward task. A
further extension of this knowledge is
sought in the coupling of the overall flow
behavior to the local microprocesses that
occur, for example, during emulsifying
(Tjahjadi and Ottino, 1991; Tjahjadi et al.,
1992, 1994; Janssen, 1993; Janssen et al.,
1993; Meijer and Janssen, 1994; Janssen
andMeijer, 1995).
1.3.3 Dispersive Mixing
As stated above, exponential mixing con-
tinuously decreases the length scale of the
dispersed phase in the direction perpendic-
ular to the flow, and once the radius of the
threads formed are of the order of 1 \m, typ-
ical for polymer blends, the interfacial ten-
sion becomes dominant and Rayleigh dis-
tortions grow with (as a driving force) the
decrease in the surface-to-volume ratio.
Threads disintegrate into lines of drops.
This process was studied in the mid 1930s
by Tomotika (1935, 1936), both in a quies-
cent surrounding and during flow. The lat-
ter proves to stabilize the threads, thus
retarding disintegration and yielding small-
er drops. His analyses were later extended
by, e.g., Stone et al. (1986), Stone and Leal
(1989 a, b, 1990, 1994), Tjahjadi and Otti-
no (1991), Tjahjadi et al. (1992, 1994),
Janssen (1993), and Janssen and Meijer
(1995), clearly showing that the effects of
both the viscosity ratio p and the absolute
values of the viscosities of both phases are
completely different from the conclusions
based on quasi-equilibrium experiments
such as the classical experiments performed
by Taylor (1932, 1934) and Grace (1982).
Details can be found in Chap. 3 of this Vol-
ume. Here only an illustration is given that
break-up processes take time (see Fig.
1-31).
 1.3 Structure Development During Flow 37

Distributions after 12 periods Distributions after 12 periods

Figure 1-30. Distribution of different mixing measures after 12 periods of mixing: square density (top), inten-
sity of segregation (middle), and entropy (bottom) for two grid sizes. The large grid size (left column) is repre-
sentative for a typical small scale laboratory mixer, while comparably the small grid size (right column) repre-
sents a larger production mixer. During scale up in the practice of mixing, the absolute sizes of the mixed domains
should stay constant and longer mixing is necessary in the larger mixers (Krasnopolskaya et al., 1996, 1997).

1.3.4 Two-Zone Models ure these thinning rates (see, e.g.,

In a real process, apart from dispersive
mixing, the coalescence of drops also
occurs, so coarsening the morphology
again. Coalescence takes place in the quies-
cent zones of the mixer, and a successful
process depends on the collision frequency
(determined by the volume fraction of the
dispersed phase and the shear rate) and the
thinning rate of the continuous matrix phase
in between the drops (which strongly
depends on the mobility of the interfaces,
which in its turn is influenced by the pres-
ence of compatibilizers). Successful mod-
els have been proposed to predict and meas-
Dell'Aversanaet al., 1996), even for partial-
ly mobile interfaces where the viscosity of
the dispersed phase plays a dominant role
(Chesters 1975, 1988, 1991; Chesters and
Hofman, 1982; Abid, 1993; Abid and Ches-
ters, 1994). Based on the original work of
Manas-Zloczower et al. (1982, 1984), who
derived a simplified two-zone model for the
dispersive mixing of carbon black (see
Fig. 1-32), Janssen and Meijer (1995) suc-
ceeded in deriving an analogous model for
liquid-liquid mixing. In these types of
dynamical models, two typical zones are put
in series: a strong zone, representing (typi-
cally) the passage of a narrow kneading
38 1 Processing for Properties

Figure 1-31. (a) Different morphologies as obtained in blends of the incompatible system HDPE/PS. The dif-
ference between (b) the threads and (c) the drops is a small increase in the air gap between the extruder die and
the quench bath, giving time for break up (Elemans, 1989).

flight in an extruder or batch mixer, and a
weak zone, representing the bulk of the vol-
ume of the mixer. The fluid is pumped
around from one zone to the other, given the
overall mixing time available. Models like
these combine all the elementary steps of
the mixing process and yield not only a
dynamic equilibrium of the distinct process-
es, the dispersive action of deformation and
break-up, and the coarsening action of
 1.3 Structure Development During Flow
STRONG ZONE
1 i
WEAK ZONE
affine stretching thread breakup at rest
thread breakup in flow drop coalescence
1.0
0.8i
. LDP
0.6 \
\
6 0.4
0.2 \
1 2 3 4 5 6
Gap height (mm)
Figure 1-33. Optimum gap size in dispersive mixing
of carbon black in styrene-butadiene rubber (SBR)
and low density polyethylene (LDPE). The explana-
tion of the differences between the matrix materials is
found in the differences in the viscosity. The high vis-
cosity of the rubber causes almost all agglomerates to
break, even if the gap height is large (and thus the
shear rate is relatively low) (Manas-Zloczower, 1994).
coalescence, but also provide tools to opti-
mize the mixing geometry. A basic design
parameter of any mixer is the ratio of the
gap height to the channel depth 8IH. If this
ratio tends to zero, a very strong zone exists,
but hardly any material will pass through
this zone, yielding zero throughput in the
available mixing time. If, on the other hand,
this ratio tends to one, no strong zone exists
at all. A clear optimum is found (see Figs.
1-33 and 1-34).
Apparently, it took more than a decade to
extend the elegant approach of dispersive
39
Figure 1-32. Schematic diagram
of the two-zone model for mixers
(Janssen and Meijer, 1995).
10" 5
10
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
6IH
Figure 1-34. Optimum gap size in fluid-fluid mix-
ing (Janssen and Meijer, 1995).
mixing of carbon black to that of emulsify-
ing flows. The reason for this is that in the
dispersive mixing of solids break-up is a
simple yes-no criterion, depending on
whether the shear stress overrules the cohe-
sive stresses and is, moreover, independent
of the absolute size of the agglomerates
(Manas-Zloczower et al., 1982, 1984;
Manas-Zloczower (1994) gives a detailed
treatment of the prediction of these cohesive
forces via a fractal analysis) and no coales-
cence takes place, where with fluid-fluid
mixing the distinct local time scales play a
decisive role, while the capillary pressure
clearly depends on the local drop (and
thread) radius; moreover, severe coarsening
can occur. Nevertheless, these basic
approaches clearly demonstrate the quality
of today's predictive power in mixing.
40 1 Processing for Properties

1.3.5 Phase Separation tion processes (L-L, G-G, or L-G), includ-

ing their driving forces, are depicted in
In membrane formation, gel applications,
Table 1-1.
and recently also in reactive molding or
Membranes can be symmetric or asym-
reactive extrusion, structures are formed via
metric with different pore sizes (typically
phase separation. Phase diagrams based on
0.2-5 |Lim) or dense. In asymmetric mem-
thermodynamics are the key to understand-
branes the skin takes care of the selectivity,
ing these processes. The attention in mod-
while the supporting porous underlayer pro-
eling is now focused on understanding the
vides a high yield. Microfiltration, ultrafil-
kinematics of the process, since mostly non-
tration, and reverse osmosis are all pressure-
equilibrium morphologies are vitrified. A
driven processes where liquids are separat-
schematic representation of different mem-
ed (Mulder, 1991; Kesting, 1985 a, b).
brane morphologies is given in Fig. 1-35
Microfiltration is used when relatively large
[after Mulder (1991)], while some separa-
particles (>100nm) have to be separated;
these membranes usually have an open
Table 1-1. Separation processes of liquid-liquid,
structure, and only low pressure drops are
gas-gas, or liquid-gas separation and their driving required. When macromolecules need to be
forces. separated from a solution, denser mem-
Process Separation Driving force3
branes are used, accompanied by a larger
pressure drop requirement. The process is
Microfiltration L-L Ap now called ultrafiltration. For even smaller
Ultrafiltration L-L Ap
molecules reverse osmosis is used, with a
Reverse osmosis L-L Ap
Gas separation G-G Ap very dense membrane and high pressure
Prevaporation L-G Ap drops [10-100 bar (10 6 -10 7 N m"2)].
Thermo-osmosis L-L AT/Ap When gas molecules need to be separated,
Membrane-distillation L-L AT/Ap
Dialysis L-L Ac the mechanism used is not sieving. Instead
Electrodialysis L-L AE a so-called solution-diffusion mechanism
a takes place (Graham, 1866). The solubility
Ap=pressure, Ac = concentration, AE=electric field,
and AT= temperature. is determined by the membrane material and

SYMMETRIC ASYMMETRIC

cylindrical pores cylindrical pores

porous porous with dense toplayer

Figure 1-35. Schematic representa-

tion of different membrane morpholo-
gies (Berghmans, 1995).
dense (homogeneous) Composite
 1.3 Structure Development During Flow 41

the molecule to be dissolved. At the per- Table 1-2. Ideal selectivities and permeabilities
meate side of the membrane, the chemical towards oxygen and nitrogen for some typical mem-
brane materials.
potential of the molecules is lower, causing
diffusional mass transport as long as a gra- Membrane a
O2/N2
dient exists. The permeability of a mem- material (Barrers5) (Barrers)
brane is the product of the solubility S and PPE 15.5 3.1 5.0
the diffusion constant D (von Wobreski, PA 1.7 0.33 5.1
1879) PC 1.5 0.27 5.6
PSF 1.2 0.20 6.0
PEI 0.4 0.05 7.6
P = DxS (1-3) PH 0.1 0.015 6.7
Since both the solubility and the diffusion a
For abbreviations, see text; Barrer=10~ lo cm 3
constant are material parameters, the perme- 2
(STP)-cm/crn -s-cm-Hg, data from Kesting and
ability of a membrane is a fundamental Fritzsche (1993) and from Smid et al. (1991).
property, independent of the thickness of the
membrane (Koros and Fleming, 1993). The
flux J can be expressed as the permeability Table 1-3. As Table 1-2, but now towards heli-
P multiplied by the pressure gradient Apld, um/methane and carbon dioxide/methane.
with d the thickness of the membrane
Membrane material He/CH4 CO2/CH4
Ap PPE 20.8 15.6
(1-4)
d PA 35 18.8
PC 51 23.6
The ideal separation of these membranes PSF 52 23.4
can be expressed with the separation param- PES 80 28.0
eter, or the selectivity, a AB , for a pair of PEI 264 37.4
PH 132 21.2
components A and B, and is defined as

(1-5)
In principle this selectivity is a fundamen-
tal property, so it has a fixed value. In prac-
tice, the selectivity is usually lower and
determined by measuring the flow rate of
both gases and taking their ratio. Polymers
used for membranes can be rubbery as well
as glassy. Typical membrane materials
include silicone rubber, polysulfone (PSF)
and polyethersulfone (PES), polycarbonate
(PC), polyetherimide (PEI), polyarylate
(PAR), polyhydroxyether (PH), polypheny-
lene-ether (PPE), and cellulose derivatives
such as cellulose acetate (CA), cellulosetri-
acetate, and ethylcellulose. For gas separa-
tion membranes glassy polymers are used,
because of their higher selectivity. Their
permeabilities are lower than for the more
rubbery polymers, but this can be compen-
sated for by reducing the thickness of the
skin. Table 1-2 gives an overview of their
selectivities and permeabilities towards
oxygen and nitrogen, indicating that the
selectivity increases when the permeability
decreases, while Table 1-3 indicates the
selectivity differences for different gases to
be separated.
In order to reach a high yield combined
with maximum selectivity, asymmetric
membranes are used, made via a phase sep-
aration process for which different tech-
niques are available. If a crystallizable poly-
mer is dissolved in a solvent, liquid-solid
(L-S) phase separation can occur. Other-
wise, liquid-liquid (L-L) phase separation
can generally take place, where the solution
42 1 Processing for Properties
DIPS
Figure 1-36. Schematic representation of the TIPS
and DIPS processes (T, temperature; P, polymer;
S, solvent; NS, nonsolvent (Berghmans, 1995).
separates into two liquids. These phase sep-
arations can be induced by either changing
the temperature (TIPS) or changing the con-
centration (DIPS) (see Fig. 1-36).
In order to freeze in the morphology
induced by phase separation, solidification
of the polymer has to be realized. This is
usually obtained by passing the glass tran-
sition temperature of the polymer, although
crystallization itself can also be used (L-L
followed by L-S). The use of TIPS in mak-
ing membranes is only recent and mostly
DIPS, as originally introduced by Loeb and
Sourirajan (1962), is applied. In this pro-
cess, no temperature change is required to
induce phase separation. Instead, a change
in concentration is induced by exchanging
solvent for nonsolvent. Of course the sol-
vent and the nonsolvent have to be mutual-
ly soluble. The formation of the structure
with both processes is schematically shown
in Fig. 1-37.
Vitrification, either by crystallization or
by passing the glass transition temperature
solvent non-solvent
Figure 1-37. (a) TIPS: mechanism of phase separa-
tion by lowering the temperature (B.P. is the Bergh-
mans point); (b): DIPS: phase separation by changing
the composition, exchanging solvent for nonsolvent
(Berghmans, 1995).
is depicted in the ternary phase diagrams of
Fig. 1-38.
As an example we will use the continuous
spinning of hollow porous asymmetric fibers
of poly(phenylene-ether) (PPE), used for
oxygen/nitrogen gas separation. Although
PPE is known as an amorphous polymer, it
can crystallize from solution. Interestingly,
the crystallization line and the liquid-liquid
demixing line almost coincide, see Fig.
1-39, which shows the phase behavior of PPE
using cyclohexanol as a solvent. In this case
L-S and L-L demixing mutually interfere.
 1.3 Structure Development During Flow 43

300
crystallization (5C/min)
o melting (10C/min)
a glass transition
cloud point

solvent non-solvent

polymer

Tg - line
0.0 0.2 0.4 0.6 0.8 1.0
W,

b 300

solvent non-solvent

Figure 1-38. Ternary phase diagrams where interfer-

ences with liquid-liquid demixing are possible: (a)
crystallization and (b) glass transition (Berghmans,
1995).

This is indirectly made use of in spinning

asymmetric hollow fiber membranes.
Initially, a homogeneous polymer solution 0.0

is prepared of PPE-TCE (trichloroethy-

lene), to which some nonsolvent (EtOH,
2-ethyl-l-hexanol) is added in order to start
at a position closer to the binodal demixing
line. This situation is enhanced by the eva-
poration of some solvent in the air gap,
yielding gradients over the thickness of the
fiber that are even more enlarged by the
introduction of temperature gradients due to
slight cooling in the same air gap (mostly
TIPS, consequently). In the coagulation
Figure 1-39. Temperature-concentration diagram of
PPE in cyclohexanol, (a) as measured and (b) sche-
matically. W2 is the weight fraction of PPE (Bergh-
mans, 1995).
bath, the solvent is replaced by nonsolvent
(MeOH, methanol), i.e., the DIPS process,
combined with efficient cooling, yielding
fast vitrification, and eventually a closed,
thin skin. From the inside, the hollow fiber
44 1 Processing for Properties
is fed with a solvent/nonsolvent mixture to
allow only DIPS here, resulting in an open,
porous structure. The process was success-
fully developed by KRITNO and Aquilo
[see Smid et al. (1991)]. Theoretical
approaches have been developed for TIPS
and DIPS processes [see Cheng (1993),
Cheng et al. (1994), and Berghmans
(1995)]. In Berghmanns's thesis, some nice
illustrations can be found using the more
accessible system poly(ethersulfone)M-
methyl-pyrolidine (PES/NMP) with water
as a nonsolvent, illustrating funny shaped
interiors of the fibers (see Fig. 1-40), and
more seriously, a closer study of unwanted
macrovoid formation, which grows from
Figure 1-40. Different cross sections of PES fibers made using different compositions of the internal bore liq-
uid causing DIPS on the inside (Berghmans, 1995).
instabilities on the surface and possesses a
kind of fractal structure (see Fig. 1-41).
In this section, it was illustrated how spe-
cific structures can be obtained in the pro-
cessing of polymers if phase separation and
early vitrification are used as a way to create
the desired morphologies. In Sec. 1-4 of this
introductory chapter, and in Chap. 10 of this
Volume, the focus will be on the chemical-
ly induced phase separation process, CIPS,
where phase separation is chemically
induced by polymerizing the (reactive) sol-
vent after molding. Upon polymerization,
the solvent converts into a nonsolvent, thus
introducing phase separation, and in most
cases, phase inversion. Finally, the solvent
 1.3 Structure Development During Flow
25 (am
Figure 1-41. Visualization of the formation of mac-
rovoids in PES placed in between two glass plates, and
at different times after being surrounded by nonsol-
vent (Berghmans, 1995).
becomes, as a second, dispersed phase, an
integral and often even structural compo-
nent of the final product. This method
proves to have great potential for creating
unique materials, on the one hand by pre-
cise control of the size of the dispersed phase
(from 1 |nm down to 20 nm) via the preven-
tion of coalescence, and on the other hand
by turning the final properties of this phase
45
from completely rubbery to glassy by start-
ing with aliphatic or aromatic epoxies as the
reactive solvent.
1.3.6 Crystallization
As already mentioned in the introduction
to this section (Sec. 1.3.1), even in one-
phase systems morphology development
during flow can be important for the final
properties, provided that we deal with crys-
tallizable polymers. Two chapters (Chaps. 4
and 5, respectively) of this Volume, are
devoted to the modeling of shear-induced
crystallization, so in this introductory chap-
ter only some examples will be given.
As in the determination of proper constit-
utive equations for the time- and tempera-
ture-dependent nonequilibrium density and
the history dependent viscoelastic stresses,
also in crystallization the problem is not so
much a mathematical one, but much more
an experimental one. In differential scan-
ning calorimetry (DSC), the crystallization
kinetics can in principle be measured. How-
ever, upon shear, drastic changes of orders
of magnitude can occur, caused by shear-
induced nucleation. Important in this
respect is the fact that the high end tail of
the molecular weight distribution will be
oriented in flow the easiest. It is this tail that
can hardly be measured using conventional
characterization equipment, e.g., gel per-
meation chromatography (GPC). These
flow-induced nuclei not only accelerate the
crystallization process tremendously, but
also cause anisotropy by directing the crys-
tal growth direction. As a particular exam-
ple, it was shown by Bevis and co-workers
at Brunei University (Allan and Bevis,
1992; Bevis, 1994) that by using a special
injection molding technique, the so-called
multi-live-feed system which keeps mildly
shearing the melt during solidification (thus
only orienting those molecules that have a
46 1 Processing for Properties

long relaxation time; i.e., the high molecu- and plate geometry, were molten at a high
lar weight tails which are close to the crys- enough temperature, usually 260 C, long
tallization temperature), a more than 90% enough to erase the crystal memory but for
shish-kebab morphology could be realized insufficient time to obtain excessive degra-
through the whole thickness of the product. dation. Subsequently the sample and the
Originally, the technique was developed to measuring chamber were brought to a lower
eliminate weld lines. Later it was used to temperature, usually 138 C, and a dynam-
control the (eventually multiaxial) orienta- ic test was started. The temperature for
tion over the thickness by shearing in dif- (slight) supercooling was chosen as such
ferent directions at different stages of the that it took a long time before any notice-
cooling process. Most interesting is that this able effect of the proceeding crystallization
technique allows, for the first time, the con- occurred in both the increasing dynamic
trol of whatever happens in the mold, inde- modulus and the decreasing loss angle. Sec-
pendent from the product design and the ondly, the samples were pre-sheared at the
position of the filling gates (the sprues), high temperature and the same procedure
since the influence of the flow during mold was repeated; the results are plotted in
filling is clearly overruled by the flow Fig. 1-42.
applied during solidification. The influence of the nucleation-induced
As a second example some recent data are crystallization is clear. Using different shear
presented, as obtained in our laboratory for histories, it could be established that the
isothermal crystallization experiments with total shear proves to be the determining fac-
slightly supercooled polypropylene (PP) tor, although a higher shear rate results in a
melts using a standard Rheometrics device high shear time. Of concern is that different
(RDSII) (Vleeshouwers and Meijer, 1996). grades of PP, with different molecular
The following procedure was adopted: PP weight (distributions), revealed completely
samples, placed between the standard cone different behavior (see Fig. 1-43).

10 7
: shearing times (s)
25
lOO/' /50 38
6
10
! 2 0 0 / / / /
/
no shearing
5
10

10 i 4 L /

Figure 1-42. Isothermal

10 3 crystallization experiments
in a Rheometrics RDSII for
a PP melt with different
10 2
pre-shear histories, 5 s~! at
260 C (tan 8 is the loss
10 1 angle and G'the dynamic
. .
modulus) (Vleeshouwers
10 i i i i i i i and Meijer, 1996).
2500 500C
time (s)
 1.3 Structure Development During Flow 47

- I KJ tt

106 I G1

/r
105 /PP3

10
To "
Q.
o t
b
10 3

r
10 2
tan 6

i i I

0 1OOO 2000 3000 4000 5000 6000 7000 1000 2000 3000 4000 5000 6000 7000
time (s) time (s)

Figure 1-43. As Fig. 1-42, for three different PP grades: a high molecular weight (PPl) a low molecular weight
(PP2), and a broad molecular weight distribution (PP3), in between the other two. The conditions were: (a) with-
out shearing before quenching to 138C, (b) after pre-shearing at 200 C and 5 s"1 for 100 s, (c) without pre-
shearing before quenching to 140 C, and (d) after pre-shearing under the same conditions as (b) with subsequent
quenching to 140 C (Vleeshouwers and Meijer, 1996).

These aspects are relevant for all polymer More research is apparently needed in this
processes where crystallization occurs after area.
pronounced shearing, and the different
behavior of different grades of, e.g., PP and
1.3.7 Liquid Crystalline Polymers
PE in fiber spinning, film blowing, and
injection molding, could possibly be Of all polymers, the liquid crystalline
explained based on these properties. Tuning polymers show the most pronounced struc-
of the molecular weight distribution still ture development during flow. Lyotropic
proves to be a powerful tool in designing systems are used in high performance fiber
optimum grades for these (bulk) processes, processes (see Chap. 11 of this Volume),
especially now the new metallocene catalyst while thermotropic systems are generally
systems, which enable previously impos- extruded and, in particular, injection mold-
sible fine-tuning, are increasingly used. ed. Numerous papers have been published
48 1 Processing for Properties
on the resulting layer structure in molded
products. It is far beyond the scope of this
introductory chapter to review all these
developments. It could even easily be stat-
ed that most of the structure development
can be considered as an unwanted effect,
yielding delamination problems. More
restrictive still, however, is the price of liq-
uid crystalline polymers, and after a boom
of attention in the late 1980s and early
1990s, industrial interest seems to have
stopped completely, apart from some niche
markets, in particular the electronics indus-
try, which requires properties such as
dimensional stability at high temperatures,
solvent resistance, etc., and of course the
fiber world. Scientifically interesting
results on the structure development of liq-
uid crystalline polymers have been obtained
on the theoretical side by Doi (1981), Mar-
rucci and Greco (1993), and Marrucci and
Maffetone (1993), and experimentally by
the group of Mewis and Moldenaers in Leu-
ven [see, e.g., Moldenaers et al. (1989,
1993), Yanase et al. (1991), Grizaud et al.
(1993), and Maffetone et al. (1994)], and in
Bristol by Fischer et al. (1996).
Also worthwhile mentioning are the
many attempts that have been made in the
direction of blending stiff molecules with
flexible ones, mainly aimed at lowering the
price of the resulting systems and reducing
the processing and delamination problems.
Interesting morphologies were obtained by
uniaxially stretching macroscopic blends in
a spinning device [see, e.g., Crevecoeur and
Groeninckx (1990 a, b, c, 1991), and Crev-
ecoeur (1991)]. The mechanical properties
of these systems, however, never exceeded
the Halpin-Tsai type rule of mixtures, and
the limitation to fiber-shaped products pre-
vented their widespread application.
More interesting in view of the perspec-
tive properties is a dispersion of single rigid
rod macromolecules in a flexible coil poly-
mer matrix, such that the rods act as a rein-
forcing component. Although a mixture of
rigid rod and flexible coil polymers on a
molecular scale is entropically unfavorable
(Flory, 1953,1969) and self alignment of the
rods via phase separation will occur, there
are ways to prevent macroscopic phase sep-
aration between the two types of polymer.
Firstly, a chemical bond between the two
polymers in terms of block and graft copol-
ymers results in a phase separation limited
to nanoscopic dimensions (Dang and Evers,
1991; Dotrong et al., 1992; Arnold et al.,
1989, 1990). These types of polymer assure
an efficient translation of the stress applied
between the reinforcing element and the
matrix material. Besides this, other chemi-
cal variations lead to molecular composites
such as the homogeneous blending of two
flexible polymers where one can be trans-
ferred at elevated temperatures into a stiff
chain configuration [so-called in situ gener-
ation of molecular composites (Arnold
et al., 1989, 1990)]. Here a phase separation
cannot occur and the stiff chain macromol-
ecules are somewhat "trapped" in the flex-
ible matrix. Finally, the use of low molecu-
lar weight stiff compounds with Y-shapes
and star shapes (multipodes) may increase
the compatibility due to the small molecu-
lar weight of the multipodes. They might act
in the same way as reinforcement on a
molecular scale (Braun et al., 1993). Most
important is the fact that such a reinforce-
ment is reported to act in all three dimen-
sions. Other investigations on polymers
with similar structural elements show syn-
ergistic effects in blends with PETP (Hin-
richsen and Rotting, 1993). However, the
processing of blends of unmodified rigid rod
and flexible chain polymers can also lead to
polymer composites with stiff reinforcing
elements on a nanoscopic scale. For that
purpose, processing via dissolving both
polymers in a common solvent is required.

The critical concentration above which
phase separation will occur even in solution,
is limited to about 4 - 5 % polymer (Flory,
1953, 1969). Rapid coagulation of such
solutions leads to the composites described
above with mechanical properties according
to the Halpin-Tsai equation, and with aspect
ratios of the reinforcing elements of above
100 (Takayanagi et al., 1980; Helminiak
et al., 1983; Kummerlowe and Kammer,
1990).
The synthesis of stiff chain polymers in
solutions of flexible chain polymers, or a
shear-induced homogenization of demixed
solutions, can shift the value of the critical
concentration to about 8% polymer in the
solution (Berger et al., 1993). Phase separ-
ation may even be completely suppressed if
specific interactions between the two poly-
mer types (ionic interactions, acid-base
interactions) exist. This has not only been
predicted theoretically (Eisenbach et al.,
1995; Noolandi and Shi, 1996), but it has
also been experimentally explored by
Eisenbach et al. (1995) and Harra and Chen
(1996). The resulting blends are on a molec-
ular scale but, more important they are trans-
parent and melt-processable. The reported
mechanical properties for these composite
materials exceed the theoretically predicted
values.
1.3.8 Discussion
In this section, it has been demonstrated
that structure development during flow is of
utmost important for the processing of poly-
mer systems. The main reason is that almost
without exception polymers are combined
with other polymers, reinforcing agents, sta-
bilizers, antioxidants, etc., to make them
really suited for their final task. Apart from
the case of reactor-modified polymers, pro-
cessing plays a decisive role. It is clear that,
despite the progress made in recent years,
1.4 Reactive Processing 49
still a lot of research is necessary in this area
to really be able to predict the performance
of polymeric systems, as obtained via pro-
cessing, depending on the properties of the
constituent phases. In the next section, reac-
tive processing is briefly reviewed.
1.4 Reactive Processing
1.4.1 Introduction
Reactive processing is traditionally
exploited in molding processes such as
(R)RIM, (S)RIM (reinforced and structural
reaction injection molding) and RTM (resin
transfer molding), also in BMCs (bulk
molding compounds) that are injection or
compression molded, and in composite pro-
cesses like GMC [glassfiber (mats) rein-
forced compounds]. They are applied in pre-
pregs and in monomer-wetted, continuous
roving processes, e.g., pultrusion and fila-
ment winding. Finally, hand lay-up process-
es exist which involve a lot of labour and
where, eventually, hot presses or autoclaves
are used to cure the product. Another
extremely important area is that of coatings
and paints. Usually epoxies, unsaturated
polyesters, and polyurethanes (PUR) are
used, although specialities like caprolactam
(anionically polymerized) also find applica-
tions. Handbooks that summarize the state-
of-the-art of the modeling of these process-
es are available, see, e.g., Macosko (1989),
Isayev (1987), and Tucker (1989). Chapter
9 of this Volume deals with (R)RIM process-
es, especially of the most important class of
materials: the PURs in RIM processes,
while Chap. 7 of this Volume treats the fun-
damentals of network formation. Today
reactive extrusion has also gained a lot of
attention, mainly because of the versatility
of the continuous compounding technique.
Since extruders can in principle be defined
50 1 Processing for Properties
as intensively stirred, self-transporting mix-
ers with a small volume (thus expensive)
and an improved heat exchange possibility
relative to stirred vessels, which is, howev-
er, still limited, especially if highly viscous
systems are used; hence severe limitations
exist in practice with respect to the number
of possible reactive systems that can be
explored successfully. The requirement of
total conversion puts an even more severe
constraint on the choice of system to be
used. Chapter 6 of this Volume gives a
detailed review on reactive extrusion, while
Chap. 8 of this Volume focuses on the reac-
tion at interfaces in polymer blends. In this
section the CIPS (chemically induced phase
separation) process will be briefly intro-
duced, in addition to the TIPS and DIPS pro-
cesses dealt with the previous section
(Sec. 1.3), while more details can be found
in Chap. 10 of this Volume.
1.4.2 Thermoplasts in Reactive Solvents
The use of reactive solvents offers an
interesting and flexible route to extend to
processing characteristics of thermoplastic
polymers beyond their existing limits. This
holds for both intractable and tractable poly-
mers. The first mainly applies for amor-
phous, high Tg polymers, where processing
is usually limited due to the high tempera-
tures required, which are close to their dete-
rioration temperature, and where the solvent
helps to reduce the processing temperature
considerably. The second mainly holds for
semi-crystalline polymers, and the attention
here is focused on obtaining low viscosities
in order to be able to apply alternative pro-
cessing routes, e.g., pouring or casting, for
those polymers that are generally easy to
process by more conventional techniques
such as injection molding or extrusion. In
both cases the solvent is polymerized after
molding, thus converting it into a nonsol-
vent, and becomes, after the concurrent
phase separation and phase inversion, an
integral and often structural part of the final
product. Interestingly, specific morpholo-
gies, in terms of the size of the dispersed
(previous solvent) phase formed or the posi-
tion and thickness of the in situ formed inter-
layers if polymerization occurs in the pres-
ence of a polar surface, can be obtained
which can otherwise be extremely difficult
to realize. Moreover, the flexibility of the
choice of the reactive solvent creates tune-
able mechanical (and if requested, other)
properties for these phases, varying from
glassy, with a Tg of typically 200 C, to com-
pletely rubbery, with a Tg far blow room
temperature. Of course a disadvantage of
the technique is that a polymerization step
must occur after the shaping process. Com-
pared to more standard reactive processing
techniques, however, clear advantages exist
with respect to the absence of the need for
100% conversion, the occurrence of early
vitrification (yielding a fast demolding pos-
sibility) produced by the reaction-induced
phase inversion, and the fact that the con-
tinuous thermoplast phase ultimately deter-
mines the main product properties, includ-
ing the possibility of second stage deform-
ability and reprocessability.
In order to meet the ever-increasing
demands put on polymeric materials in new
applications, polymer chemists continue to
synthesize new polymers that can often be
regarded as intractable from a processing
point of view. This is the case for the group
of high temperature polymers developed for
structural applications, where a high glass
transition temperature is required, and for
polymers designed for those applications
where a high molecular weight is necessary
for mechanical reasons. Basically, the main
advantage of polymers over the more tradi-
tional materials, which is their easy process-
ability, is often lost and either compromis-

es are accepted, e.g., by introducing flex-
ibility to the polymer backbone, thus low-
ering the Tg or by blending with more flex-
ible polymers, e.g., in PPE-PS blends
(Noryl from General Electric Plastics), or
expensive post-machining is used, e.g., in
products made from ultrahigh molecular
weight polyethylene (UHMWPE) pressed
and fused plates; alternatively processing
aids like volatile solvents are applied, e.g.,
in spin coating or solution spinning, for
example, of the same UHMWPE used to
produce high performance fibers. This last
solution is restricted to products with a high
surface-to-volume ratio, usually fibers and
films, and violates the air quality regula-
tions, thus necessitating the need for com-
plete solvent recovery. Moreover, the final
product is only a (often relatively small) part
of the main stream in the production pro-
cess, which almost exclusively consists of
closed loop evaporation and condensation
operations for the solvent. All these prob-
lems make the products of such a process
necessarily expensive but, more important-
ly, they limit the use of these attractive poly-
mers in many possible new applications.
Basically it could be stated that the major
part of recent polymer development, as
occurs in most of the large research labora-
tories of the main polymer producers all
over the world, and sometimes in the labor-
atories of important and big enough end-
users, can be summarized as being a contin-
uous compromise to the stated necessity of
introducing a low enough viscosity as
required for easy processing while main-
taining the most important mechanical
properties of the product: stiffness, strength,
and especially, work-to-break (impact
strength). The molecular weight (distribu-
tion) of the pure polymers is finely tuned
and/or blending/compounding with differ-
ent polymers is practised to obtain princi-
pally heterogeneous materials that should
1.4 Reactive Processing 51
possess a stable enough morphology to sur-
vive the subsequent shaping step. The easi-
ly recognized alternative of using reactive
processing techniques, as mentioned in Sec.
1.4.1, seemingly solves the problem, since
monomers are generally present during pro-
cessing and they are converted into poly-
mers only after their final shaping operation.
Disadvantages and limitations exist, how-
ever. Apart from the introduction of chem-
istry to the end-user, which does not auto-
matically guarantee the best control during
polymerization, there is a need for almost
complete conversion, since the product's
properties are directly and exclusively
determined by the chemistry, and only at the
end of the polymerization are the final
mechanical properties obtained.
A possible solution to some of the prob-
lems mentioned is to make use of reactive
solvents. Basically the idea is to sell the sol-
vent with and within the product after hav-
ing made it harmless by applying a polymer-
ization step. During processing, the solvent
either causes a strong reduction in the pro-
cessing temperature (which is important for
the intractable high temperature polymers)
or it decreases the viscosity of the polymer
such that standard (for intractable high
molecular weight polymers) or alternative
(for tractable polymers) processing tech-
niques, where a low viscosity is a prerequi-
site, come within reach. After shaping, the
solvent is converted into a nonsolvent
induced by the first polymerization steps.
Phase separation results, generally accom-
panied by phase inversion, which happens to
occur anyway if the volume fraction of the
polymer exceeds about 10%. A dispersed
phase results, locking the original solvent
inside the thermoplastic matrix material that
forms the continuous phase. A schematic
impression of this is depicted in Fig. 1-44.
In Chap. 10 of this Volume, several
systems which can be regarded as primary
52 1 Processing for Properties
PPE
epoxy resin
solvent
extruder / kneader
1 tions in other fields, making use of the flex-
Homogeneous 1 ibility of this technique, are mentioned.
solution
low Tg, viscosity
Cure solvent - > non-solvent
Epoxy particle
1 ing networks), where one monomer is poly-
'filled' PPE
SSI
Figure 1-44. Schematic diagram of the procedure for
processing polymers using reactive solvents (after
Venderbosch, 1995).
examples of this novel processing tech-
nique are reviewed: The first, and by far
most extensively investigated system, is
PPE-epoxy, an example of the processing
of an intractable polymer (Venderbosch,
1995; Venderbosch et al., 1994, 1995 a, b;
Meijer et al., 1996). The phase diagram and
the (chemo)rheology (which are important
for polymer processing) are determined and
the morphology development, which yields
the final product properties, is recorded.
Different epoxies, aromatic versus aliphat-
ic, are used to adjust the properties of the
dispersed phase. Accordingly, composite
applications have been explored, where
unique morphologies are obtained since
phase separation preferentially occurs at the
polar surfaces of the fibers and the "opti-
mal" composite could possibly be fabricat-
ed using this technique. Subsequently, the
systems polyethylene-styrene (PE-St) and
polyethylene-butylmethacrylate (PE-BA)
are reviewed as examples of tractable poly-
mers. In these cases, crystallization inter-
feres with the chemically-induced phase
separation and the focus will be on the mor-
phology development during reaction.
Some of the outlooks on possible applica-
1.4.3 In Situ Characterization
Systems like these resemble the tech-
niques used to obtain IPNs (inter-penetrat-
merized in the presence of a polymer net-
work, so forming a second, interpenetrating
network. Also, both networks can be formed
simultaneously or sequentially. Depending
on the chemical or physical nature of the net-
work, crosslinks or entanglements, or com-
binations of both, the nomenclature is dif-
ferent. The above examples can be classi-
fied as semi-IPNs. Not only is the introduc-
tion of processability an important issue in
these systems, but a controlled phase separ-
ation is also of importance for obtaining the
desired properties in the final product. As in
the in situ polymerizations of block copol-
ymers, e.g., with hard and soft segments, as
in polyurethanes, chemically induced phase
separation can yield unique morphologies
and the monitoring thereof is of great prac-
tical use. Therefore complex in situ charac-
terization methods are increasingly being
used [see e.g., Goossens et al. (1997) and
Chaps. 10 and 9 of this Volume]. Examples
of these methods are Raman spectroscopy,
which can distinguish between reaction
kinetics and the kinetics of phase separation
(see Figs. 1-45 and 1-46 for examples), and
combined time-resolved wide and small
angle scattering patterns (WAXS and
SAXS), which can distinguish between the
kinetics of phase separation and crystalliza-
tion (see Fig. 1-46). The last measurements
are usually performed using synchrotron X-

00 700 800 900 1000 1100 1200 1300
W&venumber [cm"1]
ray sources like those in Daresbury, Ham-
burg, and Grenoble.
As an example of the possible control
of the morphology of the dispersed
phase, the system poly(methylmethacry-
late)(PMMA)-(aliphatic) epoxy is used.
Polymerizing two compositions (50/50 and
70/30) at three temperatures (60, 100, and
140 C, resp.) yields not only completely
different particle sizes of the dispersed
phase, but also different trends (see Fig.
l-47)(Jansenetal., 1997).
In this case we are aiming at the smallest
possible particle sizes of the rubbery dis-
persed phase (usually ca. 20 nm) in order to
obtain the maximum mechanical properties
in terms of toughness (see Sec. 1.5 of this
Chapter and Chap. 12 of this Volume). The
explanation for the experimental findings
concerning the resulting particle size in
Fig. 1-47 is based on the understanding that,
during polymerization, coalescence of just
phase-separated particles should be avoid-
ed as much as possible. This can be realized
1.4 Reactive Processing 53
Figure 1-45. Raman
spectra of PE, PS, and
styrene.
1400 1500 1600
by either slowing down coalescence by
keeping the continuous phase highly vis-
cous, thus performing the polymerization
close to the (composition-dependent) Tg of
the matrix material, or by overcoming
coalescence by reaction kinetics. Both
aspects can be seen by inspection of the
results presented in Fig. 1-47. Given the
composition-dependent glass transition
temperature of the original solution (Fox
equation, see, e.g., Fig. 1-37), plotting
the resulting particle sizes against
r e f f =(r p o l - r g ) would result in a single
curve showing a maximum. From Teff=0,
the particle sizes increase due to the pro-
nounced effect of coalescence; after the
maximum, the particle sizes decrease due to
the temperature dependence of the reaction
kinetics. By chemically increasing the reac-
tion kinetics, independent of the polymer-
ization temperature, the whole curve would
come down. From this analysis, a time-
dependent polymerization temperature can
eventually be derived by a stepwise
54 1 Processing for Properties
20 wt% PE in styrene polymerized at 120 degC
80 1800
Wavenumber [cm~1]
Time [min]
Time [min]
q [1/A]
Time [min]
Figure 1-46. (a) Time resolved Raman spectra, and
(b) WAXS and (c) SAXS patterns measured during
polymerization at 120C of 80% styrene (slow
system) in 20 % polyethylene (Goossens et al., 1997).
increase, given the conversion-dependent
Fox equation and thus the conversion-
dependent r g (see Figs. 1-48 and 1-49).
Things become even more complicated if
both constituents are reactive, such as in the
case of MMA-epoxy (Jansen et al., 1997).
Depending on the relative reaction kinetics
of both monomers, the time- and composi-
tion-dependent glass transition temperature
will change, and thus different polymeriza-
tion protocols will result. Generally, in the
polymerization of IPNs this is not taken care
of and, almost without exception, these
materials are polymerized at a relatively
high temperature. A lack of control of the
phase separation process results unless
multi-block polymers are synthesized as in
the case of, e.g., polyurethanes.
1.4.4 Discussion
In this section the CIPS process has been
introduced, which combines easy processing
with unique properties of the resulting poly-
meric systems via a controlled, chemically
induced phase separation process. A disad-
vantage of the technique described is that
chemistry is introduced to the end-user,
since, in order to obtain small particle sizes,
CIPS should be applied in quiescent sur-
roundings, e.g., in the mold. Raw material
manufacturers are currently investigating
how the technique using reactive solvents
can be successfully exploited in the produc-
tion of feedstock polymers in the form of
(thermoplastic) granules, e.g., via reactive
compounding. From a combination of the
conclusions from Sees. 1.3 and 1.4 of this
introductory Chapter, it will be directly clear
that in this case a large number of time-
dependent processes interfere, which is com-
plicated by a shear-induced phase inversion
process. In fact, HIPS (high impact poly-
styrene) and ABS (acrylonitrile-buta-
diene-styrene) polymers are more or less
made via these routes in stirred vessels. It is
obvious that a lot of research is still neces-
sary in this field in order to be able to make
quantitative, or even qualitative, predic-
tions. Apart from the necessity to chemical-
ly stabilize the structure obtained, advantag-
 1.5 Processing for Ultimate Properties 55

6o
- = c

e= 100C

^ m

Tcure= 140C

a "
Figure 1-47. Resulting particle size after polymerizing PMMA-epoxy of two compositions: (a) 70/30 and (b)
50/50, at three different temperatures (Jansen, 1996).

es with respect to low viscosities in the sub-
sequent shaping process are naturally lost.
The next section deals with obtaining the
ultimate properties of polymers via process-
ing.
1.5 Processing for Ultimate
Properties
1.5.1 Introduction
In the preceding sections, it has become
clear that the processing of polymers, at
least partly, determines the properties of the
final product. Particularly in the area of ulti-
mate properties, processing makes all of the
difference between mediocrity and excel-
lence. This might be best illustrated by the
processing of high performance fibers
(HPF) based on flexible polymers, notably
the linear polyethylenes. The difference in
mechanical properties between a garbage
disposal bag and an HPPE ultra strong fiber
is only obtained by orienting the macromol-
ecules in a processing operation. In this sec-
tion we will briefly review some of the ele-
mentary steps in these processes. Starting
56 1 Processing for Properties

increased reaction rate

limits the available
time for phase
separation and
coalescence

Temperature T

increased reaction rate

reaction temperature
Tg(PMMA)

Temperature T

Tg(cured epoxy)

Tg(epoxy monomer)
weight fraction polymer <j)

Figure 1-48. (a) Solvent-polymer phase diagram

(schematic) and (b) epoxy-PMMA phase diagram
showing the glass transition temperature of a one-
phase epoxy monomer-PMMA solution, the glass 60 100 140
transition temperature of the molecular, dispersed,
reaction temperature Tcure
cured epoxy-PMMA solution (hypothetical), and the
coexistence curves between epoxy and PMMA which
shift in the direction of the arrow as the epoxy poly-
merizes (Jansen, 1996).

with mechanical properties such as the mod-

ulus and strength (Sec. 1.5.2; see also
Chaps. 11 and 16, respectively, of this Vol-
ume), we will continue with the toughness
(Sec. 1.5.3.; see also Chap. 12 of this Vol-
ume) and end with a short discussion
(Sec. 1.5.4). 80 120
T T rorn
L J
cure g
1.5.2 Ultimate Modulus and Strength
Figure 1-49. Resulting particle size as a function of
The invention of high performance aro- the (conversion-dependent) effective polymerization
matic polyamide fibers, such as Kevlar from temperature for aliphatic epoxy blends with either
70 wt.% PMMA or 50 wt.% PMMA; (a) schematic,
Dupont and Twaron from Akzo-Nobel, (b) as measured (compare with Fig. 1-47), and (c)
started a long time ago with the observation replotted data of Fig. l-49b in terms of Fig. 1-49 a
that, upon increasing the concentration of (Jansen, 1996).

relatively stiff aramid molecules in solution,
a tremendous drop in viscosity was sudden-
ly observed. This drop in viscosity proved
to be related to the occurrence of the so-
called nematic state: a kind of self-assem-
bling of the individual molecules into
domains: bundles of molecules. This pro-
cess is a natural one and has been exploited
through the ages, e.g., in the transport of tree
trunks via natural and cheap mechanisms
like flowing rivers. This self-assembly can
also be found in disposits and wreckwood
in natural vortices as occur, e.g., close to
waterfalls, notably Niagara Falls. Also clos-
er to home: floating fishfood in the form of
cylinders with a limited aspect ratio tends to
form bundles, even in the absence of flow,
in the backyard pond. Back to aramids: the
drop in viscosity observed, not only served
to provide easy processability of rigid rod
molecules in solution, but also made it pos-
sible to orient complete domains rather than
individual molecules, e.g., in extensional
flows. This orientation is prerequisite for
obtaining the ultimate properties of macro-
molecules, as already explained in the intro-
duction (Sec. 1.1 of this Chapter). Apart
from the problems encountered in the poly-
merization of rigid rod molecules and the
aggressive solvents that have to be used, the
spinning of these solutions into fibers is a
relatively straightforward task. The strong
elongational flow into the die, followed by
the complete irrotational flow during the
draw-down applied in the (small) air gap
between the die exit and the subsequent
coagulation bath, is sufficient to orient these
domains into the direction of the fiber axis.
Given typical polymer concentrations of
15 %, the only mismatch originates from the
removal of solvent during coagulation. This
pushes the case for high molecular weight
polymers, given their more modest off-axis
rotation during this process of removal of
the 85 % solvent, even if this is not neces-
1.5 Processing for Ultimate Properties 57
sarily required for the ultimate strength,
given the generally strong hydrogen bonds
between the individual macromolecules of
aramids (see for details Chap. 11 of this Vol-
ume).
In contrast with the processing of these
lyotropic systems, the orientation of flexible
macromolecules during processing is much
more complicated. This is mainly due to the
presence of the restoring entropic forces and
the absence of possibilities to freeze in the
ultimate flow-induced orientation. In this
respect is it worthwhile remembering that
the frozen-in orientation in, e.g., injection
molding, where both high strain rates and
high cooling rates prevail, is only of the
order of 2% of the maximum molecular
orientation that is obtainable (see Sec. 1.2 of
this Chapter). In injection molding, even the
presence of this minor orientation proved to
be relevant for long term dimensional stabil-
ity, since it introduces anisotropic relaxation
and physical ageing. Here we need to
achieve the maximum orientation since,
given the typical series character of amor-
phous and oriented structures, yielding rule-
of-mixtures type behavior with emphasis on
the enormous influence of the weakest
component, even if only a few percent of
unoriented material is present, this will ruin
our ultimate properties, e.g., in terms of stiff-
ness (see Irvine and Smith, 1986). Therefore
almost without exception [a nice example
thereof is the interlocking shish-kebab struc-
ture as obtained via a very well controlled,
directed crystallization in supercooled
melts, see Odell et al. (1985), Chap. 4 of this
Volume] drawing in the solid state is the only
way to approach maximum orientation. The
reason is that two prerequisites for orienting
flexible macromolecules exist: first, the
product of the deformation rate and the
relaxation time should be larger than one, in
order to overcome the natural tendency of
polymers to coil up, and second, the prod-
58 1 Processing for Properties
uct of the deformation rate and the deforma-
tion time, i.e., the total deformation, should
be large enough to get full extension of the
chains. In the solid state, the first require-
ment is easily met, given the long relaxation
times below the melting temperature. How-
ever, the second requirement produces
severe limitations, and naturally, there is a
molecular weight dependent limit to the
drawing, even at temperatures approaching
the melting temperature. In apolar polymers
with relatively weak van der Waals intermo-
lecular interactions, even within the crys-
tals, these constraints are caused by the pres-
ence of the entanglement network. They can
be removed by the crystallization of poly-
mers from dilute or semi-dilute solutions.
Remarkable in this respect is the fact that the
first strong PE fibers were made from
stirred, seeded, supercooled solutions in
which a gel was formed close to the rotor,
from which a fiber was drawn using a seed
that created a strong, elongational, orienting
flow near its tip (Penningset al., 1970; Zwij-
nenburg and Pennings, 1975).
As a consequence of the above, all orient-
ed structures are (in practice) nowadays
obtained in the solid state (see Chaps. 11
and 16 of this Volume). The most extreme
example is the rather academic single-crys-
tal-drawing, using coextrusion techniques
with split billets, as developed by Kanamo-
to and co-workers [see,e.g.,Kanamotoet al.
(1983, 1984)]. High draw ratios are realized
and the mechanical properties reach their
upper limit in terms of the maximum crys-
tal modulus as measured by X-ray scatter-
ing [see, e.g., Nakamae and Nishino
(1991)]. A much more practical technique
is the so-called gel-spinning process, where
semi-dilute solutions of UHMWPE are
continuously spun via a dry- or air-gap
(dry-wet) spinning process, and the gel
formed upon cooling, which is accompanied
by crystallization, is the intermediate that
arrests the disentangled state of the poly-
meric material [see, e.g., Smithet al. (1979),
Smith and Lemstra (1980 a, b, c, 1982),
Smith et al. (1981), Lemstra et al. (1987)].
Even after removal of the solvent, the dis-
entangled precursor fibers can be postdrawn
in the solid state to HPPE (high performance
polyethylene fibers). Impressive mechani-
cal properties in terms of specific strength
and modulus are today realized in continu-
ous industrial processes.
In their final application, e.g., fishing
lines, nets, wovens for impact protection,
and composites, some of the properties of
the original fibers are lost, but moreover, the
heat resistance and especially the dimen-
sionality of the fibers limits their applicabil-
ity. This is mainly reflected in the poor com-
pressive and shear strengths of some of the
high performance fibers, which is directly
related to their molecular structure. More
specifically, to their secondary bonds. The
sequence HPPE (ID), aramids (1.5D), car-
bon (2D), and glass (with 3D covalent
bonds) reveals their compressive strength
and creep resistance (Govaert, 1990; Bas-
tiaansen, 1991; Peijs, 1993). As a conse-
quence, only the latter fibers are generally
used in structural applications, whereas the
first ones give the best impact protection,
and only limited adhesion to the matrix of
the composite is necessary in this case. For
further details, see Peijs (1993), De Kok
(1995), De Kok and Meijer (1996), and De
Kok and Peijs (1996). Especially in De
Kok's thesis, the attention is focused on the
transverse properties of composites, which
often limit their applicability. Interestingly,
the use of reactive solvents in composite
applications with thermoplastic matrices
offers new routes to design interfaces be-
tween the fibers and the matrix, and to tune
both their thickness and their (eventually
rubbery) properties (see Figs. 1-50 and
1-51).
 1.5 Processing for Ultimate Properties 59

Logarithmic
plastic strain [%]

10

0.1

Figure 1-50. Plastically deformed areas in (a) carbon fiber, (b) rubber fiber, and (c) rubber-coated carbon fiber
reinforced composites, with a hexagonal fiber array, at different percentages of the transverse strain (De Kok,
1995).

80 120

glass
fibre carbon
60
fibre
80
rubber coated
cylindrical hole /
carbon fibre
40

rubber fibre

cylindrical hole

5 10 15 2 4 6 8 10

Macroscopic transverse strain [%] Macroscopic transverse strain [%]

Figure 1-51. (a) Maximum local plastic strains in fiber composites as a function of the transverse strain applied,
and (b) calculated stress-strain curves (De Kok, 1995).
60 1 Processing for Properties
The concept of (ultra)drawing of poly-
mers via control of their entanglement struc-
ture proved to contain the key to the under-
standing of their mechanical properties, in
general, and toughness, in particular, even
for unoriented amorphous polymers. This
brings us to a short review on toughness
enhancement.
1.5.3 Ultimate Toughness
As stated above, product development at
the large research laboratories of polymer
manufacturers is often aimed at reaching the
best compromise between processability
and mechanical properties. To be more spe-
cific: to compromise between stiffness and
strength on the one hand and impact prop-
erties on the other, especially in the devel-
opment of engineering plastics that are used
in structural applications. Various methods
are used to control the molecular structure,
by changing the flexibility of the polymer
backbone and of the (sub)micron structure,
or by blending different polymers, e.g., with
a large difference in Tg. The general prob-
lem is that a large number of internal and
external variables influence the toughness
of the resulting system and, more seriously,
that, as a result, experience obtained with
one particular polymer system can rarely be
used for another. Consequently, a lot of
empirical knowledge exists which is diffi-
cult, if not impossible, to transfer to the next
generation of researchers, and too many
nonconclusive experiments are carried out.
Hence the development time and the time-
to-market increase unnecessarily. The main
reason for this is that the problems met in
"jumping scales" are not yet solved, i.e., it
is relatively unknown how events on the
molecular and microstructural scale influ-
ence the resulting properties on the macro-
scopic continuum level and vice versa. In
retrospect, the secret of a material's behav-
ior is contained in how the strong localiza-
tions of strain that naturally occur can be
controlled prevented from developing into
a catastrophic event, like a crack. The intro-
duction of small rubbery particles, which
should be able to cavitate, in, e.g., a glassy
matrix, provides stress concentrations and,
as a consequence, localized plastic flow
occurs before the breaking stress of the
matrix material is reached. Given the large
number, typically 1010 per cm3, of small,
typically 1 |nm in diameter, weak inclusions
("holes"), multiple crazing or shearing
mechanisms are introduced which finally
yield volume deformation rather than in-
plane deformation (e.g., behind a macro-
scopic notch) with impact values of
105 J/m2, as compared to the 1 J/m2 which
is roughly the theoretical work to break an
interface made out of strong covalent bonds
only.
It is the control of these mechanisms that
contains the secret of successful product
development in tough engineering polymer
systems. Interesting in this respect is that,
compared to a completely covalently bonded
system, like diamond, the replacement of a
large number of the strong covalent bonds
by weak van der Waals bonds (with a bond
strength that is typically only 10~5 that of
the covalent bond), thus changing diamond
into polyethylene for example, yields a 1010
times increase in the work-to-break. It is
clear that volume deformation is the cause
and that this is controlled by the fact that
only the weak intermolecular secondary
bonds are allowed to break, while the strong
covalent bonds in the polymer backbone
survive and give rise to "strain hardening"
at some distance from the growing strain
localization induced by the plastic flow. The
oriented fibrils that occur in crazes, bridg-
ing the crack, give a good illustration of this
principle, but similar arguments hold for the
oriented molecules in shear bands. Basical-

ly it could be stated that the control of micro-
deformation in material systems, where
mainly one bond type prevails, without
exception should be realized via the intro-
duction of surviving crack-bridging ele-
ments. Metal fiber reinforced metals, or
ceramic fiber reinforced ceramics are the
logical consequence, but even the stones
added to concrete introduce a similar mech-
anism.
As an illustration, Fig. 1-52 shows the
development of crazes in a polystyrene (PS)
tensile bar tested at different deformation
rates. The number of crazes that occur,
before one of them develops into a macro-
scopic crack, increases with increasing de-
formation rate; however, their number is
limited, and brittle behavior results. As an
illustration of what might happen on a
microscale, Figs. 1-53 and 1-54 show the
deformations of (at least if unnotched) mac-
roscopically tough polycarbonate (PC)
plates with macroscopic holes of different
sizes and in different packing orders. Clear-
ly, localizations influence each other and the
macroscopic response of the system
depends on the threshold of percolation of
1.5 Processing for Ultimate Properties 61
the deformable areas. Figure 1-55 shows an
example of the calculated deformation in
one of these systems.
In order to model the deformation behav-
ior in real systems in terms of the local de-
formation on the microscale, the number of
mechanisms involved demand special
numerical techniques where either a homog-
enization procedure is adapted, using a non-
local constitutive model on the macroscop-
ic level [see, e.g., Vosbeek (1994) and Vos-
beek et al. (1997)], or the so-called "multi
level finite element model" should be used
(Smit, 1996; Smit et al., 1997). This is, how-
ever, still an area which requires a lot of
research, and from now we will focus on the
ultimate toughness concept, as introduced,
amongst others, by Van der Sanden (1993),
Van der Sanden et al. (1993 a, b, 1994 a, b)
and Van der Sanden and Meijer (1993,
1994 a, b); Chap. 12 of this Volume.
A breakthrough in our understanding of
the deformation and failure of polymer
systems originated from the work of
Kramer's group in Cornell, who carefully
measured the maximum drawability real-
ized in extremely localized deformation
Figure 1-52. Crazes in a
PS test bar, tested at (from
left to right) 10 4, 1(T3,
1CT2, and KT1 s"1 (Smit,
1996).
62 1 Processing for Properties
-*r
Figure 1-53. Macroscopic shear band development
in a PC test plate with (a) one hole, (b) four holes, and
(c) a rounded notch (Smit, 1996).
zones like crazes and shear bands [see Don-
ald and Kramer (1982 a, b, c) and Henkee
and Kramer (1984,1986)]. A comparison of
these results with those obtained on the con-
straints present for ultradrawability (a chal-
lenging discussion during a visit of Kramer
to Smith and Lemstra in the early 1980s at
the DSM central laboratories in Geleen, The
Netherlands, proved to be useful for that
purpose), revealed that locally the maxi-
mum drawability originating from the phy-
sical network was indeed realized. This
maximum drawability of polymer networks
can be measured by removing the secondary
ij O i 4
0 o ) O I
'% t
i>
%.*
Figure 1-54. Deformation behavior in PC with holes
beyond a rounded notch, with (a) a square (b) a hex-
agonal stacking, and (c) with more, smaller holes, but
with an equal volume fraction of holes (Smit, 1996).
bonds by temperature rather than by stress,
thus measuring the height of the rubber pla-
teau modulus above the Tg and applying
classical rubber elasticity theory to relate
this modulus to the effective entanglement
density (Tervoort, 1996). This density is the
reciprocal of the molecular weight between
entanglement points, Me, or alternatively
the molecular weight between crosslinks in
thermosets, Mc, which directly determines
the maximum drawability of the network;
this scales approximately with the square
root of Me or Mc. As already stated above,
this result completely changed the focus of
 Ultimate Properties 63

i>

Figure 1-55. Calculated

deformation in a PC plate
containing holes (Smit,
/\ 1996).

research via a change of the general under-

standing of the deformation of polymer
" \ PS
systems, and moreover, it changed the tar- 300 - \
gets on material development, since the
attention since then has been focused on the
question: "How to avoid catastrophic local- 200 -
^ \ ^ ^ PC
izations?" Exaggerating it could conse-
quently be stated that all polymers can prin- theory ^ ^ ^ ^ ^ ^ _ ^
100 " "--.
cipally be characterized by only one param- practice '"\
eter, their network density, and that, e.g., a
polymer like polystyrene (PS) is so ductile, n j .y , \ j

given its large Afe, that its localization is so 10 20 30 40 50

pronounced that premature failure always
occurs on too localized a scale (see Fig.
1-56).
The solution to this problem was more or
less straightforward: Make the material so
thin, by controlling its microstructure, that
its specific thickness (e.g., that of the duc-
tile fibrils within the crazes) is reached
throughout. The concept of the material spe-
cific thickness was, accordingly, proposed.
Processing proved to be able to provide the
necessary tools to reach this new goal. By
making tapes of alternating nonadhering
layers of decreasing thickness, applying the
Multiflux technique, or by adding nonad-
Network density (x1025chains/m3)
Figure 1-56. Macroscopic drawability () and
theoretical maximum (-) drawability as a function of
the network density of all polymers [after van der San-
den (1993)].
hering core-shell rubbers of typically 200
and 100 nm diameter at increasing volume
fractions, the macroscopic strain-to-break
of the polymers suddenly increased when
the local thicknesses went beyond a materi-
al-specific critical thickness and the ulti-
mate toughness was reached. These results
are summarized in Figs. 1-57 and 1-58 (see
Chap. 12 of this Volume).
64 1 Processing for Properties
0 25 50 75
Network density (x1025chains/m3)
Figure 1-57. Macroscopic ductility reached, as a
function of the network density, by decreasing the
local material thickness to a value below the materi-
al-specific critical thickness (Van der Sanden, 1993).
O developed, e.g., by Smith and Heeger at
0.01
25 50 75
Network density (x1025chains/m3)
Figure 1-58. Material specific critical thickness as a
function of the network density. Solid line: results of
a first-order theory (Van der Sanden, 1993).
The goal of the present research in our
laboratory is based on this critical thickness,
D Ic , between rubbery inclusions ("holes"),
by realizing that the smaller "holes", which
do not have to cavitate anymore and conse-
quently do not have an "optimal" (read
"minimum") size, yield the same critical
interparticle distance, Dlc, at much lower
volume fractions of the dispersed phase.
Consequently, in these polymer systems,
called engineering foams (see Fig. 1-59),
the ultimate toughness is realized as much
as possible without degrading the other
mechanical properties, so that the modulus
and yield strength of the material are pre-
served.
The use of reactive solvents provides the
necessary requirements to indeed realize
these microstructures (Jansen 1996;
Chap. 10 of this Volume).
1.5.4 Discussion
In this section it has been shown that,
especially with respect to obtaining the ulti-
mate properties of polymers, specific pro-
cessing routes proved to be of utmost rele-
vance. Basically, the same arguments hold
for other nonstructural properties of poly-
mers, such as those in functional applica-
tions, e.g., optical clarity, light emission, or
intrinsic conductivity. The conjugated poly-
mers developed for these last applications
cannot generally be processed as such, but
elegant processing methods have been
UCSB, California, and later at the Uniax
Company [see Andreatta et al. (1988,
1990), Tokito et al. (1990, 1991), Moulton
and Smith (1992 a, b, 1993),Motamediet al.
(1992), Cao etal. (1992, 1994), Cao and
Smith (1993), Yang et al. (1993), and Wes-
terweele et al. (1995)].
1.6 Extruder Modeling
1.6.1 Introduction
Although both this introductory Chapter
and the rest of this Volume of this Series on
Materials Science and Technology focus on
a coupling of the material to be processed
and the different processing techniques
employed (via, e.g., the study of structure
development during flow, reactive extru-

1.00
0.00
0.01 0.1 1 10
Ceil diameter (pm)
sion, phase separation, and crystallization),
and aim at predicting product properties
(e.g., the short and long term dimensional
stability, modulus, strength, and toughness
of polymeric systems), at least one section
of this introductory chapter should deal with
the aspects of extrusion modeling. The
majority of practical polymer systems expe-
rience an extrusion operation either during
the preparation process, e.g., the final devol-
atilization process following the polymer-
ization reactors or a compounding step, or
during the final shaping process. Extruders
can be defined as viscosity independent drag
pumps with a dramatically low pumping
efficiency. The first part of this definition
reveals why extruders are frequently used in
polymer processing, given the generally
high viscosities that prevail, while the sec-
ond part of this definition elucidates some
of the disadvantages of extruders, although
in plasticating processes most of the heat
generated can be used for melting the solid
feedstock. Nevertheless, the dangers of
unwanted local overheating and the occur-
rence of large temperature gradients always
1.6 Extruder Modeling 65
Figure 1-59. Foam density as
a function of the size of the
dispersed phase ("holes") for
given material-specific critical
(inter-hole) distances (Van der
Sanden, 1993).
100
exist. This is why efficient mixing (homog-
enizing) elements are frequently employed
or why, alternatively, gear pumps are some-
times introduced in the process to pressur-
ize the melt at higher efficiency, thus avoid-
ing too large temperature rises. In this sec-
tion we will briefly review the develop-
ments in plasticating single screw extruders
and in closely intermeshing, self-wiping,
corotating twin screw extruders. These
types of extruders are by far the most fre-
quently used in practical polymer process-
ing.
1.6.2 Single Screws
The theory of single screw extruders is
now well established, and our understand-
ing and modeling of the distinct zones, such
as solids conveying, melting, melt pumping,
and mixing, have finally led to the develop-
ment of a functional screw design, where the
distinct zones are geometrically separated
(see Fig. 1-60).
Despite numerous improvements in the
theory, developed over the years, the origi-
66 1 Processing for Properties
nal first-order models for the feed section
(Darnell and Mol, 1956), the melting section
(Tadmor, 1966), and the metering section
(Anonymous, 1922; Rowell and Finlayson,
1928), are still useful for a general under-
standing. Based thereupon, axially and heli-
cally grooved feed sections have been devel-
oped, especially by the group of Menges at
IKV, Aachen, Germany, during the 1970s
and 1980s. Efficient multichannel melting
sections with a larger (than the "square"
screws which are optimal in the solid con-
veying section) pitch and obtaining complete
phase separation via the addition of an extra
flight, combined with maximum compres-
sion in the solid plug channels and decom-
pression in the melt channels, were devel-
oped in the same period by the group of Ingen
Housz in Twente, The Netherlands, and by
Griinschloss at IKT, Stuttgart, Germany.
These concepts of functional screw design
should be combined with efficient homogen-
izers, e.g., the multichannel Maddock type
mixers, or even better, the CTM (the cavity
transfer mixer), as originally developed by
Barmag, Germany, and later by Rapra, Eng-
land, and improved with respect to its design
in Twente, The Netherlands. For a detailed
treatment, see, e.g., Meijer (1980), Ingen
Housz and Mei-jer (1981 a, b), and Rauwen-
daal (1986), who copied these analyses in his
Figure 1-60. Functional
screw design in plasticating
single screw extruders
showing the feed section
with one channel, the opti-
mal square pitch, and the
three-channel-pair melting
section with three solids
conveying and melt chan-
nels separated by an extra
flight (Meijer, 1980).
book on extrusion, and Verbraak and Meijer
(1989), who tested modern screw design in
the practice of injection molding, including
the CTM (Verheijen, 1988). It is interesting
that these approaches are now gradually
finding their way into practice, not least by
the extra stimulation of the regular VDI
courses on "Single Screw Extruders, Basic
Principles and System Optimization", as
organized by Wortberg [see Wortberg
(1991)]. The simulation code REX, "Rech-
nerunterstiitzte Extrusions Auslegung",
developed by Potente's group in a multi-
sponsored research program, executed in
Paderborn, Germany, summarizes the exist-
ing knowledge on screw design and can be
considered as a simple, but user-friendly,
development tool.
1.6.3 Twin Screws
Apart from the rotating and axially oscil-
lating Buss-cokneader, which introduces a
unique mixing operation, generated by the
relative motion of the pins in the barrel wall
that weave through the screw channel [see,
e.g., Elemans (1989), Elemans and Meijer
(1990), and Elemans (1994)], and which has
found its characteristic applications in, e.g.,
food processing and polymer blending,
especially of temperature-sensitive poly-

mers or reactive systems, the only frequent-
ly used compounding and devolatilization
extruder is the closely intermeshing, self-
wiping, corotating twin screw extruder [see
e.g., White (1990 a) for an extended review].
These types of extruder are based on the
building block principle and their variety is,
consequently, enormous and they can in
principle be designed for many different
tasks. This flexibility in screw design and
barrel choices evokes a large number of
experiments in practice, in order to optimize
the systems under consideration for their
specific task. This fact provided the need for
a comprehensive model, in order to predict
some of the main aspects of the screw per-
formance. Simple models were derived [see,
e.g., Meijer and Elemans (1988), David
et al. (1994), and White (1990 a)]. The basic
outcome of models like these is that they can
predict the lengths of those parts of the
screw that are completely filled, dependent
on the screw design chosen and the operat-
ing conditions, such as metered throughput
and screw speed. Given the large difference
in mechanical energy conversion in the part-
ly filled channels compared with that of
those that are completely filled, useful pre-
dictions are obtained for the critical screw
speeds (below which vent ports overflow),
the average residence time, the power
requirements, the specific energy used, and
as a consequence, the temperature rise of the
melt during extrusion, provided that noniso-
thermal models are used [see, e.g., Meijer
and Elemans (1988)].
As a result, a lot of the usual trial and error
could in principle be avoided. More practi-
cal is the fact that, based upon these insights,
elementary scaling concepts could be
derived. These concepts reveal why in prac-
tice problems are often met if results from
experiments on typical laboratory scale
extruders must be transferred to the large
scale of production plants and vice versa
1.6 Extruder Modeling 67
[see Elemans and Meijer (1994)]. In sum-
mary, the problems encountered stem in all
but the rather rare adiabatic cases from the
problems met in obtaining a similar temper-
ature development in both the small and the
large extruder and, consequently, in obtain-
ing melt temperature control. Given their
difference in surface-to-volume ratio, yield-
ing a different heat exchange with the sur-
roundings, specific scaling laws for equiv-
alent temperature development exist which
basically differ from the scaling laws for
constant mixing, and generally lead to dis-
appointing scaling factors for the attainable
throughput on the larger machines. The dif-
ferent scaling strategies, following from dif-
ferent requirements, clearly elucidate the
problems that can be expected and help
engineers to make proper choices for their
test conditions and plant layout. Of course,
these results are only indicative. Quantita-
tive predictions of the differences to be
expected, and the effects of the different
possible measures that can be adopted to
overcome these problems, at least partly,
can only originate from full nonisothermal
modeling. Improvements in the basic mod-
els must still be strived for [see, e.g., White
(1990a) for a detailed survey].
An interesting consequence of the present
understanding of the working principles of
these kinds of extruders is that the variety
of screw elements available only serves to
change the pumping characteristics, locally,
i.e. the throughput-pressure gradient rela-
tion, and thus helps to control the filled
lengths and the overall residence time. Thus
mixing is only indirectly controlled. This
could have been concluded before, since the
cross section of, e.g., positive or negative
transport elements with different pitch
angles, and positive, negative, and neutral
kneading blocks, etc., is exactly the same
and geometrically predicted by the self-wip-
ing requirements. These requirements can
68 1 Processing for Properties
be combined with the urgent need for min-
iaturization in product development, elimi-
nating this influence of screw design on the
residence time, as occurs in every continu-
ous extrusion operation, by designing a
small, recirculating mixing device.
Attempts to develop such useful devices
were started in the early 1980s at DSM Cen-
tral Laboratories in Geleen by Meijer and
Martens, the last as the chief designer, using
in the first instance a recirculating single
screw extruder without (generation 1) and
with (generation 2) an internal (Sulzer) stat-
ic mixer. Independently, a similar device
was constructed by Macosko's group in
Minnesota. Since these types of extruder
proved to seriously suffer from cleaning dif-
ficulties, it was decided to make use of the
self-cleaning properties of corotating twin
screw extruders. Martens proposed a basic
design of a conical version in order to reduce
the contents and still be able to design a
bearing and thrust system, which was over
Figure 1-61. Mini-mixer, allowing for mixing or dis-
solving 1, 3, or 5g of material (CPC Eindhoven,
1995).
the years improved by Martens and Bulters
at DSM, Geleen (generation 3) and by Meij-
er and Garenfeld at CPC, Eindhoven (gen-
eration 4) (see Fig. 1-61).
A number of prototypes have been build
today, and they are used by different
research groups all over the world and prove
to be successful and efficient, since only (at
choice) 1, 3, or 5 g of material is needed,
while the main characteristics of intensive
mixing and/or dissolution are preserved.
The small material samples from these
devices can, subsequently, be molded into
test plates or bars, or they can be spun direct-
ly into fibers. At DSM, Geleen, Bulters and
Martens even designed a miniature injection
molding device which can be combined with
the mini-mixer, allowing for the production
of a few test bars out of each batch.
1.6.4 Discussion
In the last few decades, a lot of attention
has been paid to the modeling of extrusion
processes, focusing on obtaining a qualita-
tive and quantitative understanding of the
(local) working principles. The theory of sin-
gle screw extruders is relatively well estab-
lished, but suffers from the uncertainties that
naturally occur when the solid bed starts to
be converted into a (initially highly viscous)
liquid by pressure-, friction-, and tempera-
ture-induced melting. Between the pumping
characteristics of the solids conveying zone,
which are based on friction and consequent-
ly yield a wall shear stress that is proportion-
al to the absolute value of the local pressure,
and those of the melt conveying zone, large
differences exist. In the latter the wall shear
stress is only related to the viscosity and to
the local velocity gradient (which is large in
the initial stages of melting given the thin
layers present), and not to the absolute pres-
sure. As a consequence, a consistent model
of the whole extruder screw is generally still

lacking. This is mainly due to the large pres-
sure gradients that can practically be real-
ized just at the end of the solid conveying
section, especially if grooved feed sections
are used, yielding the characteristic and
unique pressure build-up capacity of these
sections. A small misjudgement in the exact
axial position of the solid-to-melt transition
at the barrel wall gives rise to a substantial
change in the pressure gradients and thus to
the pressure build-up capacity, and gives a
large error in the predicted absolute pressure.
Thus the pumping characteristics of the plas-
ticating extruder (as a whole) cannot gener-
ally be predicted well. This basic problem is
unsolved, even in useful computer models
like REX (Rechner unterstiitzte EXtruder
Auslegung) (Wortberg, 1991), which are
currently being improved, e.g., by Potente in
Paderborn. A second, more scientific, prob-
lem is the missing knowledge of the exact
deformation of the solid bed which contains
large temperature gradients and is subjected
to large shear and pressure forces, and might
even break up under tension. This deform-
ability determines the pressure gradient in
the melting section and the melting length
required to a great extent (Meijer, 1980).
This, again, prevents a prediction of the
accurate total pumping characteristics of
plasticating extruders.
The theory of corotating twin screw
extruders and oscillating and reciprocating
single screw extruders with pins through the
barrel wall should be improved by adapting
a full 3D model. In particular in the inter-
meshing section, where one screw takes
over the material from the neighboring
screw, the details of the flow are extremely
important, not only for predicting the local
transport characteristics, and thus the pres-
sure gradients, but more with respect to the
exact folding and stretching that occurs
here, which is of the utmost importance for
efficient mixing. Moreover, these models
1.7 Concluding Remarks 69
should necessarily be nonisothermal, and
sometimes it is important to incorporate the
details of micro-mixing and/or devolatiliza-
tion into the overall analysis.
1.7 Concluding Remarks
In this introductory chapter it has been
demonstrated that polymer processing is an
interesting, broad, and multidisciplinary
area of research. Especially if the focus is
on predicting product properties and not
solely on the description of process param-
eters and the prediction of typical process-
related parameters such as the pressure,
torque, and power requirements, or clamp-
ing forces, the position and number of gates
to control those of weld lines, etc. The rea-
son is that in this case the necessary coupling
with typical material parameters, such as
described by their constitutive behavior, and
with local processes that occur, such as
micro-mixing or (the opposite) phase sep-
aration and coalescence, requires that the
normal methods of the researchers in this
area (advanced 3 D, nonisothermal, non-
Newtonian, transient, mathematical mod-
els) have to be extended to those of the poly-
mer physicists (theoretical and practical
rheology and rheometry, composition and
prediction of phase diagrams, inclusion of
the kinetics in the local processes), yielding
interesting challenges for coupling the mac-
roscopic flow field with the microscopic
processes. The basic reason for this is that
in polymer technology neither the chemis-
try, nor the production technology, nor the
final design solely determine the product
properties. The whole trajectory from poly-
mer synthesis, via polymer physics, poly-
mer processing, and design proves to be rel-
evant, and each discipline has its own input
in the final result. A newly synthesized poly-
mer that cannot be processed will find lim-
70 1 Processing for Properties
ited applications. More important, howev-
er, is that during processing most of the final
material properties can often be obtained, or
the materials themselves can be polymer-
ized, given the large flexibility of the inter-
mediate fluid state of matter that is often
present at intermediate temperatures during
processing. Besides, the two basic types of
bond present in polymers, with their strong
intramolecular covalent bonds in the main
chain and weak secondary intermolecular
bonds in between the chains, make these
materials unique, not only during process-
ing (the physical network of chains provides
the melt strength necessary for drawing,
spinning, blowing, or vacuum forming oper-
ations), but also in their final applications.
The ultimate properties of polymers in terms
of modulus, strength, and impact resistance
are often uniquely obtained via specific pro-
cessing routes and clearly illustrate this par-
ticular behavior and the opportunities that
polymers provide. Basically, nature is built
up from polymers. Only, nature uses much
more advanced synthesis routes, is mainly
based on hydrogen bonding, and makes
maximum use of the self-organizing pos-
sibilities of macromolecules.
In the successive chapters of this Volume,
the details of the different aspects of process-
ing for properties, as introduced in this
Chapter, are elucidated in more detail. The
Volume basically consists of four distinct
parts: 1) Introduction, 2) Structure Develop-
ment during Flow, 3) Reactive Processing,
and 4) Applications. Of course, many limi-
tations were necessary during the composi-
tion of this Volume, but the contents cover
the total area of interest to a great extent.
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H. E. H. (1994b), Polymer 35, 2995.
Van Nieuwkoop, J., Muller von Czernicki, M. M. O.
(1997), /. Non-Newtonian Fluid Metch., in press.
Venderbosch, R. W. (1995), Ph. D. Thesis, Eind-
hoven.
Venderbosch, R. W., Meijer, H. E. H., Lemstra, P. J.
(1994), Polymer 35, 4349.
Venderbosch, R. W., Meijer, H. E. H., Lemstra, P. J.
(1995a), Polymer 36, 1167.
Venderbosch, R. W., Meijer, H. E. H.,. Lemstra, P. J.
(1995 b), Polymer 36, 2903.
Verbraak, C. P. J. M., Meijer, H. E. H. (1989), Polym.
Eng. ScL 29 (7), 479.
Verheijen, J. (1988), DSM Research Report, NC
88.12566, Geleen (in Dutch).
Vinogradov, G. V., Fikman, V. D., Radushkevich,
B. V, Malkin, A. Y. (1970), /. Polym. ScL A-2 (8),
657.
Vleeshouwers, S., Meijer, H. E. H. (1996), Rheol.
Ada, 35, 391.
von Wrobleski (1879), Wied. Ann. Phys. 8, 29.
Vos, E., Meijer, H. E. H., Peters, G. W. M. (1991), Int.
Polym. Proc. 6, 42.
Vosbeek, P. H. J. (1994), Ph. D. Thesis, Eindhoven.
Vosbeek, P. H. J., Schreurs, P. J. G., Meijer, H. E. H.
(1997), unpublished.
Wagner, M. H. (1994), Rheol. Ada 33, 506.
Wagner, M. H. (1996), Polym. Eng. ScL 36, 925.
Walters, K. (1992), in: Proc. XI Int. Cong, on Rheol-
ogy, Theoretical and Applied Rheology: P. Mol-
denaers, R. Kennings (Eds.). Amsterdam: Elsevier.
Westerweele, E., Smith, P., Heeger, A. J. (1995), Adv.
Mater. 7, 788.
White, J. L. (1990 a), Twin Screw Extrusion, Technol-
ogy and Principles. Munich: Hanser.
White, J. L. (1990 b), Principles of Polymer Engineer-
ing Rheology. New York: Wiley.
Wimberger Friedl, R. (1991), Ph. D. Thesis, Eind-
hoven.

Wortberg, J. (1991), Einschneckenextruder, Grund-
lagen und Systemoptimierung, Diisseldorf: VDI-
Gesellschaft Kunststofftechnik.
Yanase, H., Moldenaers, P., Mewis, J., Abetz, V., van
Egmond, J., Fuller, G. G. (1991), Rheol. Acta 30, 89.
Yang, C. Y, Cao, Y, Smith, P., Heeger, A. J. (1993),
Synth. Met. 53, 293.
Ziabicki, A. (1976), Fundamentals of Fibre Forma-
tion. New York: Wiley.
Zoetelief, W. F. (1995), Ph. D. Thesis, Eindhoven.
Zoetelief, W. R, Douven, L. F. A., Ingen Housz, A. J.
(1996), Polym. Eng. Sci., in press.
Zwijnenburg, A., Pennings, A. J. (1975), Colloid
Polym. Sci. 452, 253.
General Reading
Agassant, J. F. (1991), Polymer Processing, Prin-
ciples and Modeling. Munich: Hanser.
Astarita, G., Marrucci, G. (1974), Principles of Non-
Newtonian Fluid Mechanics. New York: McGraw-
Hill.
Bird, R. B., Stewart, W. E., Lightfoot, E. N. (1960),
Transport Phenomena. New York: Wiley.
Bird, R. B., Curtiss, C. R, Armstrong, R. C , Hassa-
ger, O. (1987), Dynamics of Polymer Liquids, Vol.
1: Fluid Mechanics; Vol. 2: Kinetic Theory. New
York: Wiley.
Crochet, M. J., Davies, A. R., Walters, K. (1984),
Numerical Simulation of Non-Newtonian Flow.
Amsterdam: Elsevier.
Fenner, R. T. (1979), Principles of Polymer Proces-
sing. London: Macmillan.
Ferry, J. D. (1980), Viscoelastic Properties of Poly-
mers, 3rd ed. New York: Wiley.
1.8 References 75
Isayev, A. I. (Ed.) (1987), Injection and Compression
Molding Fundamentals. New York: Marcel Dekker.
Isayev, A. I. (Ed.) (1990), Progress in Polymer Pro-
cessing. Munich: Hanser.
Janeschitz-Kriegl, H. (1983), Polymer MeltRheology
and Flow Birefringence. Berlin: Springer.
Joseph, D. D. (1990), Fluid Dynamics of Viscoelastic
Liquids. New York: Springer.
Larson, R. G. (1988), Constitutive Equations for Poly-
mer Melts and Solutions. Boston, MA: Butter-
worths.
Macosko, C. W. (1994), Rheology, Principles,
Measurements and Applications. Weinheim: VCH.
Middleman, S. (1977), Fundamentals of Polymer
Processing. New York: McGraw-Hill.
Pearson, J. R. A. (1985), Mechanical Principles of
Polymer Melt Processing. London: Elsevier.
Pearson, J. R. A., Richardson, S. M. (Eds.) (1983),
Computational Analysis of Polymer Processing.
London: Applied Science.
Rauwendaal, C. (1986), Polymer Extrusion. Munich:
Hanser.
Schowalter, W. R. (1978), Mechanics of Non-New-
tonian Fluids. Oxford: Pergamon.
Tadmor, Z., Gogos, C. E. (1979), Principles of Poly-
mer Processing. New York: Wiley.
Thomson, R..D., Wood, O. C , Zienkiewicz, A. (Eds.)
(1989), Numerical Methods in Industrial Forming
Processes. Rotterdam: Balkema.
Tucker III, C. L. (Ed.) (1989), Fundamentals of Com-
puter Modeling for Polymer Processing. Munich:
Hanser.
White, J. L. (1990), Twin Screw Extrusion, Technol-
ogy and Principles. Munich: Hanser.
White, J. L. (1990), Principles of Polymer Engineer-
ing Rheology. New York: Wiley.
Ziabicki, A. (1976), Fundamentals of Fiber Forma-
tion. New York: Wiley.
2 General Principles of Polymer Processing Modeling
Jean-Francois Agassant

Centre de Mise en Forme des Materiaux, URA CNRS n 1374, Ecoledes Mines de Paris,
Sophia Antipolis, France

List of Symbols and Abbreviations 78

2.1 Introduction 80
2.2 Physical Peculiarities of Polymers and the Consequences for Processing 80
2.2.1 The Highly Viscous Nature of Molten Polymers 80
2.2.2 The Non-Newtonian Nature of Molten Polymers 80
2.2.3 The Highly Temperature Dependent Viscosity of Molten Polymers 81
2.2.4 The Low Thermal Diffusivity and Conductivity of Polymers 82
2.3 Polymer Forming Processes 82
2.3.1 Extrusion 82
2.3.2 Injection Molding 85
2.3.3 Stretching Processes 86
2.4 Governing Equations and Simplification Methods 88
2.4.1 Introduction 88
2.4.2 Governing Equations 88
2.4.3 The Simplifying Assumptions 89
2A3.1 Rheological Assumptions 89
2.4.3.2 Boundary Conditions 90
2.4.3.3 Geometrical Simplifications 91
2.4.3.4 Flow Kinematics Assumptions 91
2.4.3.5 Energy Balance Assumptions 93
2.4.4 Preliminary Conclusions 94
2.5 Examples of Polymer Flow Computations 94
2.5.1 Coat Hanger Flat Die Geometry 94
2.5.2 Tube Die Geometry 96
2.5.3 Profile Die Geometry .. 100
2.5.4 Injection Molding 102
2.5.5 Fiber Spinning 105
2.6 Conclusions and Perspectives 108
2.7 References 108

Materials Science and Technology

Copyright WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
78 2 General Principles of Polymer Processing Modeling

List of Symbols and Abbreviations

a material parameter; thermal diffusivity

A dimensionless variable
Br Brinkman number
Ca Cameron number
C
P
heat capacity
Cf, C\ constants
De Deborah number
DY draw ratio
E activation energy
F force
h flow gap
I identity tensor
k thermal conductivity
K consistency index
I length
L channel length
n power law index; normal to the wall
n vector normal to the border
Nu Nusselt number
P isotropic pressure; coefficient
pressure field
P isotropic part of the stress tensor
Q volumetric flow rate
R ideal gas constant; radius
r
e inner radius of die
?i radius of mandrel
r* location of maximum velocity within flow gap
S cross-section
So initial cross-section
T temperature
T
z glass transition temperature
Ti initial temperature
Tr controlled temperature of machinery
wall controlled temperature
To reference temperature
T mean temperature approximation
u velocity
u* velocity
U, V, W velocity components
U, V mean velocity components
V mean flow velocity; dimensionless variable
Vs slip velocity
w0 initial velocity
 List of Symbols and Abbreviations 79

x, y> z directions
7 height
z* location of maximum velocity

a coefficient; fill factor

7 shear
T shear rate
7 second invariant of rate of strain tensor; generalized shear rate
r border of the control volume
8 rate of strain tensor
ri viscosity
viscosity at reference temperature
9 constant relaxation time
X material parameter; heat transfer coefficient
nondimensional variable
P density
a stress tensor
a: 8 viscous dissipation
X extra stress tensor
Tw shear stress at wall
nondimensional variable
Q control volume area

CAD computer assisted design

PVC polyvinyl chloride
W.L.F. William-Landel-Ferry
80 2 General Principles of Polymer Processing Modeling
2.1 Introduction
This chapter deals with thermoplastic
polymers. The processing of thermosets is
generally achieved with very different tech-
niques and will not be described here. On
the other hand, elastomer compounds are
processed on the same type of machines as
thermoplastic polymers (extruders, injec-
tion molding machines, calenders, etc.), but
additional cross-linking reactions have to be
taken into account.
Most thermoplastic polymers are pro-
cessed in the following way: additives (sta-
bilizers, lubricants, plasticizers, processing
aids, etc.) are mixed with the raw polymer
to obtain a compound (powder or pellets).
This compound is then melted (semi-
crystalline polymer) or plasticized (amor-
phous polymer) by thermal conduction and
viscous dissipation. The highly viscous melt
is then forced through a die or in a mold to
obtain a preliminary shape. Finally, the mol-
ten polymer is cooled down (injection mold-
ing), sometimes simultaneously stretched
(fiber spinning, film blowing) to obtain the
final solid product. Its properties will not
only depend on the chemical species (mac-
romolecule, molecular weight distribution,
additives, etc.), but also on the thermome-
chanical parameters they have encountered
during the process.
Therefore at first glance, polymer pro-
cessing appears to be a classical problem of
fluid mechanics and heat transfer. How-
ever, some of the peculiarities of polymers,
both in the molten and the solid state, need
specific approaches, which will be high-
lighted in Sec. 2.2. This will allow us to
understand the main thermoplastic polymer
processes which will be described in
Sec. 2.3. Polymer processing modeling
requires us to solve, generally speaking, a
set of eleven equations with eleven
unknowns. Simplifying assumptions often
make it possible to obtain problems of
reduced complexity. These will be present-
ed in Sec. 2.4. Finally, the modeling of cur-
rent thermoplastic polymer processes, e.g.,
extrusion, injection molding, or fiber spin-
ning, will be summarized (Sec. 2.5).
2.2 Physical Peculiarities of
Polymers and the Consequences
for Processing
2.2.1 The Highly Viscous Nature
of Molten Polymers
The viscosity of a molten polymer in clas-
sical processing conditions is in the range
10 2 -10 4 Pas. The consequences for the
process are important:
1) The Reynolds number is low and, conse-
quently, molten polymer flows can never
be turbulent. Moreover, inertia terms can
be neglected in most engineering situa-
tions. This may not be true, for example
for high speed fiber spinning.
2) Mass forces are also generally negligible,
especially in horizontal processes.
3) Viscous dissipation is very important
(between K)6 and 108W/m3) and the
temperature of the molten polymer may
increase, even if the temperature of the
equipment is controlled.
4) High torques and pressures are encoun-
tered in most polymer processing
machines which necessitates powerful
motors, highly resistant equipment, as
well as high clamping forces in injection
molding.
2.2.2 The Non-Newtonian Nature
of Molten Polymers
At a low rate of deformation, the viscos-
ity remains constant, which means that the
 2.2 Physical Peculiarities of Polymers and the Consequences for Processing
entanglement density between macromole-
cules is constant too. At higher shear rates
(especially in the range of shear rates
encountered in most polymer processes),
macromolecules are progressively disen-
tangled and the viscosity (77) decreases sig-
nificantly. Several equations have been pro-
posed to account for this shear thinning
behavior. The most popular is the power law
(also called Ostwald-De Waele)
r\=Kyn~x (2-1)
where K is the consistency index, 7 is the
shear rate, and n the power law index.
This equation allows the development
of analytical computations for several
simple flow situations, but gives an infinite
viscosity at a vanishing shear rate. The
Carreau-Yasuda equation (Yasuda et al.,
1981) makes it possible to account simulta-
neously for a Newtonian plateau (r/0) at a
low shear rate and for a large viscosity
decrease at higher rates
77 ?7o [1+ {X y) ] (2-2) polymers (at T>Tg+ 100 C, where Tg is
where X and a are material parameters.
The high entanglement density encoun-
tered in molten polymers leads to important
viscoelastic phenomena, for example: stress
overshoot and stress relaxation in step
shearing flows, strain hardening of the elon-
gational viscosity, and important swelling at
the die exit. The fundamentals of entangle-
ment and its effects on rheology are dis-
cussed by Doi (Chap. 9, Vol. 12 of this
Series).
Rheological equations accounting for
these phenomena are numerous. Pertinent
reviews have been presented recently by
Tanner (1985) and Larson (1988). Integral
constitutive equations are the most intuitive
ones but lead to numerical difficulties in
nontrivial flow geometries [see Kiriakidis
etal. (1983)]. Differential constitutive
equations are now common practice
81
(Beraudo, 1995), but even the simplest
Maxwell model leads to nonlinear and non-
explicit equations.
a = -p'I + % (2-3 a)
(2-3 b)
where 6 is a constant relaxation time, 8x/8?
is the upper convected derivative of the
extra stress tensor T, is the rate of strain
tensor, I is the identity tensor, and// the iso-
tropic part of the stress tensor a. At present
Johnson-Segalman (Johnson and Segal-
man, 1977) or Phan-Thien-Tanner (Phan-
Thien and Tanner, 1977) equations are the
most popular.
2.2.3 The Highly Temperature
Dependent Viscosity of Molten Polymers
Increasing the polymer temperature leads
to a significant decrease in the viscosity. For
semi-crystalline polymers or for amorphous
the glass transition temperature) an Arrhen-
ius law is proposed to account for the change
in viscosity with temperature
(2-4)
R[T
where E is the activation energy, which is
very different from one polymer to another,
R is the ideal gas constant, and 7]0 is the vis-
cosity at the reference temperature TQ.
For amorphous polymers [between Tg
and (r g + 100 C)] the W.L.F. equation is
used (Williams-Landel-Ferry) (Williams et
al., 1955)
-Cf{T-Tg)
(2-5)
Cf and Cf are two constants varying with
the polymer.
82 2 General Principles of Polymer Processing Modeling
In either case, the temperature depen-
dence of the viscosity means that the
mechanical and the thermal equations have
to be solved simultaneously.
2.2.4 The Low Thermal Diffusivity
and Conductivity of Polymers
Polymers are well known as thermal insu-
lators. Typically, their thermal conductivity
k and diffusivity a are a hundred times lower
than those of steel. The obvious conse-
quence of this is that polymer parts are gen-
erally thin (less than 5 mm) in order to
obtain a reasonable cooling time. In the
same way, polymer plastication needs thin
layers, both for heat transfer and for high
viscous dissipation.
Another consequence is the high value of
the Brinkman number Br which balances
viscous dissipation and heat conduction
(Brinkman, 1951)
2
nl/
(2-6)
k(T-Tw)
where Vis the mean flow velocity and Tw is
the wall controlled temperature. In most
polymer processes, the Brinkman number
may be higher than 10, which means that the
temperature of the molten polymer cannot
generally be controlled by the regulation
temperature of the equipment.
As a last consequence, high transverse
temperature gradients may be induced, even
in thin flow geometries, because the local-
ized dissipated energy (where the rates of
strain are high) cannot be balanced by heat
transfer to the equipment.
All these physical peculiarities of poly-
mers will affect the different polymer pro-
cesses and explain the main features of poly-
mer processing modeling.
2.3 Polymer Forming Processes
Only the main thermoplastic polymer
processes will be described here.
2.3.1 Extrusion
Extruders (single screw or twin screw) are
commonly used to produce pellets as well
as to manufacture tubes, profiles, films, and
sheets, and to coat wires.
The geometry of a single screw extruder
is constituted of a hopper which is used to
feed the system with pellets (or sometimes
with powder), a heated barrel (in fact suc-
cessive zones with different controlled tem-
peratures may be observed along the barrel),
and a rotating screw whose core geometry
generally increases from the hopper to the
die (Fig. 2-1). Three different mechanisms
may be observed along the single screw
extruder:
1) The solid polymer coming from the hop-
per is progressively compacted and
simultaneously conveyed due to friction
mechanisms along screw and barrel
(Archimedes's screw principle). In the
feeding zone, the diameter of the screw
generally remains constant.
2) When the solid polymer enters the zone
where the barrel is heated (above the
glass transition or the plastication tem-
perature), a thin layer is melted along the
barrel. As long as the liquid layer remains
thinner than the leakage between the
screw flight and the barrel, it is not con-
veyed forwards. But as soon as this liq-
uid layer becomes thicker than the leak-
age, the liquid is pressurized along the
rear flight, inducing deformation of the
solid compacted polymer and the initia-
tion of a liquid pool along the rear flight.
This liquid pool will push the remaining
solid bed towards the front flight an the
 2.3 Polymer Forming Processes 83

Figure 2-1. Schematic dia-

gram of a single screw
extruder.
Feed zone Molten polymer

heated barrel. The liquid film at the solid

polymer/barrel interface develops both
by thermal conduction and viscous dissi-
pation. The liquid pool then progressive-
ly increases and the solid bed simultane-
ously disappears. This "rear flight
corotating counterrotating
plastication phenomenon" has been
described and modeled by Tadmor and Figure 2-2. Corotating or counterrotating twin screw
extruder motion.
Klein (1970). Other types of plastication
mechanism have been described by Lindt
(1976). In this plastication zone, the
ly splits the liquid pool along the rear main
diameter of the core of the screw gener-
flight and the solid bed along the front
ally increases.
main flight (Maillefer, 1959).
3) In the last zone of the extruder, the screw
Splitting of the conveying and plastication
acts like a pump on the highly viscous
functions on the one side and of the meter-
polymer in order to obtain a high and reg-
ing function on the other side using a two-
ular flow rate in the die. This is achieved
stage single screw with intermediate vent-
by adjusting the geometry of the die and
ing.
the geometry of the metering zone.
In an intermeshing twin screw extruder
Figure 2-1 presents a schematic view of
(corotating or counterrotating - see Fig.
a single screw extruder. A good understand-
2-2), the conveying mechanism is provided
ing of the physical phenomena occurring in
by the interpenetration of the two screws in
the machine has led to significant technical
an eight-shaped barrel. This allows it, in par-
developments during the last few decades:
ticular, to convey powder. The core of the
A cooled and grooved barrel in the feed- screws is generally of constant diameter, but
ing zone in order to increase the friction the screw elements (direct flight, reverse
coefficient between the solid polymer and flight, mixing geometries) may be adjusted
the barrel and thus to also increase the feed leading to quite an infinite number of geom-
rate significantly. etries. The plastication mechanism is not
The introduction of an additional flight in very well understood at present, and the
the plastication zone, which progressive- metering mechanism is generally different
(a) distribution channel (c) 00

CD
to

Wire
guider

3
CO

o
o
CD
(Si
CO

o
Q.
CD_
5'
CQ

Figure 2-3. (a) Coat

hanger die geometry.
(b) tube die geometry,
(c) wire coating die
geometry, and (d) pro-
file die geometry of
extrusion dies.
 2.3 Polymer Forming Processes 85

from the one encountered in a single screw 2.3.2 Injection Molding

extruder in the sense that the twin screw
extruder is not filled everywhere, which Injection molding is used to produce parts
allows the screw rotation speed and the flow of complex geometry in one single opera-
rate to be varied independently. tion. This is a cyclic process and its main
Extrusion dies are adjusted to a single or steps are shown in Fig. 2-4:
a twin screw extruder. Several geometries 1) First the polymer is melted in a plasticat-
are presented in Fig. 2-3: ing single screw geometry similar to the
one described in Sec. 2.3.1. During the
(a) In a coat hanger die, the molten polymer rotation stage, the screw goes backwards
is distributed in a manifold of decreas- and the molten polymer is accumulated
ing cross section before entering a nar- in front of the screw.
row slit. A straining bar and a relaxation 2) Second, the polymer is injected at high
channel make a more uniform polymer velocity in a mold which is temperature
distribution possible in the lips. Obvi- controlled (generally around ambient).
ously, the construction of the die must be During this filling stage, the pressure is
such that the extruded polymer plaque, very important due to the high viscosity
sheet, or film is of constant thickness and and also due to the fast injection rates;
uniform temperature (Fig. 2-3 a). this necessitates very high clamping
(b) In a tube die (Fig. 2-3 b), the molten forces for the mold.
polymer is distributed around a mandrel 3) During the cooling stage, additional
that is attached to the die by spider legs. polymer is fed into the mold in order to
The design must be such that uniform balance the variation of the specific vol-
tube thickness is achieved. For film
blowing, more complex tube die geom-
etries are used.
(c) In a wire coating die (Fig. 2-3 c), the wire
is fed by a guider perpendicular to the
extruder. The polymer is distributed
around the guider using a distribution Ptasticatiorr. The screw backs up
while rotating
channel, and then flows between the
wire and the axisymmetric part of the
die. The major problems encountered
are eccentricity of the wire with respect
to the insulation and rupture of the wire
due to the large forces exerted by the
polymer on the wire (especially tele-
phone wires a few millimeters in diam-
eter).
(d) In a profile die (Fig. 2-3 d), the polymer
is progressively fed from the cylindrical
The screw is at rest
geometry of the barrel to the complex
profile geometry. The objective is to Ejection of object
from the moid
obtain a uniform velocity field at the die
exit with the required shape. Figure 2-4. Injection molding cycle.
86 2 General Principles of Polymer Processing Modeling
ume of the polymer due to the tempera-
ture and pressure decrease. This is called
the packing phenomenon.
4) Finally, the solid part is ejected, and cool-
ing is achieved outside the mold.
The main problems encountered in injec-
tion molding are as follows:
Optimizing the mold filling by adjusting
the channels, gates, and runners in order
to obtain a balanced filling in the shortest
period of time with a controlled tempera-
ture.
Optimizing processing parameters (dur-
ing the filling and the packing stages) in
order to control the weight of the part as
well as its final shape (warping phenom-
ena linked to the residual stress distribu-
tion may be observed).
2.3.3 Stretching Processes
Fiber spinning represents a great variety
of processes: molten polymer spinning or
solution spinning, cooling in air over a long
distance or stretching in air over a short dis-
tance and then cooling in water, high or low
draw ratio, etc. Figure 2-5 represents the
high speed spinning process for polyamide
or polyester fibers: the molten polymer
flowing from the extruder is filtered through
a "spinning pack" and then distributed on a
plaque with several hundred holes, the
diameters of which are less than one milli-
meter. The polymer filaments emerging
from these holes are stretched over a long
distance (one meter or more) and simulta-
neously cooled by forced convection. Sev-
eral filaments are assembled as a fiber which
is wound up. The main objective is to obtain
very thin filaments (final diameter around
10 (Lim) at a high speed and without instabil-
ities.
Polymer films are obtained with two dif-
ferent techniques:
1) In the cast-film process, the film is
stretched over a short distance between
the coat hanger die exit and a chill roll.
The thickness and also the die width of
the film decrease and overthickness
defects (generally called "dogbone
defects") appear on each side of the film,
which necessitates cutting the two bor-
ders of the film (Fig. 2-6).
2) In the film blowing process, a tube of
molten polymer is simultaneously inflat-
ed under pressurized air and stretched
with the help of rollers (Fig. 2-7). Cool-
ing is generally achieved by the forced
convection of air through an air ring sit-
uated above the die. New film blowing
systems include internal air cooling.
Once the film is solidified, its shape does
not change: it is then pulled, folded, and
wound on cylindrical cores. The main
problems are the thickness regularity
along the perimeter as well as the bubble
stability.
Blow molding is used to produce bottles,
containers, and tanks. Two main processes
are encountered:
1) In extrusion blow molding, an extruded
tube is punched at the die exit in the mold
geometry. Blowing air inflates the mol-
ten parison along the cold mold walls; the
solidified part is then extracted.
2) In injection blow molding, parisons are
first injected, then reheated, and finally
simultaneously inflated and stretched
with pressurized air and a moving rod.
This second blow molding process
makes it possible to achieve a better
thickness distribution, as well as
enhanced mechanical properties (due to
biaxial stretching) (Fig. 2-8).
In all these forming processes, complex
geometries, rich flow kinematics, as well as
high thermal coupling are encountered.
 2.3 Polymer Forming Processes 87

_i m L J

ii
\ Q hopper

(2) extruder

\L V (|)

(\
spinning pack

air blowing

Q winding system

Figure 2-5. High speed spinning line.

Figure 2-6. Diagram of the cast film process. Figure 2-7. Diagram of the film blowing process.
88 2 General Principles of Polymer Processing Modeling
the preform the preform preform
is heated in is transferred biaxial
an infrared into the mold stretching
oven
Figure 2-8. Diagram of the injection blow molding
process.
Governing equations as well as approxima-
tion methods are presented in the next sec-
tion.
2.4 Governing Equations
and Simplification Methods
2.4.1 Introduction
The main objective of polymer convert-
ers is to obtain satisfactory products at a
competitive price. A satisfactory product
means achieving certain overall dimensions
as well as a nice surface aspect. It also
requires satisfactory properties, which
means a specific molecular orientation, a
minimum of residual stresses, or a specific
crystalline structure. A competitive price
means that the process rapidly attains steady
state conditions with a minimum of waste
and a maximum output in extrusion, or a
minimum cycle time in injection or blow
molding.
Polymer processing modeling is a useful
tool to achieve these objectives. Computer
assisted design (CAD) of die or mold geom-
etries is now common practice. It is never-
theless very important to keep in mind that
these numerical models have to be based on
an accurate physical description of the phe-
nomena encountered in the process: how
can we model single screw extrusion with-
out understanding the so-called "rear flight
plastication mechanism"? Also, that these
models need a lot of physical data (viscos-
ity, elasticity, heat capacity, and also density
and macromolecular orientation, etc.).
Some of these data are very difficult to
measure at present.
2.4.2 Governing Equations
A set of eleven equations must be solved
in the general case:
(i) Mass balance (one equation)
dp
(2-7)
dt
where p is the density and u is the velocity
field. The polymer may generally be con-
sidered as incompressible, which leads to
div u = 0 (2-8)
(ii) Momentum balance (three equations)
diva + F - p 7 = 0 (2-9)
As pointed out in Sec. 2.2.1, mass forces
(F) as well as inertia forces (pf) may, in
general, be neglected, which leads to
div a = (2-10)
(iii) Energy balance (one equation) - sever-
al energy balance equations are available; if
no phase transformation is considered dur-
ing the process, it may be written as
grad T) + a: (2-11)
where cp is the heat capacity, k the heat con-
ductivity, and G: 8 is the viscous dissipation,
which is the most important parameter in
most polymer processes, as pointed out in
Sees. 2.2.1 and 2.2.4.
 2.4 Governing Equations and Simplification Methods
(iv) Constitutive equations (six equations)
- a broad number of constitutive equations
are available and one of the most difficult
problems is to select a "reasonable" constit-
utive equation. This problem will be
addressed in Sec. 2.4.3.
The Newtonian constitutive equation can
only provide a crude approximation to
most processes
a = - p I + 2 7]E (2-12)
where p is the isotropic pressure and I the
identity tensor.
The generalized Newtonian constitutive
equation is often used
o = -pI + 2 r\(T, j)e (2-13)
The viscosity (77) may follow a power law
[Eq. (2-1)] or a Carreau-Yasuda law [Eq.
(2-2)] with the temperature dependance
obeying Arrhenius [Eq. (2-4)] or W.L.F.
[Eq. (2-5)] laws, ^is the second invariant of
the rate of strain tensor.
Differential as well as integral constitu-
tive viscoelastic equations are available.
The Maxwell constitutive equation has
been presented before [Eq. (2-3)].
The more general shape of the constitu-
tive equation may be written
/(T,e) = 0 (2-14)
The unknowns to be determined are the
three components of the velocity u, the five
components of the extra stress tensor T, the
hydrostatic pressure p (or the isotropic part
of the stress tensor p in the viscoelastic
case), the temperature T, and the density p.
This general problem with eleven equa-
tions and eleven unknowns remains difficult
to solve, especially for the complex process-
ing geometries described in Sec. 2.3. Sim-
plifying assumptions may be used in order
to obtain appropriate, but accurate, solu-
tions with reasonable computing costs.
89
2.4.3 The Simplifying Assumptions
Assumptions may be introduced for the
constitutive equation, the boundary condi-
tions, the geometry, the flow kinematics,
and the energy equation. The relative impor-
tance of each assumption has to be careful-
ly weighed (Agassant et al., 1993).
2.4.3.1 Rheological Assumptions
Before introducing a sophisticated con-
stitutive equation in a model, it is important
to know if it is necessary for the purpose of
the computation and if the corresponding
rheological parameters may be measured: it
is now common practice to measure the
complex modulus as a function of the fre-
quency (small deformations) or the shear
viscosity as a function of the shear rate
(large deformations). The Cox and Merz
rule (Cox and Merz, 1958) makes it possible
to superimpose these two kinds of shear
measurement for simple molten polymer
systems. This is no longer true for polymer
blends, reinforced polymers, and even PVC
formulations. It is more difficult to measure
elastic parameters, e.g., the first normal
stress difference and relaxation times; this
may only be achieved over a narrow range
of deformation rates. Measuring the elonga-
tional viscosity (in uniaxial or biaxial
stretching), the second normal stress differ-
ence, and the rheology of fiber-reinforced
polymers in relation to filler orientation
(Ausias et al., 1992) is, even now, a difficult
task. Nowadays computation facilities
make it possible to directly fit the rheolog-
ical parameters to complex but well instru-
mented experiments.
It is then interesting to know what kind of
flow situations will be encountered in the
process:
(i) In simple shear flows, or in nearly shear-
ing flow situations (as indicated in Sec. 2.5,
90 2 General Principles of Polymer Processing Modeling
nearly shearing flow situations will be
encountered in a wide range of die flow or
injection molding problems), elasticity will
mainly affect the extra stress components,
and to a lesser extent, the velocity field (i.e.,
the flow rate) and the stress normal to the
wall (which is generally called the pres-
sure). On the other hand, both the velocity
field and the pressure will be strongly
dependent on the shear viscosity. As a con-
sequence, a precise viscous constitutive
equation has to be used in order to predict
accurate pressure-flow rate relationships,
(ii) In elongational flows (or in nearly elon-
gational flows such as fiber spinning, film
blowing, and blow molding), the elonga-
tional viscosity is a key parameter and is
strongly dependent on the elasticity. For
example, if we consider the elongation of a
filament at a constant rate of strain [see
Denn and Marrucci (1971)], a Newtonian
behavior will result in a constant elonga-
tional stress (Trouton experiment), whereas
even the simplest viscoelastic Maxwell
behavior will lead to an elongational stress
increasing with both time and elongation
rate. This is qualitatively in agreement
with the experimental results observed for
molten polymers. As a consequence, viscoe-
lastic constitutive equations have to be con-
sidered to account for elongational process-
es.
(iii) A large number of confined flow geom-
etries encountered in die flows or in injec-
tion molding involve mixed flows with both
shear and elongation deformations. Two
nondimensional numbers have to be consid-
ered:
1) The Deborah number compares the char-
acteristic relaxation time of the polymer
(the mean relaxation time, for example)
with the mean residence time.
2) The Weissenberg number compares the
first normal stress difference to the shear
stress (for example, the ratio of the max-
imum first normal stress difference to the
maximum shear rate).
If these numbers are lower than one, a
purely viscous model will give a reason-
able approximation of the problem. If
not, viscoelastic computations have to
be introduced, but this may lead to
numerical difficulties if stress singular-
ities are encountered in the flow [see
Keunings (1989)], and to high computa-
tion times.
Finally, it is important to clearly identi-
fy the problem to be solved: if only
pressure-flow rate relationships have to be
established, a precise, purely viscous
description of the polymer is often suffi-
cient. On the other hand, stress distributions,
die swell prediction, macromolecule orien-
tation, and fiber orientation require sophis-
ticated viscoelastic equations.
2.4.3.2 Boundary Conditions
Only confined flow boundary conditions
will be considered here, both for the veloc-
ity and for the heat transfer.
Velocity
Generally, at reasonable flow rates, a stick-
ing contact is taken into account at the wall
(zero velocity). At very high flow rates, flow
instabilities are often observed, which may
be linked to stick-slip phenomena at the wall.
These phenomena will not be considered
hereafter. For PVC compounds as well as for
elastomer compounds, slip boundary condi-
tions may be observed, even at low flow
rates. This necessitates the determination of
a "slip constitutive equation". A power law
is often used (Mourniac et al., 1992)
T r/K Vp (9-1^
where Tw is the shear stress at the wall, Vs is
the slip velocity, and a and p are two coef-
 2.4 Governing Equations and Simplification Methods 91

ficients which may be determined experi-
mentally using capillary rheometry with dif-
ferent die diameters [see Mooney (1931)].
Heat Transfer
The simplest but crude approximation
consists of assuming a constant and fixed
temperature at the machinery wall (Tw). A
more realistic boundary condition consists
of defining a heat transfer coefficient X
between the molten polymer and the
machinery
(i) In several confined polymer forming pro-
cesses, the polymer flows as a thin layer, so
that this flow is either one-directional or
two-directional. This is, for example, the
case for the geometries encountered in a
coat hanger die (Fig. 2-3 a), in the cross head
of a wire coating die (Fig. 2-3 c), or in many
injection molds.
If we consider the flow of a Newtonian
fluid [Eq. (2-12)] in a 3 D geometry (Fig.
2-9), Eqs. (2-8) and (2-10) will lead to the
well-known stokes equations

dT d2u d2u d2u

k (2-16) (2-17 a)
dn wall dx2 dy2 dz2

where Tr is the controlled temperature of 1

V
-\2
O V
^2
O V
the machinery and n is the normal to the 2 2
(2-17 b)
dx dy dz2
wall.
w d2 w dw
2 (2-l7c)
dx dy
2.4.3.3 Geometrical Simplifications
It is often useful to unroll a three- (2-l7d)
dy dz
dimensional geometry to obtain a planar
one. This is common practice for describing The lubrication approximation [see
the flow in the channel of an extruder [see Streeter [1961)] may be introduced if the
Tadmor and Klein (1970)], but it is also used flow gap h is small compared to the length
for annular geometries encountered, for of the flow geometry L(hlL<\) and if h var-
example, in wire coating (Fig. 2-3 c) or spi- ies slowly (dh/dx< I and dhldy< I), so that
ral mandrel dies. it is possible to consider locally a pure shear
A lay flat approximation was used in the flow, with only two velocity components u
first mold-filling softwares in order to trans- and v in the x and y directions (see Fig. 2-9)
form the complex 3 D geometry of a mold
into a planar one. The two-dimensional flow (2-18 a)
2r\ dx
may then be divided into several unidirec-
tional flows [see Alles et al. (1988)]. This (2-18 b)
technique has also been used in flat die
extrusion (Vergnes et al., 1980) or in a spi- Integrating the mass balance equation
ral mandrel die (Saillard and Agassant, throughout the thickness leads to the Hele-
1984). Shaw equation (Hele-Shaw, 1899)
div(/z3grad/?) = O (2-19)
2.4.3.4 Flow Kinematics Assumptions
This may be generalized for a power law,
Confined flows and free surface flows temperature-dependent fluid: the general-
will be considered successively: ized Hele-Shaw equation is [see Vergnes
92 2 General Principles of Polymer Processing Modeling

and Agassant (1986)]

d2p d2p] + 2n(dpdh j dpdh^ h (dpdK } dp dK^
dx2 dy2] n \^ 3JC 3JC dy dy ) Kny dx dx dy dy )
dp)2d2P (dpXd2p dp dp d2p
\-nydx) dx2 \dy) dy2 dx dy dxdy
+ h- =0 (2-20)
dp
dx

The two first terms are equivalent to

Eq. (2-19); the third term corresponds to the
temperature dependence of the viscosity (if
the consistency index K is independent of
the temperature, this term is zero); the fourth
term corresponds to the shear thinning
behavior (if n- 1, this term is zero).
For more general viscous behavior
[Eq. (2-13)], the Hele-Shaw equation can be
expressed as [see Agassant et al. (1993)]
div (P grad p) = 0 (2-21 a)
where [3 is defined as
h
( *\2
nz-z*) (2-21 b)
where z* corresponds to the location of max-
imum velocity throughout the thickness.
Generally speaking, the lubrication or
Hele-Shaw approximation makes it possible
to reduce a mechanical problem with four
equations [Eq. (2-17) in the Newtonian
case] and four unknowns (u, v, w, p) to a
problem with one equation (Eq. (2-19),
(2-20), or (2-21)] with the pressure as an
unknown.
(ii) Thin film or fiber approximations may
be introduced in most stretching situations.

Swell

Water

W(L)

Figure 2-10. Fiber spinning of a unique filament.

Figure 2-9. Typical geometry of confined flow. (The notation is defined in Sec. 2.5.5.)
 2.4 Governing Equations and Simplification Methods 93

If we consider the fiber spinning of a New- differential equation, with only one veloc-
tonian fluid (Fig. 2-10), two velocity com- ity component unknown.
ponents - the longitudinal component w,
which may be considered as a constant in
each section [w(z)], and the radial compo- 2.4.3.5 Energy Balance Assumptions
nent [u(r, z)] - as well as the hydrostatic
(i) In a 2 D confined flow geometry between
pressure have to be determined.
parallel plates, the temperature balance
The continuity equation makes it possible equation [Eq. (2-11)] is, in steady condi-
to express the radial velocity component as tions and for a constant heat conductivity
a function of the longitudinal one
(2-27)
U(r,z) =~ ^ (2-22)

Shear stresses are neglected with respect Introducing a mean temperature approx-
to elongational stresses, and as a conse- imation T throughout the flow gap h leads
quence the stress tensor is diagonal to a first order partial differential equation

0
pc ox ay pc
0
(2-28)
0 pc h
where u and v are the mean velocity com-
(2-23)
ponents which may be derived from Eq.
The thin fiber approximation consists of (2-18). The Nusselt number Nu represents
assuming that if the radial stress is zero at the nondimensional value of the heat trans-
the periphery of the fiber, it remains zero fer coefficient X with the walls of the con-
everywhere. As a consequence fined geometry. This Nusselt number is a
- ^dw function of the Brinkman number [Eq.
(2-24) (2-6)] and the Cameron number
dz
which leads to the well-known Trouton Nu = /(fir, Co) (2-29 a)
equation (Trouton, 1906)
Ca (2-29 b)
Gzz=3ri
.dw
(2-25)
~vh2
dz where L is the flow length, V the mean
Assuming that the stretching force is a velocity, and a the heat diffusivity. The func-
constant results in a mean velocity balance tion/may be derived in simple flow situa-
equation tions from analytical or numerical compu-
tations [see, for example, Agassant et al.
(2-26) (1988)].
The validity of this mean temperature
where Q is the volumetric flow rate. approximation will depend on the accuracy
The same type of equation will be derived of the Nusselt number and the importance
for other elongation situations. Here again of the temperature difference between the
a set of several differential equations with polymer (f) and the wall (TJ. If (F - TJ
several unknowns is reduced to one single is small (as in many die flows or in calen-
94 2 General Principles of Polymer Processing Modeling
dering problems), the accuracy of a mean
temperature approximation may be suffi-
cient. On the other hand, if (T - Tw) is
important (as in injection molding), it
will be necessary to solve the global ener-
gy balance equation [Eq. (2-11) or Eq.
(2-27)].
(ii) In a free surface flow problem (fiber
spinning or film blowing), a mean temper-
ature approximation is again often used.
Generally, viscous dissipation may be
neglected. For example, in fiber spinning
-Nuk (2-30)
**%- R It is interesting to optimize the die geom-
where R is the radius of the fiber at height
z. Heat transfer with the surrounding air will
be governed by free convection, forced con-
vection, and radiation. It is not easy to define
the balance between these different contri-
butions. In fiber spinning, forced convec-
tion will be dominant and the Nusselt num-
ber will be a function of the Reynolds num-
ber of the surrounding air [see Agassant
etal. (1991)].
2.4.4 Preliminary Conclusions
Some of these simplifying assumptions
may be used to obtain accurate solutions for
several polymer processing geometries:
- purely viscous, Hele-Shaw and mean tem-
perature approximations, in a coat hanger
flat die geometry (Sec. 2.5.1);
- the same approximation, plus unrolling
the flow, in a tube die geometry (Sec.
2.5.2);
- purely viscous and Hele-Shaw approxi-
mations (but with a temperature profile
throughout the thickness) in injection
molding (Sec. 2.5.4);
- thin fiber approximation, but with a vis-
coelastic constitutive equation in fiber
spinning (Sec. 2.5.5).
In more complex flow geometries none of
these approximations are available. Never-
theless, 3 D, nonisothermal, viscoelastic
computations are not easy to achieve at
present. Purely viscous, 3 D, isothermal
computations in a profile die geometry will
be presented in Sec. 2.5.3.
2.5 Examples of Polymer Flow
Computations
2.5.1 Coat Hanger Flat Die Geometry
etry in order to obtain a uniform thickness
and temperature distribution at the die exit,
at the maximum possible flow rate. The flow
for the geometry in Fig. 2-3 a is nearly
shearing flow; as a consequence, a purely
viscous approximation has been used.
Lubrication approximations are available;
only the transition between the distribution
channel and the narrow slit before the strain-
ing bar presents severe flow restrictions. For
a power law, temperature-dependent poly-
mer, Eq. (2-20) will be considered with the
following boundary conditions: zero pres-
sure at the die exit, a zero pressure gradient
along the periphery of the die (which means
a zero flow rate through the die border but
not a zero velocity along the border), and an
imposed pressure gradient at the die entry
(which means an imposed flow rate).
A mean temperature approximation
[Eq. (2-28)] will be used. An imposed wall
temperature Tw and an initial temperature at
the die entry T{ will be considered; u and v
in Eq. (2-28) will be derived from the pres-
sure field using Eq. (2-18) (or equivalent
equations for power law fluids).
As a consequence, the set of eleven equa-
tions with eleven unknowns [Eqs. (2-8),
(2-10), (2-11), and (2-14)] will be restrict-
ed to a set of four equations [Eqs. (2-18),
 2.5 Examples of Polymer Flow Computations 95

(2-20), and 2-(28)] with four unknowns (p,
T, u, and v). They can be solved iteratively
using a finite difference or a finite element
method (Ito, 1970; Klein and Klein, 1973;
Matsubara, 1979; Vergneset al., 1984; Puis-
sant etal., 1994):
An initial (for example, uniform) temper-
ature field is considered.
The value of the viscosity (or the consis-
tency index K when considering a power
law) is deduced using an Arrhenius equa-
tion [Eq. (2-4)] or a WLF equation
[Eq. (2-5)].
Equation (2-20) is solved with the boun-
dary conditions presented above.
The mean velocity components u and v
are deduced.
The mean temperature balance equation
[Eq. (2-28)] is then solved with the previ-
ously determined pressure and velocity
fields.
A new temperature distribution is deduced
in the whole die which makes it possible
to define a new viscosity (consistency)
distribution and then a new pressure field,
etc., until convergence.
Generally three or four iterations are
required before convergence.
Figure 2-1 l a shows the pressure field
and the flow rate distribution in the die. If
the flow lines are equidistant at the die exit,
the flow rate distribution will be uniform.
As shown in Fig. 2-11 b, the flow rate dis-
tribution will be strongly dependent on the
power law index: for a low value of the
power law index (ft = 0.2), the flow rate is
more important in the central part of the die
than at the periphery; the opposite situation
is encountered for higher n values (n = 0.35
and n = 0.5). As a consequence, a sheeting
die has to be designed for each polymer.
Figure 2-12 a presents the mean tempera-
ture field within the die for T{ = Tw = 200 C.
The flow seems to be nearly isothermal and
it could be believed that heat transfer can-
not modify the flow distribution. In fact,
when modifying the temperature of the die,
the flow distribution is markedly affected:

100 bars

90.1 bars 802bars

6O.d r^
50.5 J
30.7 '
20.8- ______ (a)
in g 1

= 1.0-
bar
1.2

i" a
1
a) n = 0.2
b) n = 0.35
(b) Figure 2-11. (a) Coat
hanger die - pressure and
01 c) n = 0.5 flow rate distribution
^ 0.9
(lbar=lxlO5Nnr2),
J3
cc
T (b) relative flow rate distri-
0.8
bution at die exit.
96 2 General Principles of Polymer Processing Modeling

(a)

1.3
AI p
/
Wall femperafure:
t" / a) T = 180 C
b) T = 200 C
(V
c) T = 220 eC (b)
2 1.1
J c
> 1-0
Figure 2-12. (a) Coat
I 0.9 hanger die - temperature

0.8
/ distribution; (b) influence
of the temperature of the

07
v' die on the flow rate distri-
bution at the die exit.

when r w = 180C, a very bad flow distribu-

tion is obtained (30%), where as when oversweilinq
Tw = 220 C the quality of the distribution is
very even (4%) (Fig. 12b). This example
clearly points out how important the THICKNESS DEFECT SYMMETRICAL
thermo-mechanical coupling is in polymer DUE TO MANDREL THICKNESS DEFECTS
flow modeling. ECCENTRICITY

Figure 2-13. Examples of thickness defects in poly-

2.5.2 Tube Die Geometry
One of the main problems encountered in
polymer pipe processing, especially at high
output rates, is a thickness irregularity along
the perimeter of the pipe (Saillard et al.,
1984). In some cases, this defect is due to
the mandrel eccentricity, but generally, two
symmetrical swelling nonuniformities
appear, even when the mandrel is well cen-
tered in the housing (Fig. 2-13).
mer pipe extrusions
As can be observed in Fig. 2-3 b, the
geometry of the tube die is axisymmetric,
except around the spider legs. However, the
overswelling defects are not connected to
the location of these spider legs. Getting an
irregular thickness by using an axisymmet-
rical die is an unexpected result. In fact, for
PVC processing, counterrotating twin
 2.5 Examples of Polymer Flow Computations
section aa
section bb
Figure 2-14. Typical temperature profile at the exit
of a counterrotating twin screw extruder; a maximum
temperature gradient of 10C may be observed.
screw extruders are commonly used and
nonaxisymmetrical temperature profiles
may be measured at the die entry (Klenk,
1969), as shown in Fig. 2-14. It is easy to
speculate that these cool and hot areas will
be separated by the mandrel and will follow
independent ways along the die. Along a
"hot" flow line, the viscosity will be lower
and the local output rate higher, which
explains the emergence of a local overswell-
ing.
As a consequence, the flow is no longer
axisymmetrical, but at first glance, it is
tempting to assume that the flow equations
remain those of the axisymmetric calcula-
tions, but with different viscosity values in
the "hot" and the "cool" regions.
As pointed out in Sec. 2.4.3 A, lubrication
approximations can be used to reduce the
two-dimensional axisymmetric flow into
a one-directional one. The Hele-Shaw
equation is now called a Reynolds equa-
tion [Eq. (2-31)]. For a power law fluid, it
is written as
\ln
97
where Q is the volumetric flow rate, rx and
re are the radius of the mandrel and the
inner radius of the die, respectively, and
r* is the location of the maximum veloc-
ity within the flow gap (see Fig. 2-15).
The temperature balance equation is
deduced from Eq. (2-28) n .
Equations (2-31) and (2-32) are coupled
through the temperature dependence of
the viscosity [Arrhenius law - Eq. (2-4)]
Equations (2-31), (2-32), and (2-4) are
solved by using a slab method: the flow
rate Q and the initial temperature T{ in
each sector of the die entry should be
known. The polymer consistency index K
is deduced in the first slab using Eq.
(2-4). The pressure drop is then obtained
in the first slab by introducing this value
of K in Eq. (2-31). It is then possible to
compute the temperature gradient in the
first slab using Eq. (2-32). The tempera-
ture at the extremity of the first slab will
lead to a new value of the consistency
index for the second slab, and so on until
the die exist.
Figure 2-16 a presents the pressure profile
along the die; the pressure drop occurs at
the die exit, after the spider legs. In the
same way, Fig. 2-16 b shows that the mean
temperature also increases in the last part
of the die.
If different values of the initial tempera-
ture are now introduced in the axisymmet-
ric computation, corresponding to the dif-
ferent sectors of Fig. 2-14, the resulting
thickness distribution is far more impor-
tant than in the experiments (1.9 mm com-
dXdr (2-31)
98 2 General Principles of Polymer Processing Modeling

Figure 2-15. Details of the

tube flow geometry.

0.1 0.2 0.3 0.4

Axial distance, z im)

Figure 2-16. (a) Pressure

profile along the tube die,
(b) mean temperature profile
along the tube die.
0.1 0.2 0.3 0.4
Axial distance, z ( m ) * -
 2.5 Examples of Polymer Flow Computations 99

puted thickness variation as opposed to 192 190 184 180 187 190 192

0.6 mm in the experiments). This illus-

trates that this "sectorial" axisymmetric
computation is not valid and that the initial
temperature gradients promote orthoradi-
al flow velocity components within the
axisymmetric geometry.
This has been illustrated by unrolling the
flow geometry in the last part of the die (after
the spider legs), where both the pressure gra-
dient and the temperature gradient are
important. It is now a confined flow geom-
etry (Fig. 2-9) and the Hele-Shaw equations
[Eqs. (2-18), (2-20), and (2-28)] used in the
preceeding section have been solved.
For an entry temperature varying between
180 and 192 C, the isotherms and the flow
rate distribution at the die exit are indicat-
ed in Fig. 2-17, the temperature heteroge-
neity reduces from 12 C at the die entry
to 7C at the die exit (Fig. 2-17 a); the
resulting flow rate distribution is about
10% (Fig. 17b), which induces a thick-
ness eccentricity of 1.3 mm. This value
has to be compared to the axisymmetrical (b)
computation (1.9 mm) and to the experi-
mental result (0.6 mm).
In order to improve the agreement
between computation and experiment, it
would be necessary to take into account
the real experimental temperature profile DIE WIDTH Y

at the die entry (Fig. 2-14) and not aver-
aged values in different flow sectors. This
would necessitate three-dimensional
computations, which will be presented in
the next section.
Nevertheless, this computation method
makes it possible to propose technological
solutions in order to decrease these over-
swelling defects. It is suggested to use a dif-
ferential thermal regulation in order to
"heat" the cool flow lines and to "cool" the
hot flow lines. In Fig. 2-18 a we impose a
30 C temperature difference at the periph-
Figure 2-17. (a) Mean temperature distribution in the
unrolled geometry of the final part of the tube die. The
temperature of the die is uniform. Only half of the
geometry is represented, (b) Resulting flow rate dis-
tribution at the tube die exit (half of the exit section).
ery of the die (this can be achieved by set-
ting heating cartridges all around the die).
We observe in Fig. 2-18 b that the tempera-
ture field at the die exit is quite uniform. The
resulting flow rate distribution (Fig. 2-18 c)
reduces to 3%, and the thickness varia-
tions are lowered to 0.2 mm.
100 2 General Principles of Polymer Processing Modeling
(a)
(c)
Figure 2-18. (a) Differential temperature control
along the periphery of the tube die, (b) resulting mean
temperature distribution in the unrolled geometry of
the tube die, (c) resulting flow rate distribution at the
tube die exit.
This second example shows that nonuni-
formity in the temperature may transform a
geometrically axisymmetric flow into a far
more complex one.
2.5.3 Profile Die Geometry
If we consider the profile die geometry
presented in Fig. 2-3 d, the flow is really
three-dimensional and no geometrical or
kinematic assumption is a priori valid.
First, we assume a purely viscous constit-
utive equation and an isothermal flow. The
main problem in profile die extrusion is the
flow balance at the die exit; even a slight
imbalance can cause the profile to bend. The
variational formulation equivalent to mass
[Eq. (2-2)] and stress [Eq. (2-10)] balance
equations with a purely viscous constitutive
equation is the following. Find (u, p), which
gives
\ir[ e(w): E(M*) dv - \pVu * dv = 0 (2-33 a)
a Q
and
jp*Vudv = 0 (2-33 b)
a
for any arbitrary (w*, /?*).
Equation (2-33) is solved using a Galer-
kin finite element method. This leads to the
resolution of nonlinear equations, which are
solved by a classical Newton-Raphson
method. Using an isotropic mesh of the flow
domain would lead to an unrealistic storage
requirement (it is necessary to introduce a
minimum of four meshes within the finest
exit section). As a consequence, anisotrop-
ic meshes based on non-Euclidian metrics
have been introduced (George et al., 1991;
Magnin, 1994) in a three-dimensional mesh
generator (Coupez, 1994). Figure 2-19
presents an example of an anisotropic mesh.
Figure 2-20 gives the pressure field in the
half geometry (Gobeau et al., 1995). The
pressure remains quite constant in the
upstream region. The pressure drop is locat-
ed in the thinner region near the die exit. The
isobar lines seem to be parallel to the exit
section, which would lead to a uniform
velocity at the exit if the flow gap was a con-
stant. In fact, as indicatd in Fig. 2-21, the
velocity distribution is not uniform, even in
the flow regions where the gap is constant.
The mean velocity field throughout the gap
 2.5 Examples of Polymer Flow Computations 101

Figure 2-19. Anisotropic meshing of the profile die.

<imum : 20.01 MPa

18.6587

17.3019

15.9451

[> 14.5882

|> 13.2314

11.8746

|> 10.5178

i > 9.16096

7.80414

6.44732

5.09050

3.73368

2.37686

1.02004

-.336775

Figure 2-20. Pressure field in the profile die geometry of Fig. 2-19; only one half of the geometry is represented.
102 2 General Principles of P o l y m e r P r o c e s s i n g M o d e l i n g

<imum : 4.10 mm/s

I> 3.82986

> 3.SS606

> 3.28226

> 3.00847

> 2.73467

> 2.46088

|> 2.18708

!> 1.91329

|> 1.63949

> 1.36570

> 1.09190

> .818104

> .544308

> .270513

> -.328290E-02

Figure 2-21. Velocity field at the profile die exit.

has been compared to experimental meas-

urements performed on PVC compound
0)
0) profile extrudates (Fig. 2-22). The numeri-
a. cal computation overestimates the observed
o velocity gradients, but the general trends are
CO in agreement.

2.5.4 Injection Molding

2 3 4 5 6 7
Injection molding is one of the more com-
perimeter of the die exit plex situations encountered in polymer pro-
Figure 2-22. Velocity distribution at the profile die cessing:
exit; comparison between experiment () and numer-
ical computations ().
A high injection speed induces a large vis-
cous dissipation.
High temperature gradients are encoun-
tered between the hot polymer layer and
the cold mold walls.
 2.5 Examples of Polymer Flow Computations
Mold geometries are often complex.
Additional polymer is introduced after
mold filling in order to compensate for
shrinkage during cooling.
Polymer part warpage may be observed
after demolding.
The main questions polymer converters
are asking are the following:
How to design the mold and in particular
the gates and runners in order to achieve
filling in the most uniform way?
How to adjust the injection speed, poly-
mer and mold temperatures, packing pres-
sure, and packing holding time in order to
obtain a part with the required properties
(good mechanical properties, no warpage,
etc.)?
In this section, we focus our interest on
mold filling. No general three-dimensional
software is available at this time. In several
mold geometries, the Hele-Shaw approxi-
mation may be applied (the flow gap is small
in comparison with the overall mold dimen-
sions), which means solving Eq. (2-21) at
each time step with the following boundary
conditions (Fig. 2-23): zero pressure at the
flow front (/? = 0), a zero pressure gradient
along the borders (dpIdn-Q) an imposed
pressure gradient (which means imposed
flow rate Q) at the gate. Finite difference
methods (Broyer et al., 1975; Hieber and
Shen, 1978; Subbiah et al., 1989), or finite
element methods (Willien, 1992; Couniot et
dp/dn = 0
Figure 2-23. Mechanical boundary conditions dur-
ing mold filling.
103
al., 1989; Chiang et al., 1991; Boshouwers
and Van der Werf, 1988) may be used.
A mean temperature approximation is not
valid due to the high transverse temperature
gradients. As a consequence we have to
solve the following energy balance equation
pc
(2-34)
dz
The generalized shear rate f is defined by
1/2
7= (2-35)
dz)
The gapwise convection term w dT/dz
cannot generally be neglected because,
although the w velocity component is very
small in comparison with the u and v veloc-
ity components, the dT/dz temperature gra-
dient is generally very high. The boundary
conditions are as follows: a given injection
temperature at the mold entrance (r inj ), an
imposed wall temperature, interfacial tem-
perature, or heat flux condition at the mold
wall, and a zero temperature gradient along
the borders.
Equation (2-34) can be solved using finite
difference, finite element, or control volume
methods. In this last method, the control vol-
umes are built by joining the centroids of the
finite elements (which are used for the
description of the geometry and for the pres-
sure computation) to the center of each side
of the elements (Fig. 2-24 a). Then sub-
control volumes are built by discretization
through the thickness (Fig. 2-24 b), in which
a heat balance leads to the temperature.
Finally, when the pressure, velocity, and
temperature are known, the flow front posi-
tion must be updated for the next time step.
This may be achieved using temporary
meshes with a Lagrangian description of the
front (Couniot et al., 1989). Another meth-
od consists of defining for each control vol-
104 2 General Principles of Polymer Processing Modeling

(a)
0.09 s

Figure 2-24. (a) Control volumes built on the trian-

gular finite element mesh of the mid surface, (b) sub-
control volumes within the gap thickness.

ume (Fig. 2-24 a) a fill factor a varying from (b)

0.15 s
0 (empty volume) to one (filled volume). A
value of a between 0 and 1 means that the
flow front will be located within the control
volume. At each time step the value of a is
updated by solving Eq. (2-36) for each con- (c)
trol volume (Willien, 1992) 0.21

u)adl (2-36)
ut
Q r
where Q represents the control volume area,
h the local flow gap, Fthe border of the con-
trol volume, and n the vector normal to the
border. These methods are now widely used
in most of the commercially available soft-
ware packages. Figure 2-25 represents the
pressure field at successive time steps dur-
ing the filling of a rectangular box. The same
kind of results may be presented for more
complex mold geometries.
Even in a simple mold geometry, this
method is not able to capture the velocity,
stress, and temperature fields near the mold
gate and at the flow front where marked
velocity components may be observed out
of the mid-plane of the part. These velocity
components, even located in a restricted
area, are of importance in order to predict
fiber orientation (for injection molding of
short fiber reinforced thermoplastics) or
polymer crystallization. A two-dimensional
nonisothermal finite element method has
been developed by Magnin (1994).
At each time step, the velocity and
pressure are computed by solving Eq.
(2-33) (in 2 D). The evolution of the filled
(d)
0.27
Figure 2-25. Mold filling of a rectangular box; the
pressure field at successive time steps.
area is determined with an arbitrary
Lagrangian-Eulerian method. This means
that only the filled area is meshed. This
mesh is updated between two time steps but
with a velocity that is different from the
material velocity (Lagrangian method), and
which minimizes mesh distortion.
The equation of energy is solved by a
method of characteristics to account for the
convection terms. Anistropic meshes, based
on the same principle as for the 3 D profile
die calculations, are used in order to capture
the very high temperature gradients along
the mold wall.
Figure 2-26 illustrates the so-called
"fountain" flow for a Newtonian and for a
 2.5 Examples of Polymer Flow Computations 105

(a)

(b) Figure 2-26. Fountain flow

for (a) a Newtonian and (b)
a shear thinning fluid.

T100,4 200.1 T<225.0

100.4<T< 125.3 226.0<T<250.0

125.3<T< 160.3 25Q.0<T274.9

150.3<T<176.2 274.9T

17S.2T200.1

Figure 2-27. Center-gated disk geometry: (a) anisotropic meshing (b) flow lines, and (c) temperature field.

shear thinning fluid. Figure 2-27 represents
the flow lines and the temperature field in a
center-gated disk, as well as the anistropic
meshing used.
2.5.5 Fiber Spinning
Synthetic fibers are manufactured by
spinning a polymer solution or a molten
polymer. Different spinning processes are
encountered: dry, wet, and air-gap spinning,
with generally high draw ratios with air
cooling over a long distance, or low draw
ratios over a short distance in air, before
cooling in a water bath (see Fig. 2-10).
In this last case, the spinning can be con-
sidered as isothermal. As pointed out in Sec.
2.4.3.1, a viseoelastie constitutive equation
106 2 General Principles of Polymer Processing Modeling

is required for elongational flow. A Max- 150

well constitutive equation may be selected

\
as a preliminary choice. A thin fiber approx-
imation is introduced and the extra stress \
100 Unattainable
components are [Eqs. (2-37)]
\
-rrr - 77 (^z-j/aj 50 V

0 0.01 0.02 0.03 0.04

Considering that there is no force acting De-
on the surface of the filament, the stress
component in the spinning direction reads Figure 2-28. Fiber spinning of a viscoelastic fluid
showing the unattainable zone.
ozz=Tzz-Trr (2-38)
Subtracting Eq. (2-37 a) from Eq. (2-37 b)
leads to
d(Jzz dw ^ -> dw ^

It is interesting to note that a zero relax-

ation time (0=0) leads to the well-known
Trouton relationship. We need additional
equations:
A constant flow rate
= S(z)w(z) (2-39)
A constant drawing force, which means
that the mass, inertia, air drag, and surface
tension may be neglected 0.01 0.02 0.03
De
F=azz(z)S(z) (2-40)
The boundary conditions are as follows: Figure 2-29. The drawing force as a function of the
Deborah number.
the initial section 5(0) = 5 0 is supposed to be
equal to the die section, the initial velocity
w0 and the draw down velocity w(L) are
known, and we assume that the initial extra ratio Dr = w(L)/W0; the Deborah number
stress component TZZ(0) is equal to the mean De = 6W0/L; as well an a nondimensional
extra stress component in the flow direction force HE = FL/(riS0W0) into Eqs. (2-37) to
at the end of the capillary die. (2-40) yields the following set of differen-
Introducing the nondimensional vari- tial equations:
ables: V= w/W0; A = S/S09 =z/L9 *?= Tzz So/F, dV = V
and the nondimensional numbers: the draw
 2.5 Examples of Polymer Flow Computations
150
spinning length
Figure 2-31. Diameter profile along the spinning
path; a comparison between computations ( New-
tonian; Maxwell) and experiments (o).
and
(2-41 b)
DeV
with the boundary conditions: A(0)=l,
V(0) = l, V(l) = D r and *F(0)= *F* (deduced
from rzz(0)).
The solution is obtained by selecting an
arbitrary value for E and then computing
107
Figure 2-30. Velocity profile along
the spinning path for a Newtonian
fluid and for a viscoelastic one.
from the die exit to the take-up point for slab
after slab V(,) and *F() by integration
Eqs. (2-41 a) and (2-41 b).
If the calculated value of V(l) is different
from D r , E is modified and the process is
repeated until convergence, if it occurs. In
fact, for high Deborah numbers, it is not pos-
sible to find a solution. This shows the exis-
tence of an unattainable zone, which phys-
ically corresponds to conditions under
which spinning is not possible (Fig. 2-28).
The drawing force increases markedly in the
vicinity of this unattainable zone (Fig.
2-29). The velocity profile is exponential in
the Newtonian case (0= 0) and becomes pro-
gressively more linear on increasing the
Deborah number (Fig. 2-30).
The diameter of the filament may be
measured along the spinning path by using
an optical device. The diameter computed
with a viscoelastic model (D^ = 0.016) is
very close to the measured one, whereas it
is quite different for a Newtonian model
(Fig. 2-31). This clearly points out again the
great influence of viscoelasticity in elonga-
tional processes. (Denn et al., 1975; Demay,
1983.)
108 2 General Principles of Polymer Processing Modeling
2.6 Conclusions and Perspectives
Polymer processing modeling appears to
be a useful tool for optimizing die and mold
geometries and the processing conditions
(flow rate, polymer and machine tempera-
ture). Nowadays computer-assisted design
is starting to be widely used by polymer pro-
cessing manufacturers and by polymer con-
verters.
In the near future, polymer processing
modeling will be used progressively in order
to optimize the physical properties of the
part (transparency, mechanical properties,
etc.), but this will require a better under-
standing of macromolecular orientation and
crystallization kinetics under complex flow
fields and high temperature gradients.
From a numerical point of view, finite ele-
ment methods are now efficient for purely
viscous nonisothermal flow conditions. In
three-dimensional flow geometries the main
problem consists of obtaining an accurate
meshing of the geometry while saving com-
putation time and memory requirement.
Iterative solvers, parallel computing, and
error estimators are essential developments
if nontrivial flow geometries are to be con-
sidered. For viscoelastic flow computa-
tions, the choice of an accurate constitutive
equation remains open. The mixed charac-
ter of these constitutive equations (both
elliptic and hyperbolic) leads to numerical
difficulties, especially when stress singular-
ities are present in the flow geometry (reen-
trant corners, stick-slip). At this time, only
two-dimensional viscoelastic computa-
tions, mostly in isothermal conditions, are
available.
2.7 References
Agassant, J. R, Saillard, P., Vergnes, B. (1988), Rev.
Gen. Therm. Fr. 272, All.
Agassant, J. R, Avenas, P., Sergent, J. P., Carreau, P.
(1991), Polymer Processing, Principles and Mod-
eling, Chap. 3. Munich: Hanser.
Agassant, J. R, Vergnes, B., Vincent, M. (1993), Mak-
romol. Chem., Macromol. Symp. 68, 153.
Alles, H., Agassant, J. R, Vincent, M., Dehay, G.,
Lerebours, P., Ginglinger, B. (1988), Int. Polym.
Proc. 2, 191.
Ausias, G., Agassant, J. R, Vincent, M., Lafleur, P. G.,
Lavoie, P. A., Carreau, P. J. (1992), JRheol. 36, 525.
Beraudo, C. (1995), These de Doctorat, Ecole des
Mines de Paris, France.
Boshouwers, G., Van der Werf, J. (1988), Ph. D. The-
sis, Technical University of Eindhoven, The Neth-
erlands.
Brinkman, H. C. (1951), Appl. Sci. Res. A2, 120.
Broyer, E., Gutfinger, C , Tadmor, Z. (1975), Trans.
Soc. Rheol. 19, 423.
Chiang, H. H., Hieber, C. A., Wang, K. K. (1991),
Polym. Eng. Sci. 31, 116.
Couniot, A., Dheur, L., Dupret, R (1989), in: Numer-
ical Methods in Industrial Forming Processes:
Thomson, R. D., Wood, O. C , Zienkiewicz, A.
(Eds.). Rotterdam: Balkema, p. 235.
Coupez, T. (1994), in: Numerical grid Generation
in Computational Fluid Dynamics and Related
Fields: Hanser, J., Weatherhill, N. P., Eiseman,
P. R., Thomson, J. R (Eds.). Swansea: Pineridge
Press, p. 615.
Cox, W. P., Merz, E. M. (1958), J. Polym. Sci. 28, 619.
Demay, Y. (1983), Ph. D. Thesis, Nice University.
Denn, M. M., Marrucci, G. (1971), AICHEJ. 17, 101.
Denn, M. M., Petrie, C. J. S., Avenas, P. (1975),
AICHEJ. 21, 791.
George, P. L., Hecht, R, Vallet, M. G. (1991), Adv.
Eng. Software 13, 303.
Gobeau, J. R, Coupez, T., Vergnes, B., Agassant J. R
(1995), in: Simulation of Materials Processing:
Theory, Methods and Applications, NUMIFORM
'95: Shen, S.-R, Dawson, P. (Eds.). Rotterdam: Bal-
kema, p. 59.
Guillet, J., Carrot, C , Kim, B. S., Agassant, J. R,
Vergnes, B., Clermont, J. R., Normandin, M.,
Bereaux, Y. (1996), in: Rheology for Polymer Melt
Processing: Piau, J. M., Agassant, J. R (Eds.).
Amsterdam: Elsevier, p. 285.
Hele-Shaw, H. S. (1899), Proc. Roy. Soc. 16, 49.
Hieber, C. A., Shen, S.-F. (1978), Israel J. Technol.
16, 248.
Ito, K. (1970), Jpn. Plastics 4, 227.
Johnson, M. W., Segalmann, L. (1977), /. Non Newt.
FluidMech.2, 255.
Keunings, R. (1989), in: Fundamentals of Computer
Modeling for Polymer Processing: Tucker, C. L. Ill
(Ed.). Munich: Hanser, p. 403.
Kiriakidis, D. G., Park, H. J., Mitsoulis, E., Vergnes,
B., Agassant, J. R (1983),/. Non Newt. FluidMech.
47,339.
Klein, I., Klein, R. (1973), SPEJ. 29, 33.

Klenk, K. P. (1969), Thesis, Institut fur Kunststoffe
Verarbeitung, Aachen, Germany.
Larson, R. G. (1988), Constitutive Equations for Poly-
mer Melts and Solutions. London: Butterworths.
Lindt, J. T. (1976), Polym. Eng. Sci. 16, 284.
Magnin, B. (1994), Ph. D. Thesis, Ecole Nationale
Superieure des Mines de Paris, France.
Maillefer, C. (1959), Swiss Patent No. 363 149.
Matsubara, Y. (1979), Polym. Eng. Sci. 19, 169.
Mooney, M. (1931), J. Rheol. 2,210.
Mourniac, P., Agassant, J. F, Vergnes, B. (1992),
Rheol. Acta 31. 565.
Phan-Thien, N., Tanner, R. I. (1977), J. Non Newt.
Fluid Mech. 2, 353.
Puissant, S., Demay, Y., Vergnes, B., Agassant, J. F.
(1994), Polym. Eng. Sci. 34, 20.
Saillard, P., Agassant, J. F. (1984), Polym. Proc. Eng.
2,31.
Saillard, P., Vergnes, B., Agassant, J. F. (1984), Polym.
Proc. Eng. 2, 53.
Streeter, V. L. (1961), Handbook of Fluid Dynamics.
New York: McGraw-Hill.
Subbiah, S., Trafford, D. L., Guceri, S. I. (1989), Int.
J. Heat Mass Transfer 32, 415.
Tadmor, Z., Klein, I. (1970), Engineering Principles
of Plastic ating Extrusion. New York: Van Nostrand
Reinhold.
Tanner, R. I. (1985), Engineering Rheology. Oxford:
Clarendon.
Trouton, F. T. (1906), Proc. Roy. Soc, London A77.
2.7 References 109
Vergnes, B., Agassant, J. F. (1986), Adv. Polym. Tech-
nol. 6,411.
Vergnes, B., Saillard, P., Plantamura, B. (1980),
Kunststoffe 11,152.
Vergnes, B., Saillard, P., Agassant, J. F. (1984), Polym.
Eng. Sci. 24, 980.
Williams, M. L., Landel, R. R, Ferry, J. A. (1955),
J.Am. Chem. Soc. 77, 3701.
Willien, J. L. (1992), Ph. D. Thesis, Ecole des Mines
de Paris, France.
Yasuda, K. Y, Armstrong, R. C , Cohen, R. E. (1981),
Rheologica Acta 20, 163.
General Reading
Agassant, J. F., Avenas, P., Sergent, J. P., Vergnes, B.,
Vincent, M. (1996), La Mise en forme des matieres
plastiques. Paris: Techniques et Documentation.
Cours, J. A., Agassant, J. F, Diogo, A. C , Vlacho-
poulos, J., Walters, K. (1995), Rheological Funda-
mentals of Polymer Processing. Dordrecht: Kluwer.
Dealy, J. M., Wissbrun, K. M. (1990), Melt Rheology
and Its Role in Plastics Processing. New York: Van
Nostrand.
Fenner, R. T. (1979), Principles of Polymer Proces-
sing. London: Macmillan.
Tadmor, Z., Gogos, C. G. (1979), Principles of Poly-
mer Processing. New York: Wiley.
3 Emulsions: The Dynamics of Liquid-Liquid Mixing
Jos M. H. Janssen

General Electric Plastics, Bergen op Zoom, The Netherlands

List of Symbols and Abbreviations 115

3.1 Introduction 118
3.1.1 Blend Morphologies 118
3.1.2 Mixing Mechanisms 119
3.1.3 Chapter Survey 121
3.2 Stretching 121
3.2.1 Affine Deformation 121
3.2.1.1 Theoretical 121
3.2.1.2 Experimental 123
3.2.2 Stretching and Folding 125
3.2.2.1 The Cavity Flow 126
3.2.2.2 Static Mixers 127
3.2.2.3 Dynamic Mixers 128
3.2.3 Conclusion 128
3.3 Breakup 129
3.3.1 Breakup of a Viscous Thread at Rest 129
3.3.1.1 Theoretical 129
3.3.1.2 Experimental 131
3.3.1.3 Numerical 133
3.3.2 Breakup of a Viscoelastic Thread at Rest 136
3.3.2.1 Experimental 136
3.3.2.2 Numerical 139
3.3.3 Breakup of a Viscous Thread During Stretching 141
3.3.3.1 Theoretical 141
3.3.3.2 Experimental 144
3.3.4 Drop Breakup in Viscous Systems 146
3.3.4.1 Measurement of Cacrn 147
3.3.4.2 Drop Breakup Times 149
3.3.4.3 Retraction of an Extended Drop 149
3.3.5 Drop Breakup in Viscoelastic Systems 150
3.3.6 Comparison of Dispersion Mechanisms 150
3.3.6.1 Plane Hyperbolic Flow 151
3.3.6.2 Simple Shear Flow 152
3.3.7 Conclusion 153
3.4 Coalescence 154
3.4.1 Collision of Drops 154

Materials Science and Technology

Copyright WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
114 3 Emulsions: The Dynamics of Liquid-Liquid Mixing

3.4.2 Film Drainage 155

3.4.2.1 Theoretical 155
3.4.2.2 Experimental 159
3.4.3 Coalescence Probability 160
3.4.4 Combination of Breakup and Coalescence 162
3.4.5 Conclusion 164
3.5 Applications 164
3.5.1 A Two-Zone Mixing Model 164
3.5.1.1 Principle 164
3.5.1.2 Results 166
3.5.2 Passage Through a Die 171
3.5.3 Phase Inversion 172
3.5.4 A Full Continuous Phase Flow Simulation 174
3.5.5 Conclusion 174
3.6 Concluding Remarks 175
3.7 Appendices 176
3.7.1 Linear Flow Types 176
3.7.2 The Opposed Jets Device 178
3.7.2.1 Design of the Flow Cell 179
3.7.2.2 Position Control of the Drop 180
3.7.3 Characterization of the Model Liquids 181
3.7.4 Viscous Thread Breakup During Stretching 182
3.7.5 The Functions & and 186
3.8 References 186
 List of Symbols and Abbreviations 115

List of Symbols and Abbreviations

a radius of the flattened area of a deformed drop
A Hamaker constant (~ 10~20 J)
B width of a deformed drop
Bo Bond number (ApgR2/<j)
c (as superscript) conjugate
C collision frequency
C right Cauchy-Green tensor (F c F)
Ca capillary number (ricyR/a)
Cacra critical capillary number necessary for drop breakup
C collision frequency per unit volume
D drop deformation [L-B)/(L + B)]
D rate of deformation tensor [(L + Lc)/2]
De Deborah number ( # f l o w )
E residence time distribution function
ef stretching efficiency (D: mm) I / ( D : D)
F contact force
F deformation gradient tensor
g gravity constant (9.81 m/s2)
G velocity gradient
h film thickness
H channel depth
hcrit critical film thickness
h0 initial film thickness
/ mode number
I unit tensor
Io , modified Bessel function of the first kind (of order 0,1)
I{ derivative of \x with respect to x
k B o l t z m a n n ' s constant (1.38xlO~ 2 3 J/K)
K0l modified Bessel functions of the second kind (of order 0,1)
K\ derivative of Kx with respect to x
L length of a deformed drop
L velocity gradient tensor
m orientation vector
Mw molecular mass
n number of drops per unit v o l u m e ; n u m b e r of ideal mixers in a cascade;
n u m b e r of viscoelastic m o d e s
n normal vector
Af number of cycles
N{ first normal stress difference (Txx-Tyy)
p viscosity ratio (77d/7?c); pressure
Pcoa coalescence probability
P coll collision probability
^drain drainage probability
116 3 Emulsions: The Dynamics of Liquid-Liquid Mixing

q disturbance growth rate

Q volume flow rate
R radius of a drop or thread
Rb radius of a bulb
Re Reynolds number (pyR2/ri)
Rf radius of a filament
Rcrit critical radius at which the fatal disturbance starts growing
^drops radius of drops formed
R equivalent drop radius
R average radius of a disturbed thread
Ro initial radius of a thread
RX2 principal radii of curvature
s time 'slab' (time element)
t time
T absolute temperature
tb breakup time
tc critical time at which a disturbance starts growing
tg disturbance growth time
tcoll required collision time
tcrit critical time at which the fatal disturbance starts growing
Win required drainage time
tnow characteristic time of the flow
tmt available interaction time
Voc available process time
ta characteristic time for cr-driven processes (rjcR/a)
T mean residence time
t* dimensionless time (tlta or t/tnow)
u velocity vector ([u, v, w] or [w, v])
ug grid velocity
V volume
x disturbance wave number (2nR/X)
x position vector ([x, y, z] or [z, r])
xc critical x at which a disturbance starts growing
xm dominant wave number
x crit critical x at which the fatal disturbance starts growing
x0 initial wave number
x0opt optimum x0 causing breakup
V gradient operator

a disturbance amplitude; flow type parameter

ab disturbance amplitude at breakup
a0 initial disturbance amplitude
7 shear
7 shear rate [V/(2D:D)]
8 phase angle in oscillatory shear (tan S= r\'lr\")
 List of Symbols and Abbreviations 117

S gap height
strain; nonlinearity parameter in the Phan-Thien Tanner model
elongation or stretching rate (D : mm)
7] viscosity
7]c eff effective matrix viscosity
rjdc viscosity of the dispersed or continuous phase
r/s 'solvent' viscosity
r\y simple shear viscosity (Txy/y)
rj elongational viscosity [(rzz-Trr)/]
r\r dynamic viscosity in oscillatory shear
77" rigidity in oscillatory shear
1? relaxation time of a fluid
A disturbance wavelength
Am dominant wavelength
AQ initial wavelength
p density
pd c density of the dispersed or continuous phase
a interfacial tension
O Cauchy stress tensor
T shear stress (in fact, rxy)
X extra stress tensor
cp angle between longest drop/thread axis and streamlines
0 volume fraction of dispersed phase
(j)m maximum packing density
0Perc percolation threshold
0, 0 functions of the wave number x and viscosity ratio p
co frequency of oscillation
Q spin tensor [(L-L c )/2]
Q dimensionless growth rate
Qm dominant dimensionless growth rate

ALE arbitrary Lagrange Euler (mesh)

FEM finite element method
HDPE high density polyethylene
LDA laser Doppler anemometry
PS polystyrene
PTT Phan-Thien Tanner (model)
SUPG streamline upwind Petrov Galerkin
tr trace (operation on a tensor)
118 3 Emulsions: The Dynamics of Liquid-Liquid Mixing

3.1 Introduction different morphologies can be obtained.

3.1.1 Blend Morphologies
The dispersion of one liquid in another is
of indisputable relevance in many industri-
al processes. In polymer processing, for
example, melt blending of homopolymers is
a common route towards materials with spe-
cific properties that are superior to those of
the constituents. Most polymers are thermo-
dynamically immiscible in the molten state.
Hence the blending process yields a hetero-
geneous morphology that is characterized
by the shape, size, and distribution of the
constituting domains. At the end of the melt
blending process the morphology is frozen-
in in the solid state. Depending on the mate-
rials and the processing conditions, quite
Figure 3-1 shows elucidative examples
obtained from blends of polystyrene (PS)
and high density polyethylene (HDPE).
Since the properties of a blend are large-
ly influenced by its morphology, it is essen-
tial to model the development of the mor-
phology during compounding. Any mixing
model should incorporate the fundamental-
ly transient character of the governing
mechanisms in order to be applicable to a
practical situation. In particular, the time
scales of the distinct micro-rheological pro-
cesses have to be considered to see wheth-
er the available process time suffices for a
specific event to occur. A frozen-in blend
morphology is not necessarily in its equilib-
rium state. Moreover, in a subsequent pro-
cessing step, such as injection molding or

v
K V \ VH ri \ \
1 i
Figure 3-1. Typical morphologies of PS/HDPE blends: (a) spheres or (b) fibers (HDPE) in a matrix (PS), (c) a
cocontinuous, and (d) a lamellar structure (Meijer et ah, 1988).

film blowing, the morphology achieved
may alter due to the typical processing con-
ditions there. That is why fixation of mor-
phologies is essential. Possible routes for
fixation include the addition of compatibi-
lizers, electron beam irradiation (van Gis-
bergen, 1991), or, more promising, the cur-
ing of a dispersed thermoset, e.g., after
phase inversion (Venderbosch et al., 1993,
1994). All three routes aim at the prevention
of coalescence, which usually follows the
dispersion process.
Melt blending of polymers generally
involves non-Newtonian, nonisothermal,
time-dependent, complex 3-D flows. Con-
sequently, direct research on industrial com-
pounding equipment mainly yields com-
pound- and machine-limited results that
might be useful for the specific problem
under investigation, but are not conclusive
in a more general sense. Most fundamental
research on the blending of immiscible liq-
uids focuses on idealized systems, e.g, iso-
lated drops of well-characterized model liq-
uids at room temperature in elementary flow
fields. The results of this research are gen-
erally given in dimensionless representation
suitable for scaling to practical processes.
Most of the fundamental studies are restrict-
ed to Newtonian (viscous) systems, where-
as viscoelasticity is an essential feature of
polymeric melts and solutions. The question
is whether or not the influence of viscoelas-
ticity is such that it should inevitably be
taken into account in the distinct mixing
mechanisms. An analysis of its relevance
might result in approval of the usual omis-
sion of viscoelasticity, which was up to now
evidently caused by the complexity of the
)roblem.
.1.2 Mixing Mechanisms
In the mixing of immiscible liquids, the
linor component is generally (but not nec-
3.1 Introduction 119
essarily, see Sec. 3.5.3) present as the dis-
persed phase (drops or filaments) in a con-
tinuous phase of the major component. An
elementary step in the mixing process is the
deformation of a dispersed drop in a flow
field, yielding an increase in the interfacial
area between the two components and
accompanied by a decrease in the local
dimensions perpendicular to the flow direc-
tion, i.e., the striation thickness. In many
cases, e.g., for molten polymers, the viscos-
ities are large, so the Reynolds number (Re)
is small and inertia can be neglected with
respect to viscous shear stresses. Further-
more, the density difference, and hence the
Bond number, is small, implying that buoy-
ancy effects are negligible with respect to
interfacial effects. Drop deformation is then
mainly governed by the capillary number
(Ca), the ratio of the (deforming) shear
stress T exerted on the drop by the external
flow field, and the (shape conserving) inter-
facial stress alR (with crthe interfacial ten-
sion and R the local radius)
_TR _ rjcyR
Ca (3-1)
with 77C the viscosity of the continuous phase
and 7 the shear rate, which is defined as
7 = V2D:D (3-2)
D being the rate of deformation tensor. If
the capillary number is small, the interfacial
stress withstands the shear stress and a
steady ellipsoid drop shape exists. Above a
critical value, Cacriv the viscous shear stress
overrules the interfacial stress and no stable
equilibrium drop shape exists. The drop is
stretched and finally breaks into fragments.
Experimentally, Cacv[t is determined by
slowly increasing the shear rate and evalu-
ating whether or not the deformed drop
shape is stable in the long run; in fact, this
is drop breakup under quasi-equilibrium
conditions. Taylor (1934) and Grace (1971)
120 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
103
102 . r
BREAKUP
- simple shear\
101 . :
\ 1
100 .
: 2-D elongatlon^-^
NO BREAKUP
10-1
2
10-6 10-5 10-4 10-3 io- 10
p(=
showed that the critical capillary number
depends on both the viscosity ratio and the
flow type. Figure 3-2 shows Grace's experi-
mental results for Newtonian liquids in both
simple shear and 2-D elongational (plane
hyperbolic) flow for a wide range of the vis-
cosity ratio p between the dispersed and the
continuous phase
P=rid/ric (3-3)
From Fig. 3-2 it can be seen that under
quasi-equilibrium conditions it is easiest to
deform and break drops around/? ~ 1. Fur-
thermore, elongational flow is more effec-
tive than simple shear flow. If p > 4 it is
impossible to break drops in simple shear
due to the rotational character of the flow.
Bentley and Leal (1986 a, b) showed experi-
mentally that intermediate flow types (see
Sec. 3.7.1) yield values of Cacrii in between
the two curves of Fig. 3-2. Numerical stud-
ies on the critical capillary number in dif-
ferent types of flow agree with experimen-
tal data (see, e.g., Khakhar and Ottino, 1986,
and Fig. 3-28).
A useful subdivision of the mixing process
can be based on the value of the (local) cap-
illary number, which continuously decreases
Figure 3-2. Critical capil-
= lary number for drop break-
up versus viscosity ratio p
in simple shear and 2-D
elongational flow (Grace,
1971).
101 102 103
during the process due to the length scale
reduction (roughly from 1 mm to 1 |im):
(i) Stretching of dispersed drops when
Ca^>Cacrit (typically in the initial
stage of mixing when the dipersed
domains are large). Drops are stretched
affinely with the matrix into long, slen-
der threads. Since the interfacial stress
alR is overruled by the shear stress r,
the drops and threads do not (yet)
exhibit interfacial disturbances leading
to breakup; they are only distributed
over the matrix (i.e., distributive mix-
ing with passive interfaces).
(ii) Breakup of drops and threads when
Ca~\ (small radii of curvature). The
interfacial stress alR becomes signifi-
cant and favors the growth of interfa-
cial disturbances. This leads to break-
up of the formed liquid threads into
lines of small drops (i.e., dispersive
mixing with active interfaces). Depend-
ing on their size, these drops may even-
tually be stretched and broken again. If
the drops are small enough, alR protects
them against further deformation (they
become more 'rigid').

Although in reality stretching and break-
up do not occur separately during liquid-liq-
uid mixing, the above distinction is useful
for modeling the mixing process. In the case
of mixing solid agglomerates in a liquid
matrix, distributive and dispersive mixing
do proceed separately, i.e., agglomerates
have to be broken before the fragments can
be distributed. A liquid drop, on the other
hand, can be distributed (by stretching and
folding) before breakup has occurred.
Apart from a tendency towards finer mor-
phologies resulting from stretching and
breakup, a coarsening of the morphology
occurs during processing due to coalescence
of the dispersed droplets. Coalescence takes
place preferentially in quiet regions of the
mixer in contrast to the dimension-reducing
mechanism of stretching.
3.1.3 Chapter Survey
The outline of this chapter closely follows
the subdivisions of the different mixing
mechanisms. Section 3.2 discusses the prin-
ciples of stretching, including the key role
of reorientations and folds. In Sec. 3.3 the
interfacial tension is incorporated. In partic-
ular thread breakup during stretching is
emphasized. In order to determine the effect
of viscoelasticity, the breakup of viscoelas-
tic threads has been studied both experimen-
tally and numerically. Section 3.4 presents
an approach to the modeling of coalescence.
Finally, in Sec. 3.5, the assemblage of the
distinct mechanisms into an overall mixing
model is illustrated. The model simulates
the development of the morphology of a
blend in a compounder with a large amount
of freedom in the material parameters and
operating conditions. After the conclusions
in Sec. 3.6, some additional aspects are
elaborated in the appendices (Sec. 3.7).
The general emphasis of this research
focuses on the specific time scales of the dis-
3.2 Stretching 121
tinct processes. The effects of compatibiliz-
ers or surfactants were not specifically stud-
ied but are discussed where appropriate,
while the influence of viscoelasticity is
included where possible.
This chapter is based on a thesis by Jans-
sen (1993) and a number of publications,
i.e., Elemans et al. (1990, 1993), Janssen
etal. (1992, 1993), Janssen and Meijer
(1993, 1995), and Meijer and Janssen
(1994).
3.2 Stretching
3.2.1 Affine Deformation
3.2.1.1 Theoretical
As a typical starting morphology, a drop-
in-matrix structure is considered with a drop
size of the order of magnitude of millime-
ters (e.g., molten polymeric granules). In
polymer processing, some attention has
recently been given to lamellar starting mor-
phologies originating from the melting
stage (Ghosh et al., 1991; Lindt and Ghosh,
1992). These lamellae break up into threads
and subsequently into drops. In a more gen-
eral approach to the mixing process, such a
particular melting stage is omitted and a
large initial length scale is considered as the
starting point. For immiscible polymer
melts, an order of magnitude estimate of the
capillary number is
o/R~l(T2/l(r3 =
(3-4)
with Tthe shear stress (Pa), rjc the viscosity
of the continuous phase (Pa s), y the shear
rate [s~], see Eq. (3-2)], crthe interfacial ten-
sion (N/m), and R the drop radius (m).
122 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
From Eq. (3-4) it follows that in the initial
stage of mixing Ca ^> CaCTlt since Cacrit ~ 1.
In other words, the shape conserving inter-
facial stress (a/R) is overruled by the
deforming shear stress and the (millimeter-
sized) drops are deformed affinely with the
matrix, i.e., stretching with passive interfac-
es or distributive mixing. Note that for mis-
cible liquids (no interfacial tension) this
convective mixing is the only relevant pro-
cess (apart from some interdiffusion).
Figure 3-3 illustrates the affine deforma-
tion in simple shear flow of a sphere with
radius Ro into an ellipsoid with length L and
width B. The extent of drop deformation is
usually defined as
L-B (3-5)
D=
and ranges from 0 (sphere) to 1 (infinitely
extended thread). In the case of affine
motion, the deformation of the drop can be
calculated from the eigenvalue problem of
the right Cauchy-Green tensor C (= F c - F,
with F the deformation gradient tensor). In
simple shear flow this gives
(3-6a)
and
(3-6b)
so that
D= (3-6c)
The corresponding orientation angle (p
between the longest drop axis and the
Y (= Yt)
2Rn
streamlines is given by
-1
(3-6d)
Initially (7=0), the spherical drop stretches
maximally in the 45 direction. As the total
shear increases, the extending ellipsoid rotates
with its long axis toward the streamlines.
Evidently, the affine deformation of a
drop in simple shear flow only depends on
the total shear y(= ft) applied. The shear
rate y and the time t are interchangeable,
i.e., slow deformation over a long time will
give the same result as fast deformation over
a short time, leading to the same total shear.
Of course, the shear rate must be sufficient-
ly high to fulfill Ca ^>Cacriv Moreover, in
simple shear, affine deformation is princi-
pally only possible for viscosity ratios p < 4.
This additional limitation follows from the
infinite value of Cacrit for larger values of p,
see Fig. 3-2.
As a result of the 2-D character of simple
shear flow, the extending drop becomes flat-
tened (one cross-sectional axis is com-
pressed while the other one is invariant). In
reality, however, as the curvature becomes
large enough, the interfacial tension prohib-
its further flattening and favors a circular
cross-section; the width of the drop is no
longer deforming affinely. Assuming a cir-
cular cross-section, incompressibility
requires that BI{2RQ) = [LI2RO)YV1. Thus
affine length stretch [Eq. (3-6 a)] implies
(3-7a)
r +
1-1/2
(3-7b)
Figure 3-3. Affine deformation of a liquid
drop in simple shear flow.

so that
3/2
D= (3-7c)
For large shear values (y>5), Eq. (3-7)
can be approximated by
ik-~7 (3-8a)
(3-8b)
so that
(3-8c)
Most important is that in simple shear
flow the length increases almost linearly
with the total shear. As shown in Sec. 3.2.2,
this is not very efficient.
In elongational flows, an affinely ex-
tending drop remains aligned with the
principal direction of the strain rate and
the deformation proceeds exponentially.
In 2-D elongation (plane hyperbolic
flow)
= e (3-9a)
B (3-9b)
=e
so that
(3-9c)
e +1
Only the total strain e (= t, with the
elongation rate) is important. In 2-D elon-
gation, as in simple shear flow, affine de-
formation results in flattening of the drop.
Again, arriving at a certain degree of flat-
tening, the interfacial tension will make the
cross-section circular yielding 3-D elonga-
3.2 Stretching 123
tion effectively
(3-10a)
-/2
(3-10b)
so that
e3g/2-l
D= (3-10c)
The effect of the interfacial tension mak-
ing the flattened cross-section circular was
also pointed out by Mikami et al. (1975) and
Khakhar and Ottino (1987). Note that the
assumption of a circular cross-section
[Eqs. (3-7) and (3-10)] causes a slower
decay of B and thus a slower growth of D
compared to the completely affine 2-D drop
deformation with flattening [Eqs. (3-6) and
(3-9)].
As demonstrated in Fig. 3-4, affine de-
formation proceeds much faster in elonga-
tional flow than in simple shear. However,
in practice elongational flows with a con-
stant stretching rate are difficult to sustain
for long times (convergencies are either
finite or yield no throughput).
3.2.1.2 Experimental
A dispersed drop is expected to deform
affinely if the interfacial stress alR is over-
ruled by the shear stress r exerted; in other
words, if Ca C a c r i t . The question is how
large the excess of Cacrit should be in order
to allow neglect of the interfacial stress and
apply the simple rules of affine deformation.
This was investigated experimentally in
an opposed jets device (specially designed
for this research; see Sec. 3.7.2) using test
liquids at room temperature (Sec. 3.7.3).
The flow field in this device is plane hyper-
bolic. A drop of castor oil (Newtonian, vis-
cosity 0.74 Pa s) was instantaneously sub-
124 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
+ 10
o 5
x 3
* 2
1.2
Figure 3-5. Deformation of an initially spherical
drop in steady 2-D elongational (plane hyperbolic)
flow at different ratios of Ca/Cacrit (>1); both liquids
are Newtonian, p = 0.19. The full curve corresponds
to affine deformation, Eq. (3-9 c).
jected to a steady plane hyperbolic flow of
silicone oil (Newtonian, viscosity 4.0 Pa s,
interfacial tension to castor oil
4.1 x 1(T3 N/m). In different runs, the elon-
gation rate was set such that the capillary
number exceeded Cacrit with different
ratios.
In Fig. 3-5 the experimental data are
given together with the theoretical curve for
affine deformation in 2-D elongational flow.
It can be seen that the deformation tends to
Figure 3-4. Evolution of
affine deformation of a
sphere into a (flattened)
thread in simple shear and
2-D elongational flow [Eqs.
(3-6) and (3-9)].
be affine for sufficiently large values of
Ca/Cacriv say beyond an excess of a factor
of 5.
Concerning flattening of the drops due to
the 2-D character of the flow, deformation
of the cross-section is not directly observ-
able in the experimental setup used. The
drop width in the invariant z-direction can
only be estimated from the two measurable
drop dimensions using conservation of vol-
ume.
Initially the drop axis in the invariant
direction remains constant, which indeed
indicates the affine squeezing of the drop.
After a total strain e of a few units the invar-
iant axis starts contracting due to the action
of the interfacial tension. Unfortunately, in
the present experiment a circular cross-sec-
tion is not reached, since after a certain
degree of drop extension the long axis falls
outside the field of view and can no longer
be measured; consequently, it is impossible
to estimate the drop width in the unobserved
direction.
Experiments at a viscosity ratio/? = 0.80
gave similar results. For viscosity ratios far
from unity, affine drop deformation is to be

expected if 7]d<C r\c but not if 7] d 7]c, since
in the latter case the low viscosity matrix is
unable to transfer the shear stress to the
highly viscous drop (Starita, 1972). In the
case of simple shear flow, affine deforma-
tion of a drop with p > 4 is impossible any-
way, since Cacr[t is infinite (Fig. 3-2). In a
practical, complex flow field, however, a
drop once sufficiently deformed (no matter
how) always continues stretching affinely
(except for the ends).
From experiments with various visco-
elastic drops, basically the same results are
obtained, although the Cacr[t excess required
may be considerably higher than a factor
of 5, depending on the elastic contribution
of the rheological behavior of the test liq-
uids (Sec. 3.7.3). This resistance to elonga-
tion is a well-known feature of viscoelastic
liquids: the build up of a large elongational
viscosity in combination with a much small-
er shear viscosity.
In simple shear, affine deformation was
found to occur at an excess of Cacr[t of
greater than 2 (Elemans, 1989), a conclu-
sion that is in principle similar to that from
Figure 3-5. In that particular study, the theo-
retical curve was based on a circular cross-
section [Eq. (3-7 c)], so the effect of initial
flattening was neglected. Taking flattening
into account, the theoretical curve [Eq.
(3-6 c)] lies somewhat higher, so that the
criterion for the required excess of Cacrit
becomes larger than 2 in simple shear too.
3.2.2 Stretching and Folding
The main difference between affine drop
deformation in simple shear and elongation-
al flows can be shown using the definitions
of stretching rate and stretching efficiency
(see, e.g., Ottino, 1989). The stretching rate
e is defined as
= D: mm (3-11)
3.2 Stretching 125
with D the rate of deformation tensor of the
flow and m the local orientation vector of
the drop or thread under consideration. The
stretching efficiency, ef is the ratio of the
actual and its upper bound
D:mm
ef=- (3-12)
D:D
Using the definition of the shear rate
[Eq. (3-2), i.e., y= X /(2DTD)] it follows
that
(3-13)
In steady linear flows, / i s constant while
and hence ef may vary due to a transient
orientation m. In elongational flows, the
orientation of an extending drop is perma-
nently aligned with the principal axis of the
strain rate and is the usual elongation rate;
an affinely deforming drop is stretched
exponentially with the total strain applied.
In the case of 2-D and 3-D elongation, the
shear rate /equals 2 and v 3 , respective-
ly, and thus the stretching efficiency ef is
V(l/2) or V(2/3). In simple shear flow the
orientation m of the extending drop turns
away from the principal direction of strain
rate (45) toward the streamline direction;
thus in the steady case / i s constant while ef
and decay toward zero (Eq. 3-6 d)]. Affine
drop stretching proceeds almost linearly
[Eq. (3-8a)]. In general, the presence of a
rotational component in the flow is the prin-
cipal difference between so-called strong
(mainly irrotational) and weak (mainly rota-
tional) flows (Sec. 3.7.1).
By the repeated reorienting of an extend-
ing drop in simple shear, directing its main
axis perpendicular to the streamlines, the
stretching efficiency can be enhanced: the
drop axis passes through the 45 direction
again and again. Ng andErwin (1981) illus-
trated this using a Couette device with col-
ored strokes of polymer.
126 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
stretching \ folding t \ folding f1
\ /stretching
Similarly, the efficiency of mixing can be
enhanced by a combination of stretching
and folding, the so-called 'bakers'
transformation' (see, e.g., Aref, 1991),
which changes the efficiency of the distrib-
utive mixing from a linear dependence on
the total shear into an exponential depen-
dence. The principle is schematically
depicted in Fig. 3-6. Every fold doubles the
number of filaments or layers (in the 3-D
case) that are stretched simultaneously. The
quality of mixing, characterized by the
interfacial area, the number of layers, or the
reciprocal of the striation thickness, grow
exponentially.
3.2.2.1 The Cavity Flow
A beautiful visualization of stretching
and folding is obtained in the so-called 'cav-
ity flow' (see, e.g., Leong and Ottino, 1989;
Ottino, 1990). The cavity is a rectangular
cell (quasi 2-D) filled with, e.g., glycerin.
The two short walls are fixed while the two
long walls can translate as moving belts. The
deformation of an injected tracer line or
drop (passive: without interfacial tension) is
studied in relation to the protocol of wall
movements. Here, the numerical simula-
tions of some typical experiments are pre-
sented. The simulations were based on the
analytical solution of this 2-D Stokes flow
problem (Meleshko et al., 1991; Meleshko
and Peters, 1996).
Figure 3-7 shows the difference between
steady and periodic flows. In all three cases,
the initial condition is a straight vertical line
through the center of the cell, while the total
^ \ stretching Figure 3-6. The baker's
transformation: stretching
and folding leading to
exponential mixing.
wall displacement applied equals 25 times
the length of the top wall. In example (a),
only the top wall moves and mixing pro-
ceeds linearly. In example (b), both top and
bottom wall move steadily, simultaneously
at the same speed (displacement 12.5 for
each wall): the flow pattern is close to a rigid
body rotation and the tracer line is stretched
less than in the former case. In example (c),
again the top and bottom walls both move,
but now in a periodic way, one after the other
for five periods with a wall displacement of
2.5 during each half period: folds emerge
indicating deterministic chaos with expo-
nential mixing.
From Fig. 3-8 it can be seen how the folds
in the periodic flow example of Fig. 3-7c
originate. The deformation of the tracer line
is monitored during the second of the five
periods. During each half period a steady
streamline pattern holds that closely resem-
bles Fig. 3-7a or its mirror image. So, at the
switching of the walls (e.g., at period 1, 1.5,
and 2) the streamline pattern flips upside
down yielding 'crossing streamlines' in
time: locally, the flow direction changes and
the stretching line is folded.
When analyzing the periodic flow pat-
terns in the cavity, periodic points are of
interest. Periodic points (of order n) are
material points that return to their initial
position after every (n) period(s). They
characterize the local mixing ability of the
flow. Figure 3-9 shows the affine deforma-
tion of two passive drops. Per period the top
and bottom walls are subsequently dis-
placed, each over a distance of three times
the top wall length. The drop on the left is
 3.2 Stretching 127

(a) steady (b) steady (c) periodic

Figure 3-7. Deformation of a passive tracer line in a cavity (initial position: a vertical line through the center):
(a) the top wall moves steadily; (b) top and bottom wall move steadily; (c) top and bottom wall move periodi-
cally one after the other for 5 periods. The total wall displacement is 25 times the top wall length in all three
cases.

1.125 1.25

Figure 3-8. Deformation of a passive tracer line in a cavity. The second period of Fig. 3-7 c is monitored visu-
alizing the origin of folding. The numbers indicate the period.

positioned at an 'elliptic' periodic point of
order 1: during each period it travels around
the cavity as an island without being
stretched significantly. The other drop is
positioned at a 'hyperbolic' periodic point
producing exponential stretching with
folds. The goal in any mixing device is to
generate only hyperbolic points of as low as
possible order. However, the presence of
elliptic and hyperbolic points is coupled so
that islands cannot be avoided completely.
Therefore the objective is to minimize the
size of the unmixed islands. The detailed
analysis of streching and folding can be
combined with criteria for breakup and
coalescence; as discussed in Sec. 3.5.4,
Tj ahj adi and Ottino (1991) combined chaot-
ic flow and thread breakup.
3.2.2.2 Static Mixers
Application of the efficient baker's trans-
formation is realized in most well-designed
static mixers. In a static mixer both the chan-
128 3 Emulsions: The Dynamics of Liquid-Liquid Mixing

0 1 2

Figure 3-9. Deformation of two passive tracer drops in the periodic cavity flow: the left drop is positioned in
an island and remains undeformed; the other one is stretched and folded, quickly covering a large area. The bro-
ken curves at period 0 give the paths of the periodic points.

nel wall and the mixing elements are fixed
and the throughput is generated by a pres-
sure flow. Due to the specific shape of the
mixing elements, the material is repeatedly
stretched, cut, and stacked, closely resem-
bling the stretching and folding mechanism
illustrated in Fig. 3-6. The specific working
principles of four types of static mixer, i.e.,
Multiflux, Ross ISG, Sulzer SMX, and Ken-
ics, are discussed in, e.g., Meijer and Jans-
sen (1994).
3.2.2.3 Dynamic Mixers
The key principles of reorienting and
folding can also be achieved in dynamic
mixers, e.g., extruders, where the motion of
mixing and transporting elements generates
the flow of the material. An example is the
intermeshing, co-rotating twin screw
extruder. During the take-over of the mate-
rial from one screw to the other, folds and
reorientations are (partially) achieved. (The
take-over between the two screws is, in fact,
a space-periodic flow comparable to the
time-periodic cavity flow discussed above).
In an intermeshing counterrotating twin
screw extruder, effectively closed volumina
of material are transported, which is not very
efficient for distributive mixing. However,
a nonintermeshing, counterrotating twin
screw extruder can achieve efficient distrib-
utive mixing due to nonequal screw speeds.
Single screw extruders are inferior for dis-
tributive mixing since, despite the helical
movement of the flow inside the extruder
channel (Ottino and Chella, 1983; Chella
and Ottino, 1985), no reorientations or folds
are introduced. Another practical example
of efficient distributive mixing is the Buss-
Cokneader (see, e.g., Elemans and Meijer,
1990) that couples an axial oscillation to a
tangential rotation, thus weaving and fold-
ing the material during axial transport.
3.2.3 Conclusion
The stretching of dispersed drops pro-
ceeds affinely if the critical capillary num-
ber for drop breakup is surpassed by a fac-
tor of 5 or more. The key point for efficient
distributive mixing of the forming threads
is the combination of stretching and folding
that is realized in periodic flows. If the dis-
persed phase is viscoelastic, stretching is
retarded (deformation less than affine) if (i)

which means that elongational
stresses build up faster than they relax
(# being the relaxation time of the materi-
al) and (ii) e t > 1, i.e., the total strain should
be substantial (this is automatically fulfilled
when a drop is stretched into a thread).
3.3 Breakup
3.3.1 Breakup of a Viscous Thread
at Rest
3.3.1.1 Theoretical
When the original millimeter-sized liquid
drops are extended into long slender fila-
ments due to affine stretching, local radii
are decreased such that the interfacial ten-
sion starts playing a role (active interfaces).
Following the example of Eq. (3-4), the
shear stress r and the interfacial stress alR
become of the same order of magnitude if
the radius of the threads has decreased to
1 \xm
cT/R~l(T2/l(r6 =
(3-14)
a As indicated in Fig. 3-10, these so-called
The interfacial tension tends to minimize
the interfacial area between the two phases.
As a consequence, small disturbances
present at the interface of the liquid cylin-
der grow and finally result in the disintegra-
tion of the thread into a line of drops. Ana-
lyzing the interfacial area of a sinusoidally
disturbed cylinder as a function of distur-
3.3 Breakup 129
bance amplitude and wavelength, it follows
that only disturbances with a wavelength
larger than the initial thread circumference
(X>2KR0) will grow due to a monotonic
decrease of the interfacial area. For distur-
bances with smaller wavelengths the area
(initially) increases upon amplitude growth;
therefore, these disturbances damp.
Rayleigh (1879) was the first to study the
breakup of water jets in air taking into
account the interfacial tension and inertia of
the thread phase. Weber (1931) added vis-
cous stresses in the thread. In 1935 Tomoti-
ka extended the analysis by incorporating
the viscosity of the matrix. In his elabora-
tion for the entire range of viscosity ratios
(thread/matrix) he considered an infinitely
long, viscous cylinder embedded in a quies-
cent matrix of an immiscible, viscous liq-
uid; both liquids are assumed to be incom-
pressible and inertia is neglected. A small
sinusoidal disturbance is imposed on the
interface and the appropriate boundary con-
ditions are prescribed with a normal stress
jump across the interface due to the interfa-
cial tension (see Sec. 3.3.1.3). Solving the
balance equations of mass and momentum
with Newtonian constitutive equation and
boundary conditions leads to the evolution
of the initial disturbance with time.
'Rayleigh disturbances' are typically sinu-
soidal
asin(27iz/A) (3-15)
with the average radius R (in 2-D projec-
tion) smaller than the initial radius Ro
(3-16)
Figure 3-10. Sinusoidal 'Rayleigh dis-
turbance' on a liquid cylinder.
130 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
It is convenient to use the dimensionless
wave number x instead of the wavelength A
x = 2 71 Ro/X (3-17)
The disturbance amplitude a is assumed
to grow exponentially with time
a=aoeqi (3-18)
with growth rate q (s"1)
(3
it "19)
where Q is the dimensionless growth rate of
the disturbance, a function of the wave num-
ber x and the viscosity ratio p, see Fig. 3-11.
The mathematical description of Q (Tomo-
tika, 1935; Palierne and Lequeux, 1991) is
given in Sec. 3.7.5. For wave numbers x >1
(i.e., X<2nRQ), the value of JQ is negative;
these disturbances damp, as explained
before.
Initially, small disturbances of all wave
numbers are present. For a given value of/?,
the maximum of Q versus x gives the fast-
est growing or dominant disturbance that
finally causes breakup (indicated by the
drawn curve in Fig. 3-11). During the entire
process of disintegration, the same distur-
bance remains dominant. This fatal distur-
bance is characterized by the dominant
wave number xm and its corresponding
105
growth rate Qm. Figure 3-12 shows both xm
and Qm as a function of p.
As the growth rate of the fatal disturbance
is known, the time required for breakup of
a thread can be calculated using Eq. (3-18)
from the initial disturbance amplitude a0 to
the amplitude at breakup ah
(3-20)
where it should be noted that Tomotika's
growth rate Q stems from a linear (small
amplitude) analysis. So using the same
value of Q to the point of breakup is a con-
siderable extrapolation that requires verifi-
cation (Sec. 3.3.1.3). Breakup occurs when
the amplitude equals the average radius
{a-R) yieldings
p. /9 / ^ /? s; (1 R9 /? C\ 0 W
Kuhn (1953) proposed an estimation of
the initial amplitude a 0 based on Brownian
motion due to temperature fluctuations.
With T the absolute temperature and k
Boltzmann's constant (1.38 x 10~23 J/K) he
derived
21 kT
(3-22)
871'3/2,
Kuhn's prediction yields values of
a0~10~9 m (both for the model liquids used
Figure 3-11. Dimension-
less growth rate Q as a
function of the wave num-
ber x and the viscosity ratio
p(=r\Jr\c)\ in fact, co(x = 0)
does not exist but lim Q = 0
for all p. xli)

10-5 104 10 -3
and for polymer melts). Other authors
(Mikami et al., 1975) suggest 10"*-10"' m.
In Sec. 3.3.3.2 some comments are given
concerning this somewhat arbitrary param-
eter.
The combination of Eqs. (3-19) through
(3-22) results in
(3-23)
c2
In Eqs. (3-19) and (3-23) the characteris-
tic time scale for cr-driven processes
becomes evident, i.e., tG = ricR0lo, so that
the time can be made dimensionless
at (3-24)
thus
(3-25)
Note that some authors (Stone and Leal,
1989 a, b; Tjahjadi and Ottino, 1991; Stone,
1994) use ta= rjc(l +p) R0/o= (^7C+ Hd) Ro'
in order to account for the higher of the two
viscosities.
For incompressible liquids, the radius of
the droplets formed by thread breakup is
3.3 Breakup 131
Figure 3-12. Dominant
wave number xm and corre-
sponding growth rate Qm of
interfacial disturbances ver-
sus the viscosity ratio
P(=rid/ric).
obtained from the conservation of volume
3[
| 371
^drops - (3-26)
V
For instance, given the viscosity ratio
p = l , jtm = 0.56 (see Fig. 3-12) so that the
droplets formed are twice as thick as the
original thread.
3.3.1.2 Experimental
The breakup of viscous threads in a quies-
cent matrix has been the subject of many
experimental studies (Rumscheidt and
Mason, 1962; Chappelear, 1964; Elmen-
dorp, 1986, Elemans, 1989). Most results,
either on polymer melts or on test liquids at
room temperature, are in agreement with
Tomotika's (1935) linear theory. Therefore
the experimental results on this subject are
discussed only briefly.
Experiments were performed using vis-
cous model liquids at room temperature in
the opposed jets device (Sec. 3.7.2). A drop
is subjected to a plane hyerbolic flow, with
Ca > Cacriv and stretched into a long thread
with a diameter of several tenths of a milli-
132 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
O O o sion, (7.
O O o mer melts (see also Chappelear, 1964). A
Figure 3-13. Disintegration of a Newtonian thread of
0.35 mm diameter (castor oil, r\c = 0.74 Pa s) in a
quiescent Newtonian matrix (silicone oil,
7]c = 0.94 Pa s, <J= 4.1 x 10~3 N/m); photographs
taken every second.
meter. The flow is stopped and the growth
of disturbances is observed and recorded on
videotape. Figure 3-13 shows a few stages
of a typical experiment.
The experimental data show linear depen-
dence in a plot of \n(a) versus time, corre-
sponding to the theory [Eq. (3-18)]. From
the slope of the plots [and Eq. (3-19)], the
dimensionless growth rate Q is determined.
The agreement with the theoretical domi-
nant values Qm (Fig. 3-12) is satisfactory.
Also the experimentally determined wave
number and the theoretical value xm coin-
cide. The total breakup time corresponds
reasonably to the prediction of Eq. (3-23)
which includes Kuhn's estimation of the
initial amplitude (~10~9 m). As recognized
by many researchers, a0 is the most uncer-
tain parameter in the theory.
Elmendorp (1986) (using model liquids at
room temperature) experimentally deter-
mined the growth rate Q of artificially initiat-
ed disturbances with wave numbers deviat-
ing from the dominant one (xm). His results
agree with Tomotika's function Q(x) at the
viscosity ratio under consideration (p= 13).
Measurement of Interfacial Tension
Assuming Tomotika's theory to be valid,
thread breakup experiments can be used to
measure the interfacial tension in liquid-
liquid systems. Determination of the experi-
mental growth rate of the amplitude pro-
vides an estimate of the interfacial ten-
Elemans et al. (1990) applied this concept
(with a theory for viscous systems) to poly-
long polymer filament with diameter 10-50
|im is embedded between two plates of a sec-
ond immiscible polymer. The sample is
melted on a hot-stage under a light micro-
scope. The disturbances are sine waves that
grow exponentially. From the slope of the
ln(a) versus time plot, the growth rate q is
determined. Using Eq. (3-19) with 2=i2m
(Fig. 3-12), the interfacial tension a is
found. The reliability of the experiment is
indicated by the agreement between the
observed wave number and the theoretical-
ly dominant one. The extrapolation of
Tomotika's linear (small amplitude) theory
to large amplitudes is supported by the
numerical calculations presented in the next
section (see Fig. 3-16). The success of the
so-called 'breaking thread method' for
polymer blends, which are generally visco-
elastic, is due to the small deformation rates
(~10~3 s"1), and to the relaxation of stress-
es that were induced during the formation
of the thread (a typical experiment takes
minutes while the relaxation time $-10 s).
Carriere and Cohen (1991) analyzed the
retraction of embedded short fibers back to
a sphere in order to estimate the interfacial
tension between molten polymers. How-
ever, the underlying formulae are partly
empirical, which is not the case for the
breaking thread method. Tjahjadi et al.
(1994) present ready-to-use polynomial fits
(based on full numerical simulations) to

estimate the interfacial tension from both
breaking threads and retracting short fibers.
In Fig. 3-13 small satellite drops can be
seen in between the main drops. These are
formed in the last stage of the process due
to the (fast) growth of Rayleigh disturban-
ces on the fine filaments (alR large) between
adjacent drops. Tjahjadi et al. (1992)
numerically investigated the formation of
satellite droplets. They found unique radius
distributions of satellite and sub-satellite
generations for various viscosity ratios. A
general conclusion is that as the viscosity
ratio increases, fewer (but larger) satellites
emerge due to viscous damping of internal
motions.
3.3.1.3 Numerical
Numerical simulations of viscous thread
breakup in a quiescent matrix were per-
formed using the finite element method
(FEM). For the inertialess flow of incom-
pressible liquids the balance equations of
mass and momentum reduce to
V u=0 (3-27)
with V the gradient operator and u the veloc-
ity vector and
V o=0 (3-28)
with G the Cauchy stress tensor
O = -p\+i (3-29)
split into the contribution from the ambient
pressure p and the extra stress tensor T that
is given by a constitutive equation. I is the
unity tensor. In this section viscous flow is
considered, so the Newtonian constitutive
equation holds
x = 2riD (3-30)
where r\ is the viscosity. Although the flow
problem is transient, a quasi-steady
approach is applied (small Reynolds and
3.3 Breakup 133
Strouhal number): the steady solution of the
velocity field is used to displace the mesh
during the next time step. Due to axisym-
metry, the calculation can be performed in
cylindrical coordinates (quasi 2-D). Fig-
ure 3-14 shows a typical mesh with boun-
dary conditions. In the radial direction the
unbounded matrix (with zero velocity at
r=oo) is approached by 10 times the undis-
turbed thread radius. In the axial direction a
repeating unit is taken with symmetry at the
ends. As a consequence, mass is conserved
in both the thread and matrix phases and at
both ends of the thread the interface is par-
allel to the thread axis. Hence the distur-
bance wavelength A is restricted by the fact
that the mesh length must cover multiples
of A/2.
At the interface between thread and
matrix, the velocity and the tangential stress
are continuous (no slip condition). How-
ever, the interfacial tension cr, the driving
force for the evolution of disturbances,
causes a normal stress jump
+ (3-31)
with A presenting the difference between the
thread and the matrix phase, n the vector
normal to interface, and R^ and R2 the main
radii of curvature: R1 is the radius in the r-z
plane and R2 lies in a perpendicular plane.
They are given by the profile of the inter-
face R(z) (Levich, 1962)
/?i = and
d2R/dz2
=-R (3-32)
The position of the interface is deter-
mined by the kinematic condition
(3-33)
dt dz
134 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
on A, B : u = 0, = 0
dz
on C v = 0,
dr
on D u = 0,
In fact, Eq. (3-31) is an elastic constitu-
tive equation for the interface, i.e., at any
moment the normal stress jump is explicit-
ly given by the shape of the interface.
To solve the obtained set of equations, a
mixed (X, u, p) formulation is used (Baai-
jens, 1993). The stress and velocity fields
are interpolated quadratically while the
pressure field is bilinear. Moreover, the
interpolations for stress and pressure are
discontinuous across the element boundar-
ies. The position of the interface is found by
solving Eq. (3-33) with a so-called stream-
line upwind Petrov Galerkin (SUPG) algo-
rithm (Johnson, 1987), while the interfacial
tension is computed according to Keunings
(1986).
Special attention is paid to the displace-
ment of the mesh during each time step. A
Lagrangian (material) mesh treatment leads
to unacceptable deformation of the ele-
ments, while a Eulerian (spatial) mesh gives
the complication that the position of the
interface does not coincide with nodal
points and has to be interpolated. Therefore,
an arbitrary Lagrange Euler (ALE) mesh is
used that allows nodes to move radially but
not axially. Thus the interface coincides
with nodal points while deformation of
the elements in the axial direction is sup-
pressed. Each time step is normalized such
that the largest node displacement is only a
fraction of the smallest local thread radius.
11=0
v = 0
Figure 3-14. Finite element mesh (axi-
symmetric) with boundary conditions.
So, as the amplitude grows, the time step
decreases.
The FEM code used was written in Mat-
lab (1993), which is flexible and fast while
developing the code, but has the intrinsic
disadvantage of not being very efficient and
fast while performing the final calculations.
Results
The calculations on viscous systems were
performed as a first step towards viscoelas-
tic threads (Sec. 3.3.2.2). So some of the
analytical results of Sec. 3.3.1.1 were veri-
fied. Figure 3-15 shows the simulation of a
growing disturbance on a viscous thread of
1 mm diameter; both thread and matrix vis-
cosities are 1 Pa s and the interfacial
tension <7= 1(T2 N/m. Initially, half a sine
wave is prescribed with the dominant wave
number according to Tomotika (1935)
(Fig. 3-12) and an amplitude ao/Ro= 10~2.
Although the figure shows two waves, the
numerical simulation involved only half a
wave.
Figure 3-16 shows the amplitude growth
with time for the calculation of Fig. 3-15
(solid line). The dashed line gives the pre-
diction according to Tomotika's linear
(small amplitude) analysis up to
alR0 = 72 / 3, which is the amplitude at
breakup in the case of a perfect sine wave
 3.3 Breakup 135

[Eq. (3-21)]. The calculated exponential to the point of breakup, i.e., up to a/R0 = 0A
growth rate agrees with the dominant the relative error in the amplitude is less than
growth rate Qm from Fig. 3-12. Moreover, 4%, while at a/R0 = 0.6 it has only increased
Tomotika's analytical prediction derived to 10%. This verification supports the
from small amplitudes remains valid almost extrapolation of Tomotika's linear theory
for the measurement of interfacial tension,
the so-called breaking thread method (see
Sec. 3.3.1.2 and Elemans et al., 1990).
t = 0 [s] The error in Tomotika's theory at large
amplitudes is due to the fact that near the
point of breakup nonlinear effects become
3 lllil ifiil= ijilh: important and the disturbance is no longer
a perfect sine wave: in the necks it flattens
somewhat and satellite droplets emerge (see
4 Illlilfi illflff: HtlHfi IIIHIIi Fig. 3-13). The sinusoidal amplitude aloses
its sense. In the FEM calculation, the time
step (initially 0.1 s) rapidly decreases as the
point of breakup is approached, i.e., the cal-
culation stagnates in time. For a good sim-
ulation of the last stage, local mesh refine-
ment is necessary in the neck regions. Tja-
hjadi et al. (1992) performed detailed sim-
ulations of the formation of satellites in vis-
Figure 3-15. Disturbance growth with velocity fields cous systems using the boundary element
on a viscous thread in a quiescent viscous matrix; method.
rjd = r\c = 1 Pa s, a= 1(T2 N/m, 2R0 = 10"3 m, a^RQ =
10~2. Only half a wavelength was computed; the veloc- Initiating a disturbance amplitude CXQ/R0
ities are normalized separately for each picture. smaller than 10~2 only increases the time until

10

Tomotika (1935)
FEM calculation

10

Figure 3-16. Amplitude

growth in the system of Fig
3-15.
136 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
breakup; the exponential growth rate is still
the same. Another point is the pre-
scription of the dominant wave number
according to Tomotika. Variation of the wave
number x (= 2 nR0/X) was carried out by
varying the axial length of the FEM mesh; as
mentioned, the symmetry boundary condi-
tions imply that the axial length of the mesh
covers multiples of A/2. Variations of x
around Tomotika's dominant wave number
xm revealed that the maximum growth rate Q
indeed occurs exactly at xm. If a sine wave
with x=xm/3 (i.e., ^ = 3 ^ ) is prescribed
initially, this wave spontaneously rearranges
into three waves; i.e., the dominant wave
overrules nondominant ones. The expected
dominant wave also emerges spontaneously
when random noise is the initial disturbance.
Finally, the viscosity ratio p (= 77d/7]c) was
varied over the range 1(T 2 -10 2 . The growth
rate Qm at the dominant wave number xm
agreed with the theoretically predicted p
dependence (Fig. 3-12).
In summary, the numerical simulations
agree with the linear (small amplitude) the-
ory of Tomotika (1935), which is able to
describe the experiments (Sec. 3.3.1.2).
Moreover, it has been shown that for a quick
(algebraic) calculation, the small amplitude
theory can be extrapolated until the point of
breakup. A useful extension of the present
FEM program would be a nonsymmetry
boundary condition at one of the thread ends
allowing an arbitrary slope of the interface
and thus decoupling the wavelength from
the mesh length. The problem with a non-
symmetric boundary is that the boundary
condition is unknown. A second extension
could be to impose an external flow field on
the matrix (in view of Sec. 3.3.3); in that
case, a complication arises from the extreme
change in the aspect ratio of the deforming
mesh: the wave number (x c RIX) may eas-
ily decrease by several decades before the
point of breakup is reached.
3.3.2 Breakup of a Viscoelastic Thread
at Rest
3.3.2.1 Experimental
In contrast to purely viscous systems, the
disintegration of viscoelastic threads is less
well modeled. At least, no general theory
exists, which is due to the complexity of the
problem and the diversity of possible con-
stitutive equations to be used. Most of the
literature on the breakup of viscoelastic jets
is confined to jets of polymer solutions in a
gaseous matrix (Bousfield et al., 1986;
Goren and Gottlieb, 1982; Schiimmer and
Thelen, 1988). Less research incorporates a
viscous matrix phase (Elmendorp, 1986;
Chin and Han, 1979, 1980; Palierne and
Lequeux, 1991). Although the viscous the-
ory may be applied successfully to polymer
melts under specific conditions (e.g., the
breaking thread method, Sec. 3.3.1.2), poly-
mer solutions are found to exhibit more
extreme elastic effects.
Experiments were performed using
model liquids in the opposed jets device
(Sec. 3.7.2). The thread phase was visco-
elastic and consisted of a dilute (homogene-
ous) solution of poly aery lamide in a viscous
corn syrup/water mixture. The rheological
data of four such thread phases were mea-
sured and fitted to the Phan-Thien Tanner
constitutive equation (Sec. 3.7.3). Roughly,
the shear viscosity of the different thread
phase liquids used was of the order of
1 Pa s, and the major relaxation time about
15 s (Figs. 3-50 and 3-51). The continuous
phase consisted of Newtonian silicone oil
with viscosity in the range 0.1 - 1 0 Pa s.
A drop is stretched into a long thread and
then the flow is stopped. After some time,
dumbbell shapes appear (Fig. 3-17) rather
than sinusoidal disturbances. The bulbs are
not distributed uniformly and shift along the
thread in either direction. Hence there is no
sense in defining a wavelength and an

Figure 3-17. Disintegration of a 0.07 mm thick vis-
coelastic thread (80% corn syrup/20% water/0.01%
polyacrylamide, Sec. 3.7.3) in a quiescent Newtonian
matrix (silicone oil, r\c = 2.0 Pa s, <j=18xl0" 3
N/m); photographs taken every 3 s.
amplitude. Instead of growing exponential-
ly, the disturbance growth almost stagnates.
Very slowly liquid drains from the filaments
into the bulbs. If the filaments have thinned
considerably, a second generation of dumb-
bells appears. Once a filament breaks, the
force balance is disturbed and loose filament
ends quickly retract towards bulbs that are
still connected. Small and big drops shift
and, occasionally, flow together. This
dynamic phenomenon proceeds until all fil-
aments have broken. The four different vis-
coelastic liquids used gave similar results.
The explanation of the typical breakup
behavior of these viscoelastic threads lies in
the build up of orientational stresses. These
may drastically enlarge the elongational vis-
cosity of the viscoelastic thread phase
(strain thickening) and hence slow down the
elongational flow in the filaments. Stresses
may build up both during the formation of
the thread (prior to the breakup process) and
during the drainage of the filaments (in the
3.3 Breakup 137
breakup process itself). As already pointed
out, viscoelastic effects are expected to be
significant if (i) the Deborah number
De = i}>\, i.e., stresses build up faster
(time scale lie) than they relax (time scale
#) and (ii) t > 1, i.e., the total strain is sub-
stantial. During formation of the thread,
both criteria are fulfilled since ft ~ 10 s and
~ 0.1 s"1 so that De ~ 1, while it is evident
that the total strain is substantial. Hence
upon cessation of the flow, the starting point
of the actual thread breakup experiment,
considerable orientational stresses are
present. The disintegration process itself
may cause additional stress build up local-
ly where a large deformation (rate) is
present, i.e., preferentially in the filaments.
In Sec. 3.3.2.2, the development of local
stresses in a disintegrating viscoelastic
thread is studied in more detail using the
finite element method discussed in
Sec. 3.3.1.3 with the Phan-Thien Tanner
constitutive model.
Using the above-mentioned criteria, vis-
coelastic effects are expected to be negli-
gible in the thread breakup experiments of
Elemans et al. (1990) using polymer melts.
The relaxation time is typically # ~ 1 0 s ,
while disintegration of the threads takes
minutes so that De ~ 10 -1 and pre-built up
stresses easily relax before disturbances
start to grow substantially. Next, the disin-
tegration process itself proceeds too slowly
to build up stresses to a significant extent.
In contrast, fibers formed in the dynamic
mixing process in extruders are thinner, typ-
ically 1 |im, and breakup occurs within sec-
onds, just as in the case of the model liquids
(De~l). Still, elastically induced dumb-
bells (to the extent as in Fig. 3-17) are rare-
ly observed in polymer blends (e.g., Ele-
mans, 1989) where, moreover, both thread
and matrix are viscoelastic.
Few explanations are possible for the
nonuniformity of the disturbances. Firstly,
138 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
there is always some irregularity in the def-
ormation history along the thread (e.g., due
to small diameter fluctuations). Conse-
quently, for a viscoelastic fluid the stress
distribution is irregular, which may cause a
nonuniform disturbance pattern. Another
explanation is suggested by Milliken et al.
(1993) and Stone (1994). Polymer mole-
cules added in order to make the model liq-
uids viscoelastic may accumulate at the
interface and act as a surfactant. Inhomo-
geneities in the interfacial concentration of
this surfactant (and thus of the interfacial
tension) may easily lead to nonuniform
breakup patterns.
Measurement of Elongational Viscosity
As mentioned, the elongational viscosity
is a crucial material property in the breakup
of viscoelastic threads. It is also well known
that for viscoelastic liquids the Trouton ratio
Tjjrjy (the ratio of elongational and simple
shear viscosity) can be far beyond 3, the
value found in the case of a viscous liquid.
Rheological characterization of model liq-
uids, however, is mostly done in simple
shear. Measurement of r] is quite difficult;
steady state values are rarely obtained (e.g.,
Sridhar etal., 1991; Bulters and Meijer,
1990). Among the many different tech-
niques used, the one studied by Schiimmer
and Tebel (1983) is worth mentioning in
view of the topics dealt with in this chapter.
They use the disintegration of a viscoelas-
tic jet in air to estimate the elongational vis-
cosity, defined as
Tl = Tzz~Trr (3-34)
with rzz and xrr the stress components in the
axial and radial directions and the elonga-
tion rate. The dumbbell shape as shown in
Fig. 3-17 is idealized: the filaments are con-
sidered as perfect cylinders (radius Rf) and
the bulbs as spheres (radius Rb). A single fil-
ament exhibits 3-D elongational flow and is
considered as a test specimen. The (uncon-
trollable) elongation rate is generally not
constant with time, but can easily be meas-
ured
= -2Rf/Rf (3-35)
The stress difference (tzz- Trr) can be esti-
mated from the difference in the interfacial
pressure jumps between the bulb and the fil-
ament. (The assumption is made that the
ambient pressure in the matrix is constant,
which will be valid if the matrix viscosity is
not too large.) The interfacial pressure jump
is given by the Laplace equation [equivalent
toEq. (3-31)]
(3-36)
where Rx2 a r e the main radii of curvature.
A force balance leads to
ZZ rr
J? J?
(3-37)
Kb
and hence
= a/Rf-2(T/Rh
(3-38)
-2RfIRf
Following Schiimmer and Tebel, the
elongational viscosities were estimated
from the disintegration of viscoelastic
threads in a quiescent viscous matrix
(instead of a gaseous matrix). In a typical
experiment increases to about Is" 1 ; the
elongational viscosity builds up with time
and the Trouton ratio grows to the order of
103. Unfortunately, a steady state is not
reached: keeps verying during the time of
the experiment, which is limited to about 5 s
due to the resolution in measuring Rf. More-
over, the different pre-stretching in each
experiment prohibits accurate reproducibil-
ity. Trouton ratios of 10 2 -10 3 are also pre-

dieted by the Phan-Thien Tanner model
using the material parameters obtained in
simple shear. This prediction encourages the
use of the Phan-Thien Tanner model for
these liquids.
3.3.2.2 Numerical
The growth of disturbances on a visco-
elastic thread in a quiescent matrix was
numerically simulated using the finite ele-
ment technique as used for the viscous
threads (Sec. 3.3.1.3). A number of features
are identical (geometry with boundary con-
ditions, ALE mesh displacement, and the
incorporation of interfacial tension), and
some are different (the constitutive equa-
tion, of course).
As the constitutive equation, the Phan-
Thien Tanner model was used with the extra
stress tensor [see Eq. (3-29)]
(3-39)
/=!
consisting of one viscous 'solvent' mode Xs
and n viscoelastic modes X,. The solvent
contribution (in fact, a viscoelastic mode
with relaxation time $ = 0 ) is given by
Xs = 2?7S D (3-40)
with ?7S the solvent viscosity. The extra
stress contributions X, are given by
(3-41)
'li
with i}j the relaxation time, fy the viscosity,
and , the nonlinearity parameter of mode
number /. D is the rate of deformation ten-
sor and v represents the Truesdell or upper-
convected time derivative
v tion is used. The elements have quadratic
= x-L-x-x-Lc (3-42)
with L the velocity gradient tensor and t the
material time derivative related to the spa-
3.3 Breakup 139
tial time derivative by
(3-43)
dt
Multiple modes are necessary to describe
measured rheological data over a certain
range of deformation rates. The Phan-Thien
Tanner model includes the Oldroyd-B
model (, = 0), the upper-convected Max-
well model (, = 0 and rjs = 0), and the New-
tonian or viscous model (, = (), #, = 0, and
7]s = 0). The nonlinearity parameter z is
responsible for the shear thinning behavior
of the simple shear viscosity and, moreover,
it limits the steady state elongational viscos-
ity which goes to infinity [as - (2&)~l] in
both the Oldroyd-B and the upper-convect-
ed Maxwell model.
The numerical technique is based on an
operator splitting methodology in order to
handle the time derivatives of the stress ten-
sor, see Baaijens (1993). In this algorithm,
the stress of a given material point at its pre-
vious position (p) at the previous time level
(t-At) is computed first and is subsequently
used in a regular mixed (X, u, p) formula-
tion. For the ALE method applied here, the
'old' stress Tp is obtained by solving
se(t-At,t) (3-44)
with ug the grid velocity. Both time and
space are discretized in finite elements
yielding so-called 'space-time slabs'. The
time discretization is piecewise continuous,
but discontinuous across the space-time
slabs, allowing each time step to be analyzed
subsequently; a constant in time approxima-
interpolation functions for stress and veloc-
ity and a bilinear pressure. Stress and pres-
sure are both discontinuous across the ele-
140 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
ment boundaries. Consequently, they can be
eliminated on the element level, thereby
reducing the number of unknowns of the
resulting set of equations substantially.
Results
Although the model liquids used experi-
mentally have been characterized by a
5 mode Phan-Thien Thanner fit, excessive
computation times restrict the number of
modes to only 1 plus the 'solvent mode'.
(The computation time is directly propor-
tional to the number of modes.) An accept-
able one-mode fit for test liquid cs
80/20/0.01 (Sec. 3.7.3), used as the visco-
elastic thread phase in the experiment of Fig.
3-17, is given by 7]s = O.6Pa s, 77! = 0.4 Pas,
#! = 15 s, and ex = 0.01. The matrix was mod-
eled as a viscous liquid with ?7C= 1 Pa s. The
interfacial tension <7 = 10~2N/m and the
thread diameter 2R0 = 1 mm.
Figure 3-18 shows a typical flow simula-
tion. The axial length of the mesh is taken
as 2X^ with Xm the theoretical dominant
wavelength of a comparable viscous system
(using p = fld/r]c = (7]s+J,r]i)/Tic)m This was
done to allow the thread to develop a (non-
periodic) disturbance of nearly arbitrary
length. The disturbance was initiated as ran-
dom noise with amplitude a^R0 = 10~2. The
initial stress condition in the thread was esti-
mated from a typical experiment where a
thread is formed by a steady elongational
flow (prior to t = 0 in the present simulation)
with e = 0A s"1. Using the Phan-Thien Tan-
ner model with the present material param-
eters, the steady state stress component
Tzz = 29 Pa, uniformly in the thread. In the
matrix, modeled as a viscous liquid, an
initial stress condition makes no sense (#= 0
s). The disturbance is irregular and at the left
a long neck develops suggesting a dumbbell
shape as in the experiments (Fig. 3-17).
t = 0 [s]
4- ^ ~Z t J 1 > ;'.':i:v
6.4 .rr^'t ' 1 i ) ;J~J=-~~ J
>>
8.4 : : : : = = = = = = : rr ;r
L
' . ' . ; ; - .
4-4-4
10.4
10.9
Figure 3-18. Disturbance growth with velocity fields
on a viscoelastic thread (PTT with rjs = 0.6 Pa s,
rix = 0.4 Pa s, #! = 15 s, { - 0.01) in a quiescent vis-
cous matrix (j]c = 1 Pa s); a- 10~2 N/m, 2R0 = 10~3
m. Uniform initial stress xzz - 29 Pa in the thread. The
velocities are normalized separately for each picture.
Arrows indicate the positions where zzz is monitored
(Fig. 3-19).
In Fig. 3-19 the viscoelastic extra stress
component TZZ is monitored at two positions
on the thread axis, as indicated by the arrows
in Fig. 3 -18: one in a final neck and the other
in a fat bulb (solid curves). The dashed curve
indicates relaxation of the initial stress level
at a fixed point, i.e., in the absence of a
deformable interface. Initially, the stress
from the FEM simulation relaxes just like at
the fixed point. Once the interface starts to
deform significantly (after about 6 s), stress
relaxation in the bulb is enhanced due to the
compression flow. In the neck the flow is
elongational and new stresses build up.
Large Trouton ratios (rj/77y) are reached:
values of about 10 2 -10 3 , which qualitative-
ly agree with the results from the measure-
ment of 77, as discussed in Sec. 3.3.2.1.
(Note that the stresses in Fig. 3-19 are mon-
itored at specific positions in space and do

not track a single material point, as is nec-
essary to calculate the true Trouton ratio.)
Due to this high local flow resistance, the
flow in the thinner sections slows down and
the onset of filament formation can be seen.
Similar results were found by Bousfield
et al. (1986), although they considered a vis-
coelastic thread surrounded by a gas instead
of a viscous liquid. Compared to a viscous
thread they report: (i) an initial retardation
of the growth rate upon the prescription of
a tensile stress, (ii) then a stage of exponen-
tial growth, and (iii) finally necking and
flow stagnation due to a new build up of
elongational stresses. Starting with a zero
initial stress, they find an initial enhance-
ment of the growth rate with respect to vis-
cous systems, followed by the same final
stress build up and flow stagnation.
3.3.3 Breakup of a Viscous Thread
During Stretching
3.3.3.1 Theoretical
During the disintegration of a viscous
thread in a quiescent matrix, one distur-
3.3 Breakup 141
Figure 3-19. Solid curves:
evolution of the viscoelas-
tic extra stress component
Xzz in the simulation of
Fig. 3-18 at the two posi-
tions indicated. Dashed
curve: relaxation of the
initial stress at a fixed
point, i.e., ignoring the free
interface.
bance wavelength is dominant (the one with
the fastest amplitude growth) and leads to
breakup. On an extending thread, however,
the waves are continuously stretched. Hence
at any moment another disturbance wave-
length is dominant and the moment of break-
up is postponed compared to the same thread
in a quiescent matrix. Breakup occurs as
soon as the amplitude of a disturbance is
magnified such that it equals the continu-
ously decreasing mean thread radius.
In 1987 Khakhar and Ottino extended the
theory for breakup of an infinitely long liq-
uid cylinder in a 3-D elongational flow
(Tomotika, 1936; Mikami etal., 1975) to
general linear flows. Any linear flow can be
decomposed into a 3-D elongation and a
shear component. They showed that under
some circumstances the shear part may be
neglected so that the only relevant flow
parameter in the analysis is the (orientation
dependent) stretching rate e {- D mm). It
is convenient, however, to make the time
dimensionless with respect to the (orienta-
tion independent) shear rate y |= X/(2D : D) 1
* = yt (3-45)
142 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
Consequently, the ratio Ely shows up
and hence the stretching efficiency ef
[Eq. (3-13): ef = ^2e/y]. As discussed
in Sec. 3.2.2., ef is constant in steady 2-D
or 3-D elongational flow [ef= \j(V2) or
v (2/3) respectively], while it decays
towards zero in steady simple shear flow
(due to rotation of the extending thread
towards the streamline direction).
The main principle of the breakup process
at a constant stretching rate is illustrated in
Fig. 3-20. Disturbances of all initial wave-
lengths Ao/ (or wave numbers xOi = 27t/?/AO/)
evolve with time. At the same time, the
wavelengths increase and the thread radius
decreases (due to stretching). Section 3.7.4
outlines the equations governing the evolu-
tion of an initial disturbance amplitude a0
as a function of material properties, flow
conditions, and geometry. In general, the
disturbance amplitude first stays at the noise
level ((XQ), then it grows for a while and
damps again, back to the noise level. The
disturbance having one specific initial
wavelength appears to be fatal and causes
breakup. The amplitude of this disturbance
starts growing at the critical time r*rit, where
the thread radius has decreased to Rcriv After
the growth time * the amplitude equals the
ln(R/a0)
and
ln(a/a 0 )
t x
01 <x 02 <x 03 / 1
0 . / . /
momentary mean thread radius at the break-
up time f *; the extending thread breaks leav-
ing a line of drops with radius Rdrops.
For a constant stretching rate (i.e., the
external flow is either steady 2-D or 3-D
elongational), the breakup process was ana-
lyzed over a broad range of the relevant
parameters. The results are condensed fur-
ther than was done by former authors.
The independent variables are reduced to
only two relevant dimensionless groups:
77ca0/o"and/?, while only three dependent
variables are of interest: Rcv{t/a0, ^droPsM)>
and eft*. In fact, all lengths are scaled with
respect to the initial amplitude a0. More-
over, the main results of the analysis are
insensitive to the initial thread radius Ro: in
Fig. 3-20, Ro may be anywhere left of Rcrii;
Ro is only relevant for the stage of affine
deformation down to Rcr{t (> t*rii). Fig-
ures 3-21, 3-22, and 3-23 give the con-
densed results (see also Janssen and Meijer,
1993); all other dependent variables can be
derived from these plots. For instance, the
total breakup time
~~ *crit " ^g ~~
ef
23/2 j + ef *
^rit
(3-46)
,/breakup
/
1
* /
t -^
V /
- . 01
Figure 3-20. Evolution of
the undisturbed radius R of
a thread that is extending at
a constant rate (dashed
line) and of the amplitude a
of disturbances with differ-
ent initial wave numbers
(solid curves).

io-9
io- 9 IO-S io- 7 io- 6 io- 5
T| c 6a 0 /o
In a flow of constant stretching rate (with
known , ef, and y), the breakup time
fb(= t%ly) of a thread (with known p, 7]c, <7,
a0, and Ro) can be calculated from Eq.
(3-46) using the theoretical values of Rcrii
and eft* from Figs. 3-21 and 3-23. The
resulting drop size is obtained from
Fig. 3-22. Figures 3-21 and 3-22 look quite
similar since /? drops and Rcrh are coupled via
[i.e.,
3
c r i t ], which is
nearly constant (~1) in all cases.
3.3 Breakup 143
Figure 3-21. Dimension-
less critical thread radius
indicating the start of
growth of the disturbance
that leads to breakup of a
constantly stretching thread
as a function of the dimen-
sionless stretching rate; the
parameter is the viscosity
ratiop(=77 d /i7 c ).
Figure 3-22. Dimension-
less drop radius resulting
from thread breakup during
stretching at a constant rate
as a function of the
dimensionless stretching
rate; the parameter is the
viscosity ratio.
io- 4 io- 3 io- 2 io- 1 io io 1
From Figs. 3-21 and 3-22 it is evident that
upon an increase in the stretching rate the
thread is thinned further before breakup
occurs, which results in smaller drops. The
influence of the viscosities is somewhat dif-
ficult to determine from the figures since rjc
is included both in the horizontal axis and
in the parameter p(=T/d/r]c). For the
descending straight lines the proportional-
ity RdrovJa0oc(ncea0/cj)-0-9xp-0A5 holds
(see also Tjahjadi and Ottino, 1991), so that
144 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
eftg
^drops (^d^c) 45- A higher viscosity of
either phase retards interfacial motions and
postpones the moment of breakup leading
to smaller drops. At constant 7]c, any
increase in the viscosity ratio/? yields small-
er drops. Only for large values of rica/0(J
is there an optimum viscosity ratio for
obtaining the smallest drop size.
A physical lower limit for the drop size
arises from the fact that the mean thread
radius cannot decrease below a0. Kuhn's
(1953) prediction of a 0 [Eq. (3-22)] yields
values of about 10~9 m. Although Mikami
et al. (1975) suggest 10~ 8 -l(r 7 m, Kuhn's
estimate appears to be satisfactory for
the experiments of Sec. 3.3.3.2. From
Figs. 3-21 and 3-22, the value of a0 is not
as important as it seems, since a0 is includ-
ed in both the horizontal and the vertical
axes: effectively, RCTit and Rdrops <* a00A on
the linear descending parts of the plots; only
at the apparent bottom levels (for large p)
does this change to Rcrii and ^ d r o p s = a0.
In steady simple shear flow, the results are
more complicated since and hence ef
decay (as know functions) with time. Kha-
khar and Ottino (1987) elaborated this case,
but the results cannot be condensed as far as
Figure 3-23. Flow type
independent growth time of
the fatal disturbance that
leads to breakup of a con-
stantly stretching thread as
a function of the dimen-
sionless stretching rate; the
parameter is the viscosity
ratio.
in Figs. 3-21, 3-22, and 3-23, since the
initial thread radius and orientation appear
as extra independent variables. Moreover,
in simple shear flow it has to be checked
whether the influence of the shear compo-
nent on the disturbance is negligible under
the present conditions. Nevertheless, a num-
ber of trends can be derived from their
results (Fig. 8 from Khakhar and Ottino,
1987). The drop size Rdrops oc y'03 rather
than 7~ 9 in steady elongation, its depen-
dence on p is less, and the resulting drops
are bigger than in elongational flow of equal
shear rate (in 2-D elongation y=2e).
3.3.3.2 Experimental
In contrast to thread breakup in a quies-
cent matrix and drop breakup under quasi-
equilibrium conditions, the breakup of an
extending thread has rarely been studied
experimentally (Mikami et al., 1975).
Therefore the results from the above analy-
sis were verified using model liquids in an
opposed jets device generating plane hyper-
bolic flow (Sec. 3.7.2). Castor oil
(7]d = 0.74 Pa s) was used as the drop phase,
while the continuous phase consisted of dif-

ferent grades of silicone oil; the interfacial
tension amounted to 4.1 x 10~3 N/m. A drop
of a few millimeters diameter was subject
instantaneously to a steady elongation rate,
sufficiently high to deform it affinely (see
Sec. 3.2.1.2). The original drop was extend-
ed sufficiently to regard the thread formed
as infinitely long and to neglect end effects.
Disintegration of the thread during stretch-
ing was studied using a microscope and
video recordings.
Mikami et al. (1975) compared some
experimental data to calculated values;
however, not the final drop size. Fig-
ure 3-24 compares experimental drop sizes
to calculated ones derived from Fig. 3-22.
The scatter in the experimental data is due
to nonuniformity of the breakup process and
to satellite droplets emerging between the
main drops. The relevant drop size was aver-
aged over many experiments. The influen-
ces of T]ce/(jandp are predicted properly by
the theory. The value of 10~9 m for a0
(Kuhn's estimate) gives reasonable agree-
ment. A better fit is obtained using 1(T10 m;
however, such small disturbances are phys-
ically unrealistic. Moreover, the agreement
10-4
3.3 Breakup 145
is remarkable anyway since the theory is
based on an extrapolation of a linear (small
amplitude) analysis.
As well as the final drop size, the experi-
mental breakup time tb was compared to cal-
culated values (Fig. 3-25). The separate
contributions of fcrit and tg cannot be mea-
sured because it is experimentally impos-
sible to detect the critical point where the
fatal disturbance starts growing (see Fig.
3-20). Therefore only the total breakup time
is checked. The measured value spans from
an (arbitrary) initial thread radius Ro to the
point of breakup. The calculated breakup
time is obtained from Eq. (3-46) with the
experimental value of Ro and the theoretical
values of Rcrit and ef t* (from Figs. 3-21 and
3-23). So in fact the comparison of mea-
sured and calculated breakup times verifies
the theoretical plots of Rcri/a0 and eft* (the
assumption of affine stretching is certainly
valid in the experiments). With ao= 1CT9 m,
the agreement is again satisfactory, while a
better fit is obtained by increasing a0 to 10~8
m (rather than by decreasing a0 like in
Fig. 3-24). In the experiments tg is typical-
ly about 2 s. If RQ Rcrit, as is the case in
Figure 3-24. Experimental
(symbols) and calculated
(lines) drop sizes as a func-
tion of the flow parameter
r\clo in steady plane
hyperbolic flow; in the cal-
culations OQ = 10~9 m (solid
lines) or 10~10 m (dashed
lines); the parameter is the
viscosity ratio p (= T\Jr\c).
146 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
Figure 3-26. Collision of a drop onto an extending
thread; early 'scission' leads to end-pinching produc-
ing relatively large drops. Both liquids are viscous
with p = 0.35; the photographs were taken every 2 s.
most practical situations, tg becomes negli-
gible with respect to /crit and the total break-
up time can be approximated by affine de-
formation only [the first term of Eq. (3-46)
with Rcrit from Fig. 3-21].
Figure 3-25. Experimental
(symbols) and calculated
(curves) breakup times as a
function of the flow param-
eter rjc elo in steady plane
hyperbolic flow; 2R0 = 1(T3
m; in the calculations
(XQ = 1CT9 m (solid curves)
or 1CT8 m (dashed curves);
the parameter is the viscos-
ity ratio.
In practice, drop sizes are generally larg-
er than predicted by theory. Apart from
coalescence of the drops formed, one of the
possible reasons is the collision of dispersed
drops (or threads) onto an extending thread,
as illustrated in Fig. 3-26. Locally, a large
disturbance amplitude is imposed that leads
to early breakup of the thread into two parts.
Subsequently, end-pinching (Stone and
Leal, 1989 a, b) produces drops that are larg-
er than in the case where they were produced
by disintegration via uniform capillary
waves. To incorporate something of this
effect in the modeling of mixing, an effec-
tive a0 could be introduced having a prob-
ability that depends on the volume fractions,
the viscosity ratio, and the interfacial ten-
sion of the liquid phases. Even at low vol-
ume fractions the phenomenon may
increase the drop size significantly.
3.3.4 Drop Breakup in Viscous Systems
After stretching and disintegration of the
threads into drops, the drops (with R of the
order of micrometers) may finally be sub-
ject to further deformation and eventual
 3.3 Breakup 147

breakup since Ca ~ Cacriv Whether breakup 1

, . , , ,
occurs or not depends on the local velocity leading to breakup Ca
X
0.8
gradient and the type of flow, the viscosity 0.53
x x
- / . . x . - - X
. o . - < 3 o----Q
X 0.46
ratio, and the time available. 0.6 ? jfr'' o- -0- o -o 0 0.43
Drop breakup is the classical subject of I ^ O--Oo ** ^ ^
0 0.39
study in dispersive mixing. Excellent 0.4 ;' ."-'

: . Q .' 0
0 0--..<). Q

^o O o - "
^J. O-
0
" " 0
"
O
0 0.35
0 0.30
reviews are given by Acrivos (1983), Ralli- 0 0.25
son (1984), and Stone (1994). Experimen- 0.2 ^ p = 0.09 -
tally, drops (with R~ 1 mm) of model liquids
1 1 1

at room temperature are studied in well- 0 20 40 60

defined flow fields. Commonly used flow t'H
devices are the Couette and the parallel band Figure 3-27. Deformation of a spherical drop in
device for simple shear flow and the four- steady simple shear flow as a function of dimension-
roll mill for plane hyperbolic flow (see, less time. The parameter is the capillary number
(Meijer and Bos, 1989).
e.g., Taylor, 1934; Grace, 1971; Bentley,
1985; Elmendorp, 1986; Stone and Leal,
1989 a, b; Meijer and Bos, 1989; Elemans, acteristic time of the flow (tf\ow=l/y)
1989; de Bruijn, 1989; van der Reijden- resembles the capillary number
Stolk, 1989;Milliken and Leal, 1991,1992).
For the present study an opposed jets device Ca = f (3-47)
was developed (Janssen et al., 1993 and Sec. flov
3.7.2) to generate plane hyperbolic flow. usually interpreted as the ratio of shear and
interfacial stress [Eq. (3-1)].
Depending on the viscosity ratio p (drop/
3.3.4.1 Measurement of Cacrit
matrix), different characteristic drop shapes
The most well-known study on drop can be distinguished (Rumscheidt and
breakup originates from Grace (1971). He Mason, 1961): For/? > 1 the deformed drops
determined the critical capillary number have rounded ends, while for smaller values
under more or less equilibrium conditions of p these become pointed. If p > 0.1 in sim-
(Fig. 3-2), i.e., by slowly increasing the ple shear flow, extremely small droplets
velocity gradient until a stable drop shape break off from the sharply pointed ends.
could no longer be obtained. Figure 3-27 This phenomenon, called tipstreaming, is
illustrates the deformation of an initially caused by gradients in the interfacial ten-
spherical drop [D = 0, Eq. (3-5)] into an sion due to the convection of surfactants
ellipsoid. Below CaCYit the interfacial ten- along the drop surface accompanied by dif-
sion dominates and the drop is only slight- fusion from the bulk. At the tips the interfa-
ly deformed. A typical internal circulation cial tension decreases and tiny droplets
maintains a stable equilibrium drop shape. break off (de Bruijn, 1993).
Above Cacrit no stable drop shape exists: the Another effect of surfactants is that they
shear stress dominates and leads to irrever- immobilize the interface. Hence the internal
sible stretching and breakup. Time has been flow in the drop is suppressed, which may
made dimensionsless with respect to the retard deformation and breakup (compare
characteristic time for interfacial tension with interface immobilization in coales-
driven processes, t(7=ricR0/a' [see Eq. cence, Sec. 3.4). In a full analysis the con-
(3-24)]. Note that the ratio of r^and the char- vection/diffusion problem of the surfactant
148 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
concentration has to be solved (Stone and
Leal, 1990; Milliken et al., 1993; Janssen
and Boon, 1993). Chang and Olbricht
(1993 a, b) investigated the effect of immo-
bile interfaces using viscous drops that were
encapsulated by a thin polymeric mem-
brane. This closely resembles the behavior
of red blood cells in blood vessels (Fischer
et al., 1978).
Determination of the critical capillary
number of viscous drops in the opposed jets
device (plane hyperbolic flow) yields
results that agree with literature data. It is
interesting to show the influence of the flow
type on Cacrit as measured by Bentley
(1986 b). In Fig. 3-28 the parameter a (see
Sec. 3.7.1) characterizes the flow type,
ranging from simple shear (a=0) to plane
hyberbolic flow (a = l). Intermediate flow
types ( 0 < a < l ) give critical capillary
numbers in between the curves for the two
'regular' flow types. The numerical results
of Khakhar and Ottino (1986) agree reason-
ably well with the experimental data of
Bentley; Grace's (1971) experimental
results, from Fig. 3-2, show some deviation.
Interestingly, for moderate viscosity ratios
102
Khakhar k Ottino (1986)
a= 0 .2 .4 .6 .8 1
Bentley & Leal (1986 b)
a = .2 .4 .6 .8 1
Grace (1971)
0 1
10
105 10- 4 10-3 10-2 io-i
p(=
both Bentley's and Khakhar's curves for dif-
ferent flow types practically reduce to one
curve. (Bentley's results do not include sim-
ple shear flow). This cannot be recognized
in the original figures of Bentley (1986 b)
and Khakhar and Ottino (1986), where a
broader range of curves are presented due
to an improper definition of the capillary
number, i.e., Ca = r\cGRIo with G being the
velocity gradient of the flow, instead of
Ca = ricyR/a [Eqs. (3-1) and (3-2)] with y
the shear rate [=V(2D:D=G(l + a)l that
automatically accounts for the rotational
contribution of the flow.
As for distributive mixing, for dispersive
mixing elongational flow is more efficient
than simple shear flow, especially for p > 4
where the presence of rotational compo-
nents in simple shear flow prevents drop
breakup. Independent of the flow type, the
minimum in Cacrit is found around p = 1. As
emphasized in Sec. 3.3.6, this does not nec-
essarily imply that the finest morphology is
always obtained at p = 1, since a dispersion
mechanism via stepwise equilibrium break-
up at Cacrit (the typical experiment underly-
ing Figs. 3-2 and 3-28) is unlikely to occur
Figure 3-28. Critical capil-
lary number as a function
of the viscosity ratio for
different types of flow
ranging from simple shear
(a = 0) to 2-D elongation
(a= 1). Solid curves:
numerical, others: experi-
mental.
100 101 102

in a practical situation. A transient disper-
sion mechanism of thread breakup during
stretching generally gives a smaller drop
size that, moreover, reduces upon increas-
ing the viscosity ratio (see Sec. 3.3.6).
3.3.4.2 Drop Breakup Times
Apart from Cacr[i measurements, Grace
(1971) experimentally determined breakup
times of drops above Cacriv The breakup
time of a drop at Cacrit (in fact, slightly
above Cacrit since exactly at Cacrlt the break-
up time is infinite) increases with the vis-
cosity ratio. Breakup times for Ca far above
Cacrit are given in a plot of the dimension-
less breakup time versus Ca/Cacrit. As sug-
gested by Meijer and Janssen (1994), this
plot is ambiguous since the measured break-
up time is the sum of three distinguishable
stages each with a different characteristic
time scale. The first stage is the initial de-
formation of the original drop, which takes
more time as Ca tends to Cacrit; the relevant
time scale is ta=ricR/a. The second stage
involves the affine stretching of the unstable
drop; the relevant time scale is tnovv=l/y.
The last stage is growth of the fatal distur-
bance leading to breakup of the filament,
with ta= rjcRf/a. Consequently, it is not very
conclusive to cover all three stages by only
one dimensionless time based on the first
o
flow on
t = 0 sec.
o o
10
3.3 Breakup 149
stage. Moreover, the breakup time depends
on the initial drop size because the second
stage concerns extension from Ro down to
Rcriv the onset of thread breakup during
stretching (see Sec. 3.3.3.1).
3.3.4.3 Retraction of an Extended Drop
Retraction of extended drops in a quies-
cent matrix is another typical experiment
that has been studied in the opposed jets
device. On an extended drop two competi-
tive processes occur: (i) overall retraction
towards a sphere, driven by the pressure dif-
ference between the ends and the drop cen-
ter [Eq. (3-36)] and (ii) growth of capillary
waves leading to breakup. Depending on the
initial extension of the drop and the viscos-
ity ratio, either total retraction or breakup
results. Figure 3-29 shows an experiment
with viscous liquids where, apparently, the
time scale of disturbance growth is smaller
than that of total retraction. This type of
breakup of a slightly extended drop via a
dumbbell shape is called 'necking' and is
different from 'end-pinching', the break-off
of drops from the ends of a moderately
extended drop. In fact, the experiment sim-
ulates the passage of a drop through a con-
verging channel.
Stone and Leal (1989 a, b) extensively
studied the retraction of extended viscous
flow off
Figure 3-29. Deformation
of a 1.5 mm drop in the
opposed jets device (2-D
elongation) and breakup via
necking after cessation of
the flow; castor oil drop
and silicone oil matrix both
with viscosity 0.7 Pa s.
150 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
drops. Both experimentally, using Bentley
and Leal's (1986 a) four-roll mill, and
numerically, using the boundary element
method in axisymmetric elongational flow,
they elaborated a whole range of possible
flow situations. For example, they deter-
mined the maximal extension from which a
drop still retracts without breaking. Upon
increasing the viscosity ratio (?7d/77c), the
growth of instabilities is retarded with
respect to overall retraction; this results in
a larger critical extension. Uniform Ray-
leigh disturbances develop only on suffi-
ciently long threads (except near the ends).
In practical situations this breakup via uni-
form capillary waves is the main mecha-
nism, because end-pinching and necking
involve only a small fraction of the dis-
persed phase volume.
3.3.5 Drop Breakup in Viscoelastic
Systems
Contradictory results are reported in the
literature concerning the effect of viscoelas-
ticity on drop deformation and breakup.
Generally, it is assumed that the viscoelas-
ticity of both the drop and the matrix phase
retards deformation and breakup.
For viscoelastic drops (Sec. 3.7.3) in a
viscous matrix, Cacrit values have been
determined in the opposed jets device (2-D
elongation). For viscosity ratios of the order
of 1, no significant difference from Newton-
ian drops was found. Milliken and Leal
(1991, 1992) studied viscoelastic drops in
linear 2-D flows over a broader range of vis-
cosity ratios. For p > 1 they reported no dif-
ference with respect to Newtonian drops.
For small values of /?, smaller values of
Cacrii were found. De Bruijn (1989), on the
contrary, reported a slight increase of Cacrit
in simple shear flow upon introducing vis-
coelasticity to the drop phase. However, in
all cases the change in Cacrit is not too sig-
nificant (e.g., a factor of 2). Moreover, the
definitions of viscosity (ratio) and Deborah
number are arbitrary in such systems.
In general, viscoelasticity only plays a
significant role if the deformation is fast and
large enough (#>1 and et >1). In quasi-
equilibrium drop deformation experiments,
the total strain may be sufficient but the de-
formation rate is quite small, so that stress-
es quickly relax. Consequently, viscoelas-
ticity in drop breakup is not as significant
as in thread breakup (Fig. 3-17).
The tipstreaming that Milliken and Leal
(1991) observed using viscoelastic drops is
probably not caused by the viscoelastic
behavior of the fluid. It may in fact be a con-
sequence of polymer molecules (added in
order to modify the rheological behavior)
accumulating at the interface and acting as
a surfactant (Milliken et al., 1993; Stone,
1994), as indicated by de Bruijn (1993).
Experiments on the retraction of an
extended drop back to a sphere also proved
to be quite insensitive to the viscoelasticity
of the drop phase. Again, the total strain
appears to be insufficient or applied too
slowly to build up a significant level of
orientational stresses. Moreover, stresses
that have eventually built up relax faster
than expected from the relaxation time of
the liquid, #, due to the free interface which
induces a compression flow (compare with
Figs. 3-18 and 3-19). The maximum exten-
sion from which a viscoelastic drop still
retracts without breaking is much larger
than in the case of viscous drops, since dis-
integration by capillary waves is largely
retarded (Sec. 3.3.2.1).
3.3.6 Comparison of Dispersion
Mechanisms
Now that the breakup of drops and threads
has been discussed, it is possible to compare
the final drop sizes resulting from the

(a) (b)
o o4
o'o o o I
oooooooo
T y v v
OOOOOOOO
two dispersion mechanisms depicted in Fig.
3-30: (a) a stepwise increase in shear stress
breaking drops repeatedly under quasi-equi-
librium conditions (at Cacrit) until the
machine dependent maximum shear stress
is reached, or (b) the transient mechanism
of exerting the same maximum shear stress
directly on the original drop, thus inducing
one-step thread breakup during stretching
(Janssen and Meijer, 1993).
Often, the stepwise equilibrium mecha-
nism is considered in order to predict the
minimum attainable drop size of a disper-
sion. This can easily be done using the crit-
ical capillary number (Fig. 3-2): knowing
the material properties and estimating the
maximum deformation rate in the mixing
device, the value of Cacrit gives the small-
est drop size that can still be broken. Assum-
ing the drop breaks into two equal parts
without satellite droplets in between, the
minimum drop size resulting rom the step-
wise dispersion route is
3
P
(3-48)
77,7/CT
Since the value of Cacvit is a minimum at
p 1 , it is often concluded that the finest
morphology is obtained if both viscosities
match. The stepwise breakup mechanism,
however, is unlikely to occur in real mixing
processes and, moreover, the time necessary
for drop breakup should be taken into
account. More realistic appears to be the
transient breakup mechanism, where a rel-
3.3 Breakup 151
Figure 3-30. Schematic representation of
the two dispersion mechanisms: (a) the
stepwise equilibrium mechanism of
repeated breakup at Cacrit: (b) the tran-
sient mechanism of thread breakup during
stretching.
atively large drop (with Ca Ca c r i i ) is
stretched affinely into a thin liquid thread
that finally disintegrates into a line of drops
(Sec. 3.3.3.1).
3.3.6.1 Plane Hyperbolic Flow
Figure 3-31 compares the drop sizes gen-
erated by the two distinct mechanisms in
plane hyperbolic flow (Janssen and Meijer,
1993). The solid curves are deduced from
Fig. 3-22, the transient process with a con-
stant stretching rate; the dashed lines from
Eq. (3-48), the stepwise equilibrium mech-
anism. Generally, the transient mechanism
yields smaller drops, and it is evident that
p-\ is not the optimum viscosity ratio. In
fact a higher viscosity ratio yields a finer
dispersion, as already noted by Tjahjadi and
Ottino (1991). If drops are formed by the
transient mechanism, whereas the equilib-
rium mechanism would have resulted in
smaller droplets (typically at high values of
r]clo), they just break once more. Note that
the dashed curves in Fig. 3-31 continue
down to unrealistic length scales. Of course,
a lower limit exists due to the length scale
below which continuum mechanics fails
(~10~9 m). To deduce the full curves, a0 was
taken as 10~9m. As explained in Sec.
3.3.3.1, changing the arbitrary value of a0
has a minor effect on the drop size. The value
of the flow parameter r\celotypically rang-
es from 1 - 1 0 5 nT1 for model liquids in an
experimental device (e.g., opposed jets or
152 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
10-2
10-3
Nv \ ^ & v
R drops
ml 10-5
io- 6
10-7
10-8 NO BREAKUP
10-9
10-1 10 101 10 2 103
Couette) and from 10 5 -10 8 m l for poly-
mer melts in compounding equipment (e.g.,
extruders).
In a practical situation, a point to consid-
er is whether the time available for each of
the idealized processes in Fig. 3-30 is suffi-
cient. For the transient mechanism, the
breakup time is given by Eq. (3-46). For the
stepwise equilibrium route the breakup time
is generally longer. The time for breakup at
CaCYh was measured by Grace (1971). (Note
that Grace's experiments must have been
performed slightly above Cacrit since exact-
ly at Cacrit, th = oo.)
3.3.6.2 Simple Shear Flow
For simple shear flow, the drop size
resulting from the stepwise equilibrium
mechanism is, again, easily obtained from
Eq. (3-48). Drop sizes resulting from tran-
sient thread breakup in steady simple shear
were deduced from Fig. 8 of Khakhar and
Ottino (1987). Both the initial radius and
orientation of the thread have to be chosen.
In Fig. 3-32 a comparison is made using two
initial radii Ro and viscosity ratios p; with
p = 10"3 .
1
BREAKUP 103 -
Figure 3-31. Minimum
attainable drop size in plane
- hyperbolic flow resulting
from (i) the step wise equi-
librium mechanism of drop
y p breakup at Cacrn (dashed
lines) and (ii) the transient
mechanism of thread break-
up during stretching with
^ (XQ - 10" m (solid curves);
the parameter is the viscos-
ity ratio p(=T]d/T)c).
10 4 105 106 107 10 8 10 9
r|cs/a
ao=l0 9 m and the initial angle between
thread axis and streamlines (po = 27 (corre-
sponding to 2 tan <Po=l> a n upper limit).
Upon decreasing % to 3 (corresponding to
2 tan <p0 = 0.1, a lower limit), the solid curves
shift one decade to the right. Note that along
the horizontal axis the (constant) shear rate
7 is used rather than the time-dependent
stretching rate ; for comparison with plane
hyperbolic flow, in Fig. 3-31 should be
replaced by y/2.
Again, the transient mechanism may
yield smaller drops than the stepwise equi-
librium route, but the difference is much less
pronounced than in elongational flow. The
influence of the viscosity ratio is extreme in
the equilibrium process (see also Fig. 3-2):
for p > 4 the equilibrium mechanism is not
able to break drops since Cacrit goes to infin-
ity. For the transient mechanism, an increas-
ing p keeps reducing the drop size. Beyond
p = 4, stretching of the original drop into a
thread is impossible in simple shear; how-
ever, it is sufficient that it occurs only
once, e.g., in a local region of elongational
flow.
In simple shear flow, reorientations and
folds can enhance the mixing efficiency

r\cy/o [m"- l1- ]i
exponentially (see Sec. 3.2.2). In such flows
the analysis for the constant stretching rate
may hold just as for steady elongational
flows. Hence periodic reorientations and
folds improve not only distributive mixing
but also dispersive mixing by postponing
thread breakup.
Practical flow situations bring arbitrary
histories of the deformation rate. The
analysis of thread breakup during stretching
can accordingly be performed using the
local function e{t)\ results of general valid-
ity are hard to obtain. If, however, the
local stretching rate varies slowly with
respect to the disturbance growth time (g),
the results for constant can be used (see
Sec. 3.5.4). In practice, complications
arise due to the presence of many drops
and threads. For instance, the collision of a
drop onto an extending thread, as illustrat-
ed in Fig. 3-26, which leads to early scis-
sion and larger drop sizes than predicted by
uniform disintegration. The drop sizes
from Fig. 3-31 actually represent a lower
limit. Another, more important, aspect caus-
ing dispersions to be coarser than suggest-
ed here is the coalescence of drops
(Sec. 3.4).
3.3 Breakup 153
Figure 3-32. Minimum
attainable drop size in sim-
ple shear flow resulting
from (i) the stepwise equi-
librium mechanism of drop
breakup at Cacrit (dashed
lines) and (ii) the transient
mechanism of thread break-
up during stretching with
ao= 10~^m, % = 21, and
2R0 = 3x l(T 4 m(A)or
10~5 m (B) (solid lines); the
parameter is the viscosity
ratio.
3.3.7 Conclusion
In dispersive mixing the deformation rate
and time are both important, and not only
their product, as in distributive mixing. The
main dispersion mechanism is the breakup
of long liquid threads due to capillary waves
at the interface. Thread breakup in Newton-
ian systems both at rest and during stretch-
ing can be calculated. Other breakup mech-
anisms involve end-pinching at the ends of
moderately extended drops and necking of
slightly deformed drops.
For Newtonian liquids it has been shown
that the more realistic transient mechanism
of thread breakup during streching general-
ly results in smaller drops than the stepwise
equilibrium mechanism of repeated drop
breakup at Cacvit. The transient mechanism
predicts a finer morphology upon increas-
ing the viscosity of either phase. This is
quite different from the commonly used rule
of thumb that the viscosities of both phases
have to match. In fact, the two dispersion
mechanisms mentioned could have been
compared in the 1930s (Taylor, 1934; To-
motika, 1936). Only the complexity of the
transient analysis and the lack of computa-
154 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
tional facilities apparently delayed the inter-
pretation of the consequences of these clas-
sical studies.
The influence of viscoelasticity is signif-
icant if the applied deformation is suffi-
ciently fast (De =$>l) and large
(e = t>l); in other words, if substantial
orientational stresses build up. Particularly
in the breakup of viscoelastic threads, these
circumstances are realized and the disinte-
gration process is largely retarded, while
typical dumbbell shapes evolve instead of
sine waves. In situations where drops are
moderately deformed, viscoelastic effects
are not observed. For example, for viscos-
ity ratios of the order of unity the critical
capillary number for the breakup of viscoe-
lastic drops is roughly the same as that for
Newtonian drops. Also, in drop retraction
from an initially deformed shape, the effect
of viscoelasticity is not very significant.
3.4 Coalescence
3.4.1 Collision of Drops
Up until now, the disperson of isolated
drops and threads has been discussed. Most
practical applications, however, involve
blends that are sufficiently concentrated to
exhibit coalescence of the drops formed.
Elmendorp (1986) experimentally showed
that even at a volume fraction of a few per-
cent dispersed phase, the morphology is sig-
nificantly coarsened by coalescence. At
high volume fractions (around 50%, see
Sec. 3.5.3), phase inversion may occur.
In the modeling of coalescence, two
aspects have to be considered: (i) do drops
collide within a given process time and (ii)
will a collision be successful, i.e., does the
film between the drops drain sufficiently
during the available interaction time? Fig-
ure 3-33 shows two colliding drops in sim-
Figure 3-33. Collision of two deformable drops in
simple shear flow with drainage of the film in between.
pie shear flow. The 'external flow' and the
volume fraction of dispersed phase govern
the collision frequency. In addition, the
external flow is responsible for the contact
force and the interaction time of the colli-
sion, the boundary conditions for the film
drainage or 'internal flow'.
For equal spheres following the basic
external flow, the collision frequency can be
estimated (e.g., Smoluchowski, 1917; Ches-
ters, 1991). In simple shear flow the colli-
sion frequency of an individual drop is given
by
C = ^yR3n (3-49)
where n is the number of drops per unit vol-
ume. Upon multiplication with n/2 the col-
lision frequency per unit volume is obtained
(the factor of 1/2 accounts for the fact that
each collision involves two drops)
c' = fc=fr*V (3-50)
The number of drops per unit volume (n)
can be expressed in terms of the volume
fraction of dispersed phase (/)
hence (3-51)
30
n = 3^
4nR
The elimination of n in Eq. (3-49) yields
the collision frequency of a drop as a func-

tion of the shear rate and the volume frac-
tion
C = ~y(j)
independent of the drop radius. So, on aver-
age, a drop collides after every time
In other words, a drop collides after every
shear y= ytcoll = 7i/(80).
The ratio between the required collision
time tcoll and the available process time tproc
indicates whether or not a collision is to be
expected. However, tcoU is the idealized
value of a distribution (reality implies
complications such as varying collision
angle, nonspherical drop shape, and poly-
dispersity). An exponential function of
the ratio tcoU/tproc provides a continuous col-
lision probability function (Ross et al.,
1978)
proc
tending to zero if /proc <C tcoU, and to unity
in the other extreme. Evidently, the collision
probability increases with the shear rate
applied and the volume fraction, whereas it
is independent of the drop size.
Usually, drop collisions are accounted
for directly by the collision frequency or
the collision rate. Here, the approach with
J /
-dh/dt h
YR "
drainage/
model/
/
k h
3.4 Coalescence 155
probabilities has been chosen in view of
the 2-zone mixing model of Sec. 3.5 that
deals with a given process time (or resi-
(3-52) dence time) in each zone. An extra advant-
age of using the collision probability is
that drop collision and film drainage (next
section) are now treated in a similar way,
so that they can easily be combined after-
(3-53) wards.
3.4.2 Film Drainage
3.4.2.1 Theoretical
The second part of the modeling of
coalescence deals with drainage of the liq-
uid film between the colliding drops. Fig-
ure 3-34 schematically shows how the film
drainage proceeds when drops collide.
Initially, at a large separation, the drops
approach according to the velocity gradient
of the external flow field: the drainage rate
-dh/dt is of the order of yR. At a certain sep-
aration (h0) hydrodynamic interaction
becomes significant (the drops 'notice' each
(3-54) other) and the collision starts. The driving
force for film drainage is now the contact
force F that acts during the interaction time
tinV The drainage rate -dh/dt decreases and
the film thickness h asymptomatically
decays to zero. However, when a critical
film thickness (hcrit) is reached, instabilities
grow at the interfaces and film rupture sud-
denly occurs: the drops coalesce. If the
interaction time of the collision is insuffi-
. V.-dh/dt = Figure 3-34. Schematic plots of the
film drainage between two colliding
drain drops: first, at large separations, they
approach affinely with the external
drainage \ flow (~ yR); at h0 the collision 'starts'
and the drainage rate decreases, at hcrh
crit \ the film suddenly breaks and the
drops coalesce.
 3 Emulsions: The Dynamics of Liquid-Liquid Mixing

(b) ^ - \ (c)

Figure 3-35. Internal flow field of

film drainage between colliding
deformable drops with (a) immobile,
(b) partially mobile, and (c) fully
mobile interfaces.

cient to reach hcriv the drops do not coalesce, for partially mobile interfaces
but tumble and separate.
Several theories are available to model 717/j F 1
^drain (3-56b)
the process of film drainage. They differ in 2(2KOIRY11 ^/icrit h
the mobility of the interfaces: immobile,
and for fully mobile interfaces
partially mobile, or fully mobile interfaces.
Figure 3-35 schematically depicts the
velocity profiles. The model with partially ^draii (3-56c)
2(7
mobile interfaces is the only one that
accounts for the flow inside the drops. The contact force F is the Stokes drag
Assuming (i) deformable drops with a par- force acting on the drops; it can be estimat-
allel-sided film in between, (ii) a constant ed from the external simple shear flow con-
contact force F, and (iii) viscous flow, the sidered
rate of film drainage for immobile interfac- F~6TI77C7R2 (3-57)
es is given by (MacKay and Mason, 1963)
As indicated in Fig. 3-34, the initial film
dh 8TI a2 h3 thickness h0 corresponds to the separation at
(3-55a)
dt 3/7c R lF which the constant approach velocity at large
for partially mobile interfaces (Chesters, separations yR equals the decaying approach
1988) velocity -dhldt from the drainage models
[Eq. (3-55)]; for immobile interfaces
dh 2(2na/R)3'2 h2 (3-55b) 1/3
dt KI (3-58a)
and for fully mobile interfaces (Chesters,
1975) for partially mobile interfaces
dh 2a h y/4
(3-55c) - p112 Ca3/4 (3-58b)
dt 377, R
The required drainage time tdmin to reach and for fully mobile interfaces
coalescence is obtained by integration from
h0 to hcriv In the case of immobile interfac- ho~R-Ca (3-58c)
es this gives
with Ca the capillary number (=7icyR/(j)
^drain ~ (3-56a) and/? the viscosity ratio (=
Krit h)

The critical film thickness hcrit at which
sudden rupture of the film and thus coales-
cence occurs is governed by van der Waals
forces destabilizing the thin film; it can be
approximated by (Chesters, 1991)
1/3
AR
( ) (3-59)
with A as the material-dependent Hamaker
constant (typically 1(T20 J). For micrometer-
sized drops with a- 5 x 10~3 N/m, the
resulting value of hCTit is about 5 x 10~9 m. Its
dependence on the drop radius is fairly weak.
From Eq. (3-56) it is clear that all three
models predict that larger drops need more
time to drain the film. This is mainly due to
the smaller pressure peak at the center of the
film at larger drop radii; in addition, a larger
radius gives a larger flattened area so that
there is more liquid to drain. The conse-
quence is that small drops coalesce preferen-
tially: above a certain drop size they do not
coalesce further under given conditions.
Interfacial tension tends to make the drops
more spherical, resulting in a smaller flat-
tened area and a shorter drainage time. The
model with partially mobile interfaces is the
only one that includes the viscosity of the dis-
persed phase (and thus the viscosity ratio/?).
Furthermore, it is interesting that accord-
ing to two models, a larger value of F leads
to slower drainage of the film. The reason
is the larger flattened area between the
drops at a higher contact force [i.e., with a
the radius of the flattened area, it follows
from the pressure balance F/na2~2o/R
than a ~ ^{FRIlno) or, using Eq. (3-57),
a ~ Ry]'(3Caj]. Hence, at larger F (or Co)
more liquid has to drain over a larger dis-
tance which, of course, increases the drain-
age time. An important consequence is that
coalescence preferentially takes place in rel-
atively quiet zones of the mixer with soft
collisions ( small drainage time required
3.4 Coalescence 157
and large interaction time available) and not
in regions with high deformation rates
(large drainage time and small interac-
tion time). The interaction time, i.e., the
duration of the collision, can be approximat-
ed from the external shear rate
hm ~ i/y (3-60)
A few words can be said about the effect
of the assumptions made (flat, parallel-
sided film and constant contact force). If
instead of prescribing a flat film the inter-
face is free to deform, a dimple is formed
that influences the drainage time. However,
in the case of liquid-liquid systems, Ches-
ters (1991) and Abid (1993) showed that the
flat film approximation does quite a good
job. Due to the tumbling of colliding drops,
the contact force generally shows a maxi-
mum (at a collision angle of 45 with respect
to the streamlines in simple shear flow). In
particular the decay in F at the end of the
collision may favor coalescence since it
reduces the flattened area, thus increasing
the drainage rate [Eqs. (3-55 a, b)]. So, in
the present modeling with constant F,
coalescence is probably underestimated. An
additional point is that the Stokes drag force
[Eq. (3-57)] should, in fact, contain the
effective viscosity of the dispersion, which
depends on the volume fraction 0 and may
be considerably larger than rjc. In the numer-
ical simulations in Sec. 3.5 this effect is
included; here, it is omitted in order to serve
the clarity of the analysis.
Up until now, the collisions of equally sized
drops have been considered. For unequal
drops, the same equations for the film drain-
age hold provided that an equivalent drop
radius is used (Chesters and Hofman, 1982)
(3-61)
so that Req ranges from /?, (if R2=/?,) to 2/?,
158 3 Emulsions: The Dynamics of Liquid-Liquid Mixing

Restrictions of the Drainage Models
The transitions between the different
drainage models follow from the restric-
tions of the partially mobile interfaces
model, as obtained by equaling the drainage
rates of the different models (Chesters,
1988; Abid and Chesters, 1994). In the equa-
tions below, the transitions to other models
are first given in terms of a the radius of the
flattened area (Fig. 3-35). In the second part
of each equation, a is substitutd by R^j (3Ca)
so that the restrictions can be transcribed in
terms of R and the flow parameter rjc y/<7(in
view of Fig. 3-40). The validity of the model
with partially mobile interfaces requires all
of the following conditions:
inside the drops); p d is the density of the dis-
persed phase.
A proper choice for h is the value of hcriv
since the last stage of the film thinning is
rate determining. The first two restrictions
indicate the transition to the extreme mod-
els: for too small p{- T]d/77C) the drops can
be considered inviscid, yielding fully
mobile interfaces, while for too large p the
drops become rigid with immobile interfac-
es. An additional restriction follows from
the estimation of <zl~ R^j(3Ca) I, since a
cannot be much larger than the original drop
radius R. In fact, this restricts all three mod-
els
< 1 hence

p> hence -l (3-66)

a
1/3 -1/3 (3-62)
12/z2
2
R>
U a Note that the flow parameter rjc y/<j (com-
parable to 77c/crin Sec. 3.3) is welcome in
or transition to fully mobile interfaces, and view of the combination of all the mixing
mechanisms in Sec. 3.5.
p< ^h hence
(3-63)
Drainage Probability
R>
{ 27 j uJ A few simplifications are now introduced
or transition to immobile interfaces, and
to maintain a clear view on the main points of
hence the modeling of coalescence. First, the terms
l/h0 and 1/(/IQ) in Eqs. (3-56 a, b) are neglect-
U2 1/2 (3-64)
ed since generally ho^>hcrit; in Eq. (3-56c),
(4h) (n c/y
R>
UJ I o J h0 is approximated by the drop radius R. Sec-
ondly, the value of hCTit is taken as constant at
or transition to drainage without flattening, 5 x 1CT9 m. (In the numerical simulations of
and Sec. 3.5, h0 and hcrit are computed correctly.)
By analogy with the collision probability,
/z < -r-^ hence the drainage probability is defined as
(3-65)
-l
fdrain_
R< (3-67)
48/z2zpdz CJ
or transition to boundary layer growth and ranges from zero if tint <C tdmin to unity
(instead of a stationary boundary layer in the other extreme. Substitution of the

required film drainage time according to the
three models, together with the proposed
expressions for F and tmv gives for immo-
bile interfaces
9
~ exP < * I Ca- (3-68a)
for partially mobile interfaces
(3-68b)
and for fully mobile interfaces
R
~ exP -Cain (3-68c)
Again, it can be seen that a weak flow
(small Ca) favors film drainage.
3.4.2.2 Experimental
Experimental work on coalescence has
been performed using Newtonian model liq-
uids in the opposed jets device (Sec. 3.7.2).
After the breakup of a drop, the directions
of flow are reversed and the drops formed
are forced to collide very softly head-on
(typically ~ 0.1 s"1). Since it is not pos-
sible to keep two drops positioned near the
stagnation point at the same time, the dura-
tion of an experiment is limited; coalescence
events may take place outside the field of
view. The total time for coalescence was
measured, which is, in this case, the drain-
age time. The results show unacceptable
scatter. Only the order of magnitude (-10 s)
seems reliable and corresponds to the par-
tially mobile interface model, but definite-
ly not to the models for immobile interfac-
es (103 s) and fully mobile interfaces (Is).
Although the quantitative results are not
very satisfying, a nice sequence of coales-
cence events is visualized in Fig. 3-36: a
typical experiment where a string of drops
3.4 Coalescence 159
O
Figure 3-36. A cascade of coalescence events in a
string of drops that are pushed together; both liquids
are Newtonian.
is pushed together softly in (reversed) plane
hyperbolic flow. Upon coalescence with the
first drop from the left, the second drop is
slightly released from the third one. Conse-
quently, the contact area reduces to a con-
tact point favoring drainage, and confluence
of the third drop with the first two is the
result. Similarly, a cascade of coalescence
events occurs with each event inducing the
next one.
Other experiments have been carried out
by letting a drop sink in a layer of a less
dense, immiscible liquid towards a bottom
layer of its own liquid. In fact, this is a col-
lision of two drops (one of radius <) driven
by gravity. These experiments give basical-
ly the same result as the previous ones: the
order of magnitude of the model with par-
tially mobile interfaces seems the best of the
three, but reproducible data cannot be
obtained. A probable explanation is the fact
that the critical film thickness is occasion-
ally affected by disturbances or dust parti-
cles. Variation of hcrit has a tremendous
effect on the drainage time, as is evident
from Fig. 3-34. Therefore it appears that
experiments are only useful if the entire
160 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
decrease of the film thickness is measured
instead of only the total drainage time (see
Abid, 1993).
In polymer blending only a few experi-
mental studies concerning film drainage are
available. Elemendorp (1986) showed that
the model with fully mobile interfaces pre-
dicts too small coalescence times, whereas
immobile interfaces predict too large times,
thus supporting the partially mobile inter-
faces model. Elemans (1989) and van Gis-
bergen and Meijer (1991) also found experi-
mental support for the use of the partially
mobile interfaces model in polymer blend-
ing.
3.4.3 Coalescence Probability
In the former sections expressions have
been presented for both the collision and the
drainage probability. From these the overall
coalescence probability can be calculated
*coa "" *c
(3-69)
R[m]
i.e., the probability that a collision takes
place within the (given) process time avail-
able and, additionally, that this collision is
successful and leads to coalescence. In
Fig. 3-37 the behavior of the probabilities
P coll , Pdrain, and P coa is shown for a specif-
ic situation.
Evidently, collisions occur more readily
if the deformation rate is high enough, inde-
pendent of the drop radius [Eq. (3-54)]. On
the other hand, soft collisions are more suc-
cessful in draining the film than fast ones.
The transition of P drain from 1 to 0 depends
on the drop radius: smaller drops coalesce
in faster flows than larger ones. The combi-
nation of P coll and P drain results in a bound-
ed hump, an area in the (R - r\c yld) plane
where coalescence occurs: collisions take
place and succeed in sufficient drainage of
the film to reach the point of film rupture
and coalescence. In too slow flows no col-
lisions take place within the given process
time. In too fast flows the required drainage
time has increased beyond the decreasing
interaction time. For drops that are too large,
the above two boundaries intersect and
coalescence is impossible for any value of
Figure 3-37. (a) Collision, (b)
drainage, and (c) overall coales-
cence probability as a function of
the radius R and the flow parame-
ter r\c ylo. Conditions: simple
shear flow, tproc = 50 s,
7]d = 7]c = 1 Pa s, (7= 1(T2 N/m,
hCTit = 5 x 1(T9 m, 0 = 0.1, drain-
age with partially mobile interfac-

r/c y/<x On the other hand, there is no lower
limit for the drop radius below which
coalescence cannot take place. The hump
even diverges along the r\cylo axis for
smaller drops.
Variation of the material and flow param-
eters has the following qualitative effects.
First it should be noted that the left side of
the P coa hump is determined only by the
occurrence of collisions [Eq. (3-54)]. The
volume fraction and the process time both
exhibit the same influence, i.e., increasing
the product 0 fproc enlarges the hump to the
left, without affecting its right side. The
right side is governed by the process of film
drainage [Eq. (3-68)]. A larger viscosity of
the dispersed phase retards the drainage of
the film and suppresses coalescence. Fully
mobile and immobile interfaces respective-
ly enlarge and diminish the coalescence
window but are insensitive to r/d, which is
quite unrealistic. The influences of the inter-
facial tension and the continuous phase vis-
cosity look somewhat more complex since
both are included in one of the axes. In short,
it can be said that a larger interfacial tension
accelerates the film drainage according to
COALESCENC
io-7 io-6 io-5
j. v
io-4 io-3
3.4 Coalescence 161
all three models and thus enlarges the
coalescence window. A higher value of 7]c
reduces the window.
It is possible to imagine cross-sections
through the 3-D P coa graph at constant val-
ues of the drop radius (Pcoa versus TjQ y/afor
different values of/?). These are even more
illustrative after multiplying the flow
parameter r\c y/crby R yielding the capillary
number. Figure 3-38 shows the coalescence
probability as a function of the capillary
number for different drop radii. Smaller
drops coalesce more readily than larger
ones, but most striking is the fact that coales-
cence typically occurs at capillary numbers
that are considerably smaller than necessary
for drop breakup (Cacrit ~ 1). So coalescence
and breakup take place in different regions
of a mixer: breakup (and stretching) in
strong, and coalescence in weak regions.
It should be noted that the restrictions of
the partially mobile interfaces model
[Eqs. (3-62) to (3-66)] have not been
applied to the results given in Figs. 3-37 and
3-38. Actually, for very small drop radii
(roughly below 10~7 m) these graphs lose
validity.
Figure 3-38. Coalescence
probability as a function of
the capillary number; the
parameter is the drop radi-
us. The partially mobile
interfaces model is used;
the conditions are the same
as in Fig. 3-37.
162 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
3.4.4 Combination of Breakup and
Coalescence
In order to compare the distinct criteria for
drop breakup and coalescence in a simple
way, a few assumptions are made. First, a
flow is considered that acts for sufficiently
long to reach the final equilibrium state. So
transient effects are not considered here
although they are essential, as indicated
throughout this chapter. Just as in Sec. 3.3.6,
the breakup criterion for stepwise equilibri-
um drop breakup is obtained from the criti-
cal capillary number. The coalescence crite-
ria given in the former sections are partly
restricted to simple shear flow, but give a
good insight into the main phenomena. Final-
ly, the continuous coalescence probability
(Pcoa) is transformed into a simple criterion.
The overall coalescence probability
Pcoa is made up of P coll and P drain . Both
contributions are defined as
P = exp (-*required"available)
A simple way of making them binary is
to use the criterion P = 1 if ravailable > frequired
and P = 0 otherwise. With respect to the col-
lision probability, it is assumed that the
available time tproc is sufficiently long so
that P coll = 1 and thus Pcoa = P drain . The cri-
terion for coalescence now simply reads
'yes' if tint > tdmin and 'no' otherwise.
Elaboration of the equality ^nt-^drain [Eqs.
(3-56) and (3-60) with the assumptions for
h0 and hCYlV as mentioned just before Eq.
(3-67)] yields a critical drop size below
which coalescence takes place and above
which it does not. For the drainage model
with immobile interfaces
1/4 -1/2
h 1/2
R= (3-70a)
for partially mobile interfaces
and for fully mobile interfaces, R has to be
solved from
(3-70c)
crit O
Evidently, the radius of the drops formed
(^drops)is 2 1/3 (1.26) times that of the orig-
inal drops (R). The minimum attainable drop
size due to coalescence is now known as a
function of the flow parameter r\c yla. The
viscosity ratio p only shows up in the model
with partially mobile interfaces for which
,-6/13
the proportionality R x 77c can
be derived from Eq. (3-70b) (taking into
account that /zcrit c Rl/3). Figure 3-39
shows the maximum drop size resulting
from the coalescence of smaller drops after
a sufficiently long time (i.e., long enough to
reach the limiting drop size given by [Eq.
(3-70)]. The fully mobile interfaces model
(dash dotted curve) predicts fast film drain-
age and allows for the coalescence of larg-
er drops than the immobile interfaces model
(dashed line). The partially mobile interfac-
es model (solid lines) is restricted by
Eqs. (3-62)-(3-66). These restrictions more
or less coincide with the intersections of the
curves. (Not exactly because of the assump-
tions on h0). For smaller drop sizes the pre-
dictions of the two extreme models
approach each other, and the range where
the partially mobile interfaces model holds
becomes narrower.
Now coalescence and quasi-equilibrium
breakup can be compared. In Fig. 3-40
the maximum drop size resulting from
coalescence is given for the three curves of
Fig. 3-39 corresponding to the different
drainage models (p= 1). The (steepest) solid
line stems from Eq. (3-48) and gives the
smallest possible drop size from stepwise
equilibrium breakup in simple shear (as
depicted in Fig. 3-30). It is clear that drops
that are too large will break while drops that
are too small coalesce. The area between the
 3.4 Coalescence 163

Figure 3-39. Drop size

resulting from the coales-
cence of drops after a suffi-
ciently long process time
according to the different
film drainage models: (i)
immobile interfaces
(dashed), (ii) partially
mobile interfaces with p
dependence (solid), and
(iii) fully mobile (dash dot-
ted).
102 103 104 105 1Q7 iO8 1Q9
1
r\j/o [m" ]

Figure 3-40. Comparison

of drop sizes resulting from
stepwise equilibrium break-
up and coalescence after a
long process time in simple
shear.
1 10 101 102 1Q3 104 1Q5 1Q6 1Q7 1Q8 10

breakup curve and one of the coalescence
curves gives the possible range of drop sizes
after a long process time as a function of the
flow parameter 7]cy/<x In most cases the
model with partially mobile interfaces is the
most realistic. For viscosity ratios deviating
from unity, the picture looks similar,
although the choice of drainage model may
be different. Generally, the 'steady state'
drop size decreases almost proportionally
with the flow parameter.
Surfactants (or compatibilizers) present
in the drop phase may immobilize the inter-
face and thus retard film drainage and pre-
vent coalescence. Surfactants present in the
continuous phase are generally much less
164 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
effective, since they cannot reach the inter-
face as easily as surfactants dissolved in the
drop phase (Ivanov, 1980). A complete anal-
ysis of the film drainage with a surfactant
includes the convection/diffusion problem
giving concentration and thus interfacial
tension gradients. In specific cases, surfac-
tants may also suppress coalescence by ster-
ic hindrance.
Apart from the prevention of coalescence,
the finer morphology usually experienced
upon the addition of surfactants is due to a
decrease of the interfacial tension a induc-
ing (i) a delay in the thread breakup, so
allowing for thinner threads prior to break-
up, and (ii) an increase in the local capillary
number, so allowing for the breakup of
smaller droplets. Viscoelasticity is expect-
ed to retard film drainage, since (biaxial)
elongational viscosities may build up, espe-
cially in the squeezing film.
3.4.5 Conclusion
The modeling of coalescence consists of
two parts: (i) collisions, the easier part and
(ii) film drainage, for which three models
are available. The elaboration of simple
analyses leads to important conclusions.
Coalescence preferentially takes place in
regions with small deformation rates: not
too small, to ensure a certain collision fre-
quency, but especially not too large, since
in a fast collision the liquid film cannot drain
enough. The capillary numbers at coales-
cence are typically much smaller than those
required for breakup.
Simplification of the criteria for coales-
cence leads to a comparison with stepwise
equilibrium breakup in simple shear. In the
long run, a possible range of drop sizes is
found, descending with the shear rate. Drops
that are too large break, drops that are too
small coalesce.
3.5 Applications
3.5.1 A Two-Zone Mixing Model
3.5.1.1 Principle
In the preceding sections, the most rele-
vant stages of the blending process of
immiscible liquids have been discussed, i.e.,
affine stretching of dispersed drops includ-
ing reorientations and folds, disintegration
of the formed liquid threads, further drop
deformation and breakup, and the coales-
cence of small drops into larger ones. The
resulting criteria for Newtonian liquids are
quite complete and can be combined into an
overall mixing model that describes the
development of the morphology during the
blending process (Janssen and Meijer,
1995). A schematic 2-zone model has been
chosen that has an analogy with the mixing
model for carbon black in rubber, as pro-
posed by Manas-Zloczower et al. (1982).
The 2-zone model is depicted in Fig. 3-41.
The material cycles through alternating
'strong' and 'weak' zones. A diversity of
practical mixing devices can be modeled by
variation of the flow conditions in the zones
(residence times and deformation rates).
The 2-zone model is directly applicable to
stirred vessels (with the impeller region the
strong, and the macro circulation, the weak
zone), but it can also be applied to complete-
ly different types of mixers. Here the model
STRONG ZONE WEAK ZONE
affine stretching thread breakup at rest
thread breakup in flow drop coalescence
Figure 3-41. Principle of the two-zone mixing
model: material cycles through alternating strong and
weak flow zones.

is treated mainly in view of polymer blend-
ing in melt extruders.
The strong zone represents regions of a
mixer where high deformation rates are
present. It is modeled by an elongational
flow with a high elongation rate and a short
residence time t. In this zone exponential
stretching of dispersed drops and threads
takes place unless drops with Ca/Cacr[i< 5
are considered (see Sec. 3.2.1.2). During
stretching it is checked whether the threads
formed are thin enough to disintegrate in the
flow (Sec. 3.3.3.1). Although the strong
zone is modeled by elongational flow, sim-
ulating, e.g., the entrance of a narrow gap
before a kneading disk, it may also repre-
sent a sequence of stretching and folding in
a simple shear dominated region. In both
cases stretching proceeds exponentially.
The weak zone represents quiescent
regions of the mixer and is modeled by sim-
ple shear; the shear rate y is small, and the
residence time t is large. Threads entering
this zone may break up at (almost) rest if the
residence time suffices (Sec. 3.3.1.1).
Drops coalesce if the remaining residence
time allows for collisions with successful
film drainage (Sees. 3.4.1 and 3.4.2.1).
Repeated coalescence may take place dur-
ing each passage through the weak zone if
there is time available. In order to get a dis-
tribution of drop sizes, the residence time in
the weak zone is distributed as a cascade of
n ideal mixers (Levenspiel, 1972)
iln\iln) (n-l
with E the distribution function and t the
mean residence time in the entire cascade of
ideal mixers, i.e., the residence time of one
passage through the weak zone. (An ideal
mixer is a hypothetic mixer in which differ-
ent components are homogenized perfectly
after zero mixing time.) The residence time
distribution becomes narrower as the num-
3.5 Applications 165
ber of ideal mixers in the cascade increas-
es, with the limiting case of plug flow if
n = oo. In the simulations a cascade of two
ideal mixers is used to generate a broad res-
idence time distribution in the weak zone.
Numerical Approach
The numerical simulation of the 2-zone
model is performed as follows. Since the
number of drops increases enormously
(a lmm sized drop yields 109 micrometer
sized drops), drop 'families' are considered
rather than individual drops. Each family
contains a number of identical drops/threads
that are characterized by a single radius R,
an aspect ratio L/B (with B = 2R), and a
cumulative residence time. Within a family
no time distribution is applied, so a number
of different drop families have to be used
(instead of one) in order to generate a dis-
tribution of drop sizes. This distribution is
initiated artificially to have a certain range
from the start. Further distribution is
achieved as a result of the residence time in
the weak zone. All drop families start in the
strong zone, pass through a specified num-
ber of cycles, and finally leave from the
weak zone. Passing each zone, subroutines
check for each drop family whether or not
the current size and flow conditions give rise
to stretching, breakup, or coalescence.
Concerning the distinct stages of the mix-
ing process, a number of assumptions have
been made. Drops with 1 < Ca/Cacvh < 5 are
not deformed in the strong zone although
they are unstable. The reason for this is that
they would only stretch slowly (less than
affine, Sec. 3.2.1.2), while the residence
time in the strong zone is short. Further-
more, affine deformation is calculated
according to 3-D elongational flow, where-
as values of Cacrlt are taken from 2-D elon-
gation. Coalescence only takes place with-
166 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
in each drop family because it is computa-
tionally intractable to give an individual
drop the opportunity to collide with all indi-
vidual drops in the system; moreover, the
collision frequencies of unequal drops are
still quite poorly modeled. Consequently,
the number of collisions would be underes-
timated; this is prevented here by taking the
total volume fraction 0 (summarized over
all drop families) into account within each
drop family. Film drainage prior to coales-
cence is modeled with partially mobile
interfaces unless restrictions are met that
indicate a transition to immobile or fully
mobile interfaces. The values of the initial
(h0) and the critical film thickness (hcrit) are
computed using Eqs. (3-58) and (3-59).
Becher and McCann (1991) propose a sim-
ulation of the emulsification process in which
the time dependence of the different stages is
'hidden' in rate constants. Hence the effect
of varying material parameters and process-
ing conditions is less clear than in the two-
zone model. Both models may predict over-
emulsification: a morphology that is tempo-
rarily finer than in its final steady state.
Effective Viscosity
In the detailed analysis of stretching,
breakup, and coalescence, the volume frac-
tion of the dispersed phase (0) is only taken
into account in the collision frequency
involved in coalescence; all other rules and
criteria hold for an isolated drop or thread
in an unbounded matrix. To incorporate the
volume fraction in the entire model, individ-
ual drops and threads are assumed to expe-
rience an effective matrix viscosity (7]c eff)
that is larger than the viscosity of the pure
continuous phase component (?]c) due to the
presence of neighboring drops and threads
that immobilize the dispersion. Throughout
the entire model rjc is replaced by r\c eff; only
in the local process of film drainage prior to
coalescence is r\c of the pure component
maintained.
For the effective viscosity of the emul-
sion, the Krieger and Dougherty (1959)
equation for monodisperse rigid spheres is
used with a modification to account for fluid
spheres. The modification is similar to Tay-
lor's (1932) extension of Einstein's (1911)
expression for rigid spheres at small vol-
ume fractions (Einstein Tjceff/ric= 1 + 2.50;
Taylor rjceff/ric = 1 + 2.5 0(p + 0.4)/(p + 1)
with/? the viscosity ratio 77d/f7c). The mod-
ified Krieger and Dougherty equation is
(3-72)
with 0m the maximum packing density. For
p oo the ratio (p + 0.4) /(p + 1) approach-
es unity and the original Krieger and Dou-
gherty equation for rigid spheres results.
The value of 0m may range from 0.6 for ran-
dom packing to 0.74 for closest packing of
monodisperse rigid spheres. For fluid drops,
0m depends on the viscosity ratio p and the
interfacial stress alR (due to the deformabil-
ity of the dispersed particles), and may even
approach 1 (foam). In the simulations, a
maximum packing density of 0.8 was cho-
sen, which is close to l-0 perc with 0perc the
percolation threshold (-0.156), as pro-
posed by Utracki (1993). The exact value of
the factor 2.5 in the above equations (in fact,
the intrinsic viscosity) holds for an ideal
diluted dispersion but may deviate signifi-
cantly in practical systems. Following
Eq. (3-72), the effective matrix viscosity
ranges from r\c for 0=0 to infinity for
0 -> 0m ( s e e curve in Fig. 3-45).
3.5.1.2 Results
As a typical illustration of the two-zone
model, the melt blending of polymers in an

extruder is simulated. Although most poly-
mer melts exhibit viscoelastic behavior, the
simulation is based on analyses for Newton-
ian liquids. The relevant material parame-
ters are chosen as follows: rid=ric =
100 Pas, (j = 5 x l 0 - 3 N / m , a o =10~ 9 m,
and 0 = 0.2. The strong zone is modeled
using = 30 s"1 and t=0.l s (yielding
L/# = e3/e~3/2 = 90 upon affine stretching of
a sphere); in the weak zone y= 3 s~] and the
residence time distribution resembles a cas-
cade of two ideal mixers with a total mean
residence time t - 10 s. A population of 100
drop families is initiated with diameters
around 1 mm. Figure 3-42 shows the evolu-
tion of the drop size distribution as the pop-
ulation cycles through alternating strong
and weak zones. The probability density is
calculated after discretization of all the drop
families into equal intervals; it is defined as
(y,/ytotal)/A(log R), with Vt the volume
occupied by drop families with a radius in
the interval A(log R) around Rt.
During the first three cycles of alternat-
ing strong and weak zones, all the drops are
stretched affinely in the strong zone and
threads of about 10|Lim thick are formed.
This is too thick to break up either during
stretching or at rest in the weak zone (given
the residence time), so nothing happens in
the weak zone. The extremely large aspect
ratios (L/B) represent packages of folded
threads (see Figs. 3-6 to 3-9). During the
fourth cycle, after further stretching in the
strong zone, some of the threads break up
into droples (L/B = 1) in the weak zone. The
breakup time required at rest has decreased
with the radius [Eq. (3-23)] and has now
reached the mean residence time in the weak
zone. In the fifth cycle the drops and remain-
ing threads are stretched again. All threads
formed are thin enough to disintegrate dur-
ing the residence time available in the weak
zone. At this point, submicron drops appear
that may easily coalesce: the lower limit of
3.5 Applications 167
the drop size is reached. After six cycles a
dynamic steady state is reached: drops that
are too small coalesce (repeatedly) and
drops that are too large stretch and break
again.
This simulation is supported by existing
experimental studies. For example, in the
work of Elemans (1989) the blending of
PS/HDPE on a corotating twin screw
extruder (25 mm screw diameter) yields a
typical length scale in the micrometer range
after a similar residence time in the extrud-
er. Evidently, the neglect of viscoelasticity
in the present two-zone mixing model is not
too serious for a global simulation of the
blending of polymer melts. As mentioned,
the strong zone represents both a convergen-
cy before passage over a kneading flight and
linear stretching in simple shear dominated
flow regions accompanied by folding
(Sec. 3.2.2). Generally, an extruder screw
has a large number of kneading disks but,
depending on the gap width between flights
and barrel, only a fraction of the material
actually passes through. The majority is
pushed sideways by an approaching knead-
ing flight (in the axial direction) and avoids
the gap. The weak zone represents transport
through the screw channel at low deforma-
tion rates.
Influence of Material Parameters
Before discussing simulations with dif-
ferent constituent viscosities, an overview
is first given of the scaling laws for the dis-
tinct stages (valid under limited conditions).
For drop stretching and breakup, governed
by Ca/Cacriv Eq. (3-1) and Fig. 3-2 show
that around p l:R c r]"1 xp or T]~x.
For thread breakup during stretching,
Fig. 3-22 indicates thatR oc 77~09x/?~45or
(7]d77c)~045. For coalescence with partially
mobile interfaces, Eqs. (3-70b) and (3-59)
168 3 Emulsions: The Dynamics of Liquid-Liquid Mixing

Q ir ii' 1r 1i n
i nr nn i
iii
i i Il IiMn I nI '"i JIr
i 1rr
1 1Ml! I PTTTTTTI ^

after 0 cycles after 1 cycle

L/B = l L/B = 90.02
1
4

I I Mill I I I I III
01 f mi i i i i IIIII i i i i mn

10-7 10-
6
10-5 10-4 10-6 io- 5 io- 4 io- 3
R[m] R[m]

-mmi 1 i i nun

after 2 cycles after 3 cycles

L/B = 8103 L/B = 7.294e+05
4 -

I
l0^ 10- 10-5
L 10-t 10-3
0'
io- 7 io- 6 io- 5 io- 4 io- 3
R[m] R[m]

after 4 cycles
L/B = 6.565e+07

I I I I 1 Illlr-iIII I I I I l l l l l ' I i Mini i i i

10-5 IO-4 IO-3

R[m] R[m]

Jflll
io- 7 io- 3

Figure 3-42. Morphology development in the two-zone mixing model with rjd = r\c = IO2 Pa s, o= 5x10 3 N/m,
^ = 10~9 m, and 0 = 0.2; strong zone f = 30 s~x and ? = 0.1 s; weak zone / = 3 s"1 and 7 = 10 s. Note that after
four cycles two distributions with different L/B apply.

(a)
p=100 p=l p=0.01
8
i 2
o io-6 10-5
10-7
R[m]
Figure 3-43. (a) Steady state morphology from the two-zone mixing model with rjc = 102 Pa s and r\d = 104,
102, or 1 Pa s (p = r\dlr\c = 102, 1, and 10~2); other conditions are the same as in Fig. 3-42. (b) Residence time
distribution characteristic for all three cases.
yidd/?oc n ^'3 x ^6/,3 or
thread breakup at rest, Eq. (3-26) and
Fig. 3-12 (around p l ) show that the
resulting drop radius depends mainly on the
initial radius and only slightly on the p-
dependent wave number; hence a scaling
law between R and r\d c is only of little use.
However, for the required breakup time of
a thread at rest, Eq. (3-23) and Fig. 3-16 (for
0.1 < p < 4 where Qm ^ p~0'5) lead to
tb~ricxp0-5 or (/7dr?c)0-5.
Figure 3-43 shows the steady state drop
sizes (after 10 cycles) for different viscos-
ity ratios p, and the residence time distribu-
tion that is characteristic for all three cases.
(The probability density for t is defined as
(Yi /^totaiVAO- The drop size distribution for
p-\ corresponds to Fig. 3-42 and confirms
that the result after six cycles is indeed the
steady state. Keeping 7]c constant, a larger
Tjd (p = 100) promotes a finer dispersion due
to retardation of both thread breakup (allow-
ing for further stretching) and coalescence
(eventually switching to immobile interfac-
es). The dispersion route is mainly the one-
step breakup of highly extended threads.
Upon decreasing 7]d (p = 0.01), threads break
up more quickly implying a stepwise
stretching and breakup route. As empha-
sized in Sec. 3.3.6, this results in coarser
3.5 Applications 169
(b) 0.03
after 10 cycles
H 0.02
c
o.oi
.nf
f -
50 100 150
t[s]
morphologies. In addition, the smaller value
of ?]d favors coalescence (eventually switch-
ing to fully mobile interfaces). From the
scaling laws given above, it is evident that
systems with higher viscosities favor a
thread-like dispersion route (larger time
required for thread breakup) with the sup-
pression of coalescence. A similar effect of
the viscosity ratio on the dispersion route
and the drop size was reported by Tjahjadi
and Ottino (1991) and Muzzio et al. (1991):
in addition, they found a broader drop size
distribution upon increasing /?, which is
probably due to their omission of coales-
cence.
In general, for a given set of processing
conditions a lower level of both viscosities
yields a coarser morphology, while highly
viscous systems can be dispersed more fine-
ly. However, given, e.g., the processing
conditions of Figs. 3-42 and 3-43, highly
viscous systems cannot be dispersed finer
than 10~7 m, since for smaller drops coales-
cence becomes dominant. Evidently, a
decrease in the interfacial tension yields a
proportionally finer morphology: olR
affects all stages in a similar way. Only
coalescence is favored less than proportion-
ally [Eqs. (3-70b) and (3-59): Roc a 9713 ],
causing the lower limit of the drop size.
170 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
Influence of Processing Conditions
The two-zone model is flexible for com-
paring the influence of processing condi-
tions. Increasing the strain (e t) applied in
the strong zone yields thinner threads with-
in a single passage. In the extreme, thread
breakup during stretching results in drop
sizes according to Fig. 3-22. In most cases,
however, the final drop size strongly
depends on the occurrence of coalescence.
In the weak zone, a longer residence time
favors thread breakup at rest and thus
implies a stepwise breakup route. Whether
coalescence is also favored by a longer
residence time in the weak zone depends on
the shear rate; this should be not too small
to be sure of collisions and not too large to
assure successful film drainage (the 'coales-
cence window' in Fig. 3-38). The volume
fraction (j) affects the model via both the
enlarged effective matrix viscosity and the
collision frequency for coalescence: gener-
ally, a larger (j) gives a coarser morphology.
Moreover, in reality a larger 0 generates a
higher level of initial disturbances oc0 due to
the pushing of neighboring drops and
threads (Fig. 3-26). This accelerates thread
breakup and makes the dispersion route
more stepwise, resulting in a coarser mor-
phology.
An interesting example of varying the
processing conditions is the optimization of
the gap height ^between the screw or knead-
ing flight and the barrel wall. By decreasing
the gap height, the converging flow at the
gap entrance becomes more effective for
stretching, but at the same time less materi-
al will pass through. Two extreme cases are
(i) 5=0, so that = <*> but no material can
pass, and (ii) 8=H (the channel depth), i.e.,
no flight at all, so that all the material will
pass, but with = 0. Somewhere in between
these extremes is an optimal gap height S/H.
In Fig. 3-44 such an optimization is illus-
trated based on the two-zone mixing model.
The resulting mean drop size is calculated
as a function of 8/H. Therefore the process-
ing conditions are varied as follows. As a
reference case, the calculation of Fig. 3-42
after six cycles is used with identical
material parameters (rjd= rjc = 102 Pa s,
G = 5 x 10~3 N/m, aQ= 10"9 m, and 0 = 0.2).
In the strong zone (the gap entrance)
the strain is determined by the compres-
sion from H to S: =-2 In (8/H) since
S/H = c~/2. (In the reference case =3,
which corresponds to S/H = 0.223). Taking
the time in the strong zone as constant at
0.1 s, the stretching rate is (s~l) =
/0.l =-20 \n(8/H). In the weak zone, the
shear rate is constant at y=3 s"1, and the
mean residence time t = ttotai/N with ttotal the
(mean) total residence time fixed at 60 s.
The number of cycles (or flight passages) TV
within this total mixing time is taken as pro-
portional to the relative gap height N c 8/H
with N=6 if S/H=0.223 (the reference
case).
The points in Fig. 3-44 represent the
mean drop diameters resulting from the sim-
ulations; the curve is a fit. For very narrow
gaps (regime I), the stretching rate is large
(e.g., = 44 s"1), but only a few cycles are
performed within the residence time given
(e.g., N=3). The dispersion route contains
a few large stretching operations followed
by final breakup. In regime II more cycles
are included, while is still substantial
(e.g., in the reference case, indicated by the
arrow, N=6 and = 30 s"1). The dispersion
route includes stretching, breakup, and
coalescence. In regime III the value of
becomes quite small, but the number of
cycles is large enough the obtain a steady
state morphology. In regime IV, although N
is large (e.g., Af=20), the strain per passage
is so small that it takes this many cycles to
thin the stretching threads down to the
micrometer range. At the same time, the res-

10-6
0 0.1 0.2 0.3 0.4 0.5 0.6
idence time in the weak zone becomes so
short (e.g., t =3 s) that only very thin
threads (R < 1 \im) break up.
If, in the simulations underlying Fig.
3-44, threads result after the last cycle, they
are broken artificially to obtain drops. (Thus
mixing ends with a long stay in a weak zone
in all cases.) The presence of an optimum
gap height S/H of about 0.25 is evident. For
large 8/H values, however, the simulations
are questionable since some basic assump-
tions no longer hold. In particular, the strong
zone becomes weaker and loses its charac-
ter. Irrespective of the exact values, the main
message from this exercise is that 'worn'
extruder screws or kneader wings might
be superior to new (more closely fitting)
ones, as already pointed out by Manas-
Zloczower et al. (1982). Moreover, this sug-
gests that in the scaling up of a compound-
er, the gap should be scaled accordingly in
order to keep 81H optimal (instead of to min-
imize it).
The two-zone model is relatively simple
but clearly illustrates the dynamics and
interaction of the relevant mechanisms.
Instead of simulating many drops using a
3.5 Applications 171
Figure 3-44. Mean drop
size as a function of the gap
height using the two-zone
mixing model with the
material parameters from
Fig. 3-42. Symbols give
simulation results; the
curve is a fit. The arrow
indicates the reference case
(i.e., conditions as in
Fig. 3-42 after 6 cycles).
0.7 0.8 0.9
computer, it is also possible to simulate a
single drop using the appropriate graphs and
equations in order to gain some insight.
Complications, such as shear rate dependent
viscosities or different flow conditions in
subsequent cycles, can easily be incorporat-
ed. An important conclusion after many
simulations is that the final drop size can-
not be predicted just by the critical capillary
number for drop breakup under quasi-equi-
librium conditions. The transient character
of the mechanisms (including coalescence)
has to be taken into account to predict the
typical trends observed in practice.
3.5.2 Passage Through a Die
In the examples of Figs. 3-42 and 3-43,
the blending process ended with quite a long
stay in the weak zone, which resulted in a
drop-in-matrix morphology. Practical poly-
mer blending may also yield thread-in-
matrix structures. As shown by Elemans
(1989), this is due to quickly quenching the
strand in a water bath on leaving the extrud-
er die. In terms of the two-zone mixing
172 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
model, the die is a strong zone and the stage
between the die and the quenching bath a
weak zone (in fact, a one-cycle case of the
two-zone model). A simple example illus-
trates what may happen to a dispersed drop
that passes through a die.
Consider a drop of 1 |am radius and vis-
cosity 10 3 Pas that is suspended in an
immiscible molten polymer of equal viscos-
ity; the interfacial tension between the mate-
rials is 5x10~3 N/m. The material passes
through the die of an extruder, experiencing
a mainly 3-D elongational flow with a total
strain =4.2 (convergence from 25 to 3 mm
diameter). Since the residence time in the
die is about 0.1 s, the elongation rate
e = 42 s"1. The drop experiences a capillary
number of 17 so that Ca/Cacrit = 75. Conse-
quently, the drop is stretched affinely
[according to Eq. (3-10 b)] into a thread of
0.12|nm radius. From Fig. 3-21 it can be
seen that the thread is about 40 times too
thick to disintegrate during stretching, so it
stays stable during its passage through the
die. After the strong die region, the polymer
strand is transported through the air towards
the quenching bath. During this time the
threads inside the strand may disintegrate as
the required time for thread breakup at rest
amounts to 3 s [see Eq. (3-23)]. Hence a
thread-in-matrix morphology is obtained if
the blend is quenched within these 3 s. Oth-
erwise the thread disintegrates into 64 drop-
lets of diameter 0.5 |um [Eq. (3-26) with
xm= 0.56]. So in polymer blending, thread-
in-matrix morphologies in the micrometer
range can easily be obtained in a strand.
This example illustrates that the last stage
of the blending process, including the
moment of quenching, is important for the
final morphology. Unless a specific resi-
dence time is required, such as for reactive
extrusion, most extruders are probably over-
designed for their mixing job. Of course,
some length is required for melting and
stretching, but a large part of the compound-
er just transports particles that are already
on the final length scale. At the end, the die
generates threads that eventually break up
into drops. In order to avoid coalescence in
the almost quiescent strand, the time before
quenching should be minimized.
3.5.3 Phase Inversion
At large volume fractions, phase inver-
sion may occur, i.e., the dispersed phase
becomes continuous and vice versa. A sim-
ple criterion for phase inversion is obtained
by comparing the effective viscosities of an
A in B and a B in A emulsion: a flowing
system will choose the emulsion with the
lower viscosity. Thus the critical fraction
can be estimated from Tjceff(A in B)
= 7]ceff(B in A) (see also Utracki, 1991,
1993). Figure 3-45 shows this concept for a
system with viscosities that differ by a
decade using Eq. (3-72), with the maximum
packing density of the dispersed particles
0 m = O.8.
Determination of the intersection point as
a function of the viscosity ratio of the con-
stituents leads to the phase inversion dia-
gram of Fig. 3-46. Upon addition of B to
pure A, phase inversion occurs at an even
smaller value of fa if the viscosity ratio
T7B/i]A is smaller; in other words, the low
viscosity constituent is more ready to serve
as the continuous phase than the high vis-
cosity component. The phase diagram pre-
sented strongly depends on the maximum
packing density (f)m required in Eq. (3-72).
The value of 0m depends on the viscosity
ratio 7]B/riA. In addition, (j)m depends on the
polydispersity and the shape of the dis-
persed particles, the latter of which is cou-
pled to the interfacial stress (a/R) and thus
to the particle size. These complications
have not yet been modeled for a general
case.
 3*5 Applications 173

IU c 1 1 1 n

IN 1 I-l1
1
103:

Mil 1 1 1
: \

102: phase inversion /

- \ /
AinB Figure 3-45. A criterion
101 . - . for phase inversion [using
I B in A Eq. (3-72) with 0m = 0.8]:
at the intersection the
system chooses the lower
viscosity case.
\

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Figure 3-46. Phase inver-

sion diagram predicted
from the principle of Fig.
3-45 for three values of the
maximum packing density

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

The kinetics of phase inversion are not
included. The mechanism is probably based
on the inclusion of continuous phase
domains upon multiple coalescence in a
highly concentrated emulsion. Also, small
drops of the continuous phase included by
dimple formation during coalescence might
play a role. Evidently, in a system with
higher viscosities, the inversion process will
proceed more slowly than in a low viscos-
ity system; in the high viscosity case (e.g.,
molten polymers), the value of the critical
volume fraction even seems to degenerate
to cover a range. In the melt blending of
polymers (high viscosities) this may give
rise to frozen-in cocontinuous structures (or
interpenetrating networks). Experimental
data on phase inversion are given by, e.g.,
Elemans (1989); qualitative agreement is
found with the concept presented here.
174 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
3.5.4 A Full Continuous Phase Flow
Simulation
The two-zone mixing model includes all
relevant mixing mechanisms, while the flow
is extremely simplified in comparison with
a practical, complex flow field. A different
approach is applied by Ottino and cowork-
ers: The complexity of the original flow is
maintained, while not all relevant mixing
mechanisms are included. Only stretching
and folding accompanied by thread break-
up during flow are considered; coalescence
is omitted. Tjahjadi and Ottino (1991) stud-
ied drop breakup in chaotic flows using the
'journal bearing flow', i.e., the 2-D flow
between two eccentric cylinders. The device
allows for the independent rotation of each
rotor in either direction, implying periodic
motion and chaotic flow patterns compar-
able to the cavity flow (Sec. 3.2.2.1).
A drop of an immiscible liquid (now with
interfacial tension) is stretched, folded, and
eventually disintegrates. Numerical simula-
tion of the flow provides the stretching his-
tory along the extending thread. If locally
the thickness of a thread segment goes
below the critical value given in Fig. 3-21,
this thread segment disintegrates into drop-
lets. The use of this criterion for thread
breakup at constant e is allowed since
e changes only slowly in comparison with
the growth time of disturbances (tg in Fig.
3-20). In other words, the local stretching
rate can be assumed to be constant during
the time interval of fatal disturbance growth.
Simulations of the local stretching history
in combination with the thread breakup cri-
teria closely resemble experimental obser-
vations (see Tjahjadi and Ottino, 1991).
[Note that an extending liquid filament
breaks if it is thin enough, i.e., Cafcrit
(Fig. 3-21), whereas a drop breaks if it is
thick enough, i.e. Cad > Cadcrit (Fig. 3-42).
This is due to the fact that the interfacial ten-
sion stabilizes drops, whereas it destabiliz-
es threads].
A special phenomenon occurs at the folds
of the threads. Around a fold the stretching
rate changes sign, producing local compres-
sion of the thread. While stretching sup-
presses thread breakup, compression pro-
motes it. So at a fold the thread is relative-
ly thick and breaks easily. Additionally,
at the ends of a thread large drops break
off by end-pinching (Stone and Leal, 1989 a,
b).
Clearly, some stages of the mixing pro-
cess, from affine stretching of large drops,
via distintegration of threads, to deforma-
tion and breakup of relatively small drops,
are present in this experiment. However, to
simulate a real mixing operation using vol-
ume fractions that do not tend to zero,
coalescence has to be included. The combi-
nation of transient, complex flow simula-
tions and all relevant mixing mechanisms is
a challenging next step in the modeling of
multiphase mixing. Even complex 3-D
flows are accessible (see, e.g., Avalosse
et al., 1992,1993) provided that sophisticat-
ed software and powerful hardware are
available.
3.5.5 Conclusion
It has been shown that a highly simplified
flow model combined with the relevant
(Newtonian) mixing rules provides a pow-
erful tool for simulating the development of
immiscible liquid-liquid morphologies. The
model predicts drop dimensions that coin-
cide, at least by an order of magnitude, with
the experimental data of even viscoelastic
blends. Moreover, the dependencies on the
different material parameters and process-
ing conditions are illustrative and indicate
guidelines for the preparation of blends with
desired morphologies. Clearly, quasi-equi-
librium data are insufficient as the dynam-

ics and interaction of all relevant mecha-
nisms are indispensable for making realis-
tic predictions. The two-zone mixing model
can serve as a guideline both in analyzing
existing mixers and designing new ones.
Moreover, it can be used as a guideline for
developing blends.
In order to attain the finest possible mor-
phology, use should be made of thead break-
up during stretching, although this demands
a high stretching rate for a sufficiently long
time (or 'smart' mixing with stretching and
folding). This mechanism of thread break-
up is favored in particular in the case of high
viscosities of both phases, while coales-
cence is suppressed. The required breakup
time of a thread largely increases with the
viscosities, which may result in thread-in-
matrix structures. With a little more time a
very fine dispersion may finally result.
In the melt blending of polymers, the pas-
sage through the die and the moment of
quenching are crucial, while part of the
screw length may be omitted. In many cases,
a morphology once obtained is not stable
and may change during subsequent process-
ing steps that could also be taken into
account in a simulation of mixing. In food
technology the viscosities are generally
smaller (~1 Pa s) than in polymer blending
(~103Pa s) so threads disintegrate faster.
Consequently, the dispersion route in food
technology is more stepwise than in poly-
mer processing where a one-step thread
mechanism is dominant.
3.6 Concluding Remarks
In the initial stage of blending immiscible
liquids, dispersed phase domains are so
large that Ca Cacrii\ they deform affine-
ly with the global flow and the deformation
rate and time are interchangeable (distribu-
tive mixing with passive interfaces). Most
3.6 Concluding Remarks 175
important is the introduction of folds and
reorientations leading to exponential mix-
ing. In the analysis and design of mixing
equipment, attention should be focused par-
ticularly on the minimization of islands
where no effective deformation occurs.
Affine deformation of large drops renders
long slender threads that keep thinning until
a local radius is reached at which the inter-
facial tension becomes active. The threads
become unstable with respect to interfacial
disturbances and disintegrate (dispersive
mixing with active interfaces). Deformation
rate and time are not interchangeable, but
are important separately. Therefore atten-
tion has been paid to the time scales of the
competitive processes such as flow induced
deformation and the growth of interfacial
disturbances. The breakup of viscous
threads both in a quiescent matrix and dur-
ing stretching can be calculated. Interesting-
ly, for identical final deformation rates a
one-step process of breaking an extending
thread yields smaller drops than the repeat-
ed breakup of drops under equilibrium con-
ditions (at Cacrit). Moreover, the transient
one-step mechanism predicts a finer disper-
sion upon increasing either viscosity (dis-
persed or continuous phase). This is quite
different from the commonly accepted rule
(based on the stepwise equilibrium route)
that both viscosities should match.
A morphology once formed generally
becomes coarser due to coalescence of the
dispersed phase. Although a larger velocity
gradient of the flow implies a larger colli-
sion frequency, these fast collisions do not
generally lead to coalescence, since the
short interaction time is insufficient for
drainage of the liquid film between the col-
liding drops, and so they tumble and separ-
ate. Consequently, coalescence takes place
preferentially in quiescent regions of a mix-
ing device (small Ca) while stretching
occurs in strong flow regions (large Ca).
176 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
The proposed two-zone mixing model
combines a largely schematized flow model
with all the relevant mixing rules and crite-
ria. It provides a useful tool for simulating
the morphology development during blend-
ing. The influence of the different process-
ing conditions and material parameters on
the transient mixing process and its final
result is illustrative and indicates guidelines
for the preparation of desired morphologies.
It is evident that quasi-equilibrium criteria
are insufficient; modeling the transient
character of the mixing mechanisms is
indispensable. To attain a fine morphology,
thread breakup during stretching should be
aimed at. High viscosities of both phases
especially favor this mechanism and, more-
over, suppress coalescence. Note that the
breakup time of threads also increases with
the viscosities, which may lead to thread-in-
matrix structures after quenching. Small
viscosities induce stepwise drop breakup
and lead to coarser morphologies. The last
steps of the blending process (e.g., die flow,
filament stretching, and quenching) are cru-
cial for the final morphology.
Viscoelastic effects play a significant role
if stresses are built up quicker than they
relax (# >1) and if the total strain is sub-
stantial (et >1). Under these conditions,
orientational stresses lead to a high elonga-
tional viscosity that considerably hinders
further flow. Particularly, in the breakup of
stretched viscoelastic threads the criteria are
fulfilled. Typical dumbbell shapes emerge
and breakup is largely retarded, at least for
the (extremely) elastic model liquids used.
The deformation of drops is less sensitive
to viscoelasticity. The value of Cacrit is
not affected as significantly as thread break-
up. Also the retraction of moderately
deformed drops in a quiescent matrix back
to a sphere is rather insensitive to viscoelas-
ticity. For coalescence, it is expected that
the film drainage between colliding drops
(biaxial extension) be retarded by the vis-
coelasticity of the continuous phase in par-
ticular.
A challenging next step in the current
modeling is the extension of the present
two-zone model to more complicated flow
fields. In principle, a full 3-D flow simula-
tion (using a quasi-homogeneous continu-
um) could be combined with all kinds of
local processes such as stretching, breakup,
and coalescence, but also mass transfer and
chemical reaction. An effort should also be
made to investigate the role of surfactants
on these local processes.
3.7 Appendices
3.7.1 Linear Flow Types
Most flow types used in experimental
studies are linear 2-D flows. These can be
described by the velocity vector
u = (Vu)c =L x (3-73)
where V is the gradient operator, x the posi-
tion vector, and L the velocity gradient
tensor (Giesekus, 1962; Fuller and Leal,
1981)
1 + a 1-a 0
L - G -1 + a -1-a 0 (3-74)
2 0 0 0
with - 1 < a < !
In a Cartesian coordinate system x (x, y, z)
the components of u (u, v, w) are
(3-75)
where G(s l) is the (scalar) velocity gradi-
ent and a indicates the type of flow [the ratio
 3.7 Appendices 177

a= -1

Figure 3-47. Streamlines

of specific linear 2-D
flows: a = 1, plane hyper-
bolic (or 2-D elongational)
flow; a- 0, simple shear
flow; a- - 1 , pure rotation-
a = -0.4 al flow.

between vorticity and strain rate is given by As usual, L is split into the rate of defor-
(l-a)/(l +a)]. In Fig. 3-47 the streamlines mation tensor D [=(L + Lc)/2] and the spin
are shown for various values of a. tensor Q[=(L - L c )/2]. For the linear 2-D
flows, Eq. (3-74), gives
F o r a = l , the velocity components are
u = Gx, v - -Gy, w = 0. This l+a 0 0
represents plane hyperbolic or G 0 -1 - a 0
2-D elongational flow, where G 2
0 0 0
is usually denoted , the elonga- (3-76)
tion rate. 0 1-a 0
G -l + a 0 0
Fora=0, the velocity components are ?
given in a basis that is rotated by 0 0 0
45: u' = Gy', i/ = 0, w' = 0. This
Plane hyperbolic flow (a = l) is free of
is simple shear flow, where G
rotation (Q = 0) and therefore called strong
is usually denoted y, the shear
in terms of deformation. In pure rotational
rate.
flow (a = - l ) , no effective deformation
For a = - l , the velocity components read
results (D = 0). Simple shear flow (a= 0)
u = Gy, v = -Gx, w = 0. This
includes contributions from both D and Q.
represents pure rotational flow.
In order to define the capillary number for
For values of a in between these specif- drop breakup in all these different flow
ic values, combined flow types are obtained. types, it is necessary to use a scalar value
The four-roll mill is able to generate the for the shear rate. Using the definition
entire range of linear 2-D flows; this is 7 = v (2D: D), the rotational components of
accomplished by varying the ratio of the L are subtracted and only effective defor-
speeds of the diagonal roller pairs (Giesek- mation is considered. For the linear 2-D
us, 1962; Bentley, 1985; Bentley and Leal flows this yields
1986a). a) (3-77)
178 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
and hence the capillary number
_rjcyR _
Ca = (3-78)
In this way, the vorticity of the flow type
is automatically taken into account. For
example, it is evident that a pure rotational
flow (a = -1) is unable to exert a deform-
ing stress on a dispersed liquid drop (Ca = 0
no matter how large the velocity gradient
G). Dispersive mixing generally considers
only the so-called strong flow types (0 <
a < 1) and not the weak flow types (-1 < a <
0). The definitions of y and Ca given here
are in accordance with those used by Taylor
(1934) and Grace (1971). Bentley and Leal
(1986b) use the velocity gradient G in the
capillary number instead of the shear rate
y[=G(l + a)], thus omitting (1 + a). In Sec.
3.3.4 the present choice is supported by
Fig. 3-28.
In numerical studies, 3-D elongational
flow is popular due to its rotational symme-
try. It is a linear 3-D flow with the velocity
field again given by Eq. (3-73), but now
with the velocity gradient tensor
2 0 0
G 0 - 1 0 (3-79)
2 thinning fluids, a steep velocity gradient is
0 0 - 1
so that u = GJC, V = -Gy/2, and w = -Gz/2,
with G usually denoted as , the elongation
rate. As in 2-D elongational flow, here also
Q = 0, i.e., the flow is free of rotation. The
shear rate y equals GA/3 , so that Ca = r\cGR
V3/C7.
3.7.2 The Opposed Jets Device
In experimental studies on drop breakup,
commonly used flow devices are the
Couette device (simple shear) and the four-
roll mill (plane hyperbolic flow or even all
linear 2-D flow types, as discussed in
Sec. 3.7.1). For the present study, however,
an opposed jets device was developed in
order to generate plane hyperbolic flow.
This appendix outlines the main features of
the opposed jets device (details are dis-
cussed in Janssen et al., 1993).
In order to explain the choice for a new
device, first some (dis)advantages of the
conventional four-roll mill are discussed.
The four-roll mill consists of four parallel
cylinders positioned in a square. It is flex-
ible in generating the entire range of linear
2-D flow types by variation of the speeds of
the diagonal roller pairs (Giesekus, 1962;
Bentley and Leal, 1986 a). However, a dis-
advantage is its complexity: the roller
speeds not only determine the velocity
gradient G and the flow type parameter
a (Sec. 3.7.1), but are also used to keep the
deforming drop at its unstable position at
the center of the device. In addition, a four-
roll mill does not allow for highly viscoe-
lastic fluids, because the shear stresses
generated by the rotating rollers may be too
weak to overcome the large elongational
stresses that occur at the inflow between two
rollers; so the fluid may not enter the cen-
tral region between the rollers (Metzner and
Metzner, 1970). In the case of strongly shear
present at the roller walls and the rollers can
hardly get the bulk flowing. Finally, the
large volume of fluid required and the
mobile parts of the setup may give rise to
practical problems when using specific
fluids like, e.g., molten polymers (at
200-300 C).
Given the above considerations, the aim
was to design a device that can generate lin-
ear 2-D flows (in particular plane hyperbol-
ic flow), but is smaller and easier to con-
struct and to operate than the four-roll mill,
and has the potential to be suitable for
experiments with viscoelastic fluids. The
concept is shown in Fig. 3-48 and is based

y
position x
T velocity u
wu
thickness 4 cm 2 cm
i 1 cm
Figure 3-48. The opposed jets device: drop deforma-
tion in 2-D elongation.
on the stagnation flow of opposed jets
(Muller et al., 1988). The liquid is pumped
in from two opposite directions and the two
flows impinge at the center of the cell, which
consists of four solid blocks between two
parallel, transparent plates.
In comparison with the four-roll mill,
the opposed jets device generates a similar
flow field in the central region. The three
'functions' (G, a, and the position control
of the drop) are completely independent:
the velocity gradient G is determined by
the flow rate, the flow type parameter a is
related to the shape of the cell, and the posi-
tion control is governed by the ratio of the
exit flow rates. Separation of these functions
makes the device less complex than the
four-roll mill. Furthermore, the opposed
jets device is expected to allow for highly
viscoelastic and shear thinning fluids, since
the fluid is pushed directly into the cell
(instead of driven indirectly by rollers; i.e.,
pressure instead of drag flow). The small
and closed flow cell can be made suitable
for polymer melts as well. The main disad-
vantage of the opposed jets device is the fact
that a different shaped cell has to be installed
in order to change the type of flow, in con-
trast to the four-roll mill that allows for the
variation of a even during a single experi-
ment.
3.7 Appendices 179
3.7.2.1 Design of the Flow Cell
In order to select the shape and dimen-
sions of the device, numerical flow simula-
tions were performed for the base flow
(without a dispersed drop). Using the finite
element package Sepran (Sepran, 1991), the
steady (Navier-)Stokes flow problem was
solved. For various shapes and flow condi-
tions, 2-D calculations yield the distribution
of G and a over the flow domain. The
dimensions given in Fig. 3-48 result in a
central region of 1 cm2 where the flow field
is quite uniform (less than 10% deviation in
G) and plane hyperbolic (a= 1) with
u = Gx, v = -Gy, w = 0. Several full 3-D
flow simulations, taking into account the
finite thickness of the cell, showed that at
least up to G - l O s " 4 (i.e., Re-I), the
velocity component w is negligible with
respect to u and v; in other words, the geom-
etry indicated in Fig. 3-48 produces an
acceptable 2-D flow. The calculated veloc-
ity field was verified experimentally using
laser Doppler anemometry (LDA). The area
of uniform velocity gradient (1 cm2) suffic-
es for drop breakup experiments with milli-
meter-sized drops.
Compared to the flow in a four-roll mill
of similar dimensions, the velocity gradient
in the opposed jets device is more uniform
over a larger area. Shear thinning fluid
behavior reduces the influence of the walls
and even enlarges the area of constant G, in
contrast to the (wall driven) four-roll mill.
The present geometry just consists of circu-
lar parts and straight lines. It was shown that
variation of the angle between entering and
exiting streams (other than 90) leads to lin-
ear 2-D flow types in between plane hyper-
bolic and simple shear flow (0 < a< 1).
After the selection of a suitable geome-
try, the flow field was calibrated in order to
carry out quantitative measurements on
drop breakup. Under Stokes flow condi-
180 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
tions, the velocity gradient is directly pro-
portional to the flow rate through the cell.
Calibration of the proportionality constant
was carried out in three different ways: (i)
from the numerical flow simulations, (ii)
from the LDA velocity measurements, and
(iii) from experimental particle tracking
using x = x0 exp(G0 (since u = Gx) in the
central area. The results of all three
techniques confirmed the scaling between
the velocity gradient G and the flow
rate Q with reasonable agreement (5%):
G(s"1) = 0.13 x 106 Q(m3/s) for the dimen-
sions of Fig. 3-48.
3.7.2.2 Position Control of the Drop
As mentioned before, the position of a
dispersed drop at the stagnation point is
unstable to disturbances; the drop tends to
leave the device. For studying the deforma-
tion behavior of the drop, the flow has to be
adjusted to keep the drop at the center. This
is done by frequently shifting the stagnation
point beyond the displaced drop, forcing it
to return towards the origin. In the opposed
jets device, a shift of the stagnation point is
achieved by variation of the ratio of the exit
flow rates as illustrated in Fig. 3-49. The
actual stagnation point shifts to the exit with
the smallest flow rate. The more the ratio of
the exit flows differs from unity, the further
the stagnation point is shifted from the ori-
gin. The two entrance flows are kept equal
to maintain a constant velocity gradient G
(a) (b)
and to restrict the stagnation point to the
x-axis. In practice, the ratio of the exit flows
is varied using a special valve in which both
exits are combined to one flow. Rotating this
valve increases one of the two flows and
automatically decreases the other one. Thus
the rotation of the valve is the only variable
in this 1-D control problem.
For the opposed jets device, a computer-
based control system was developed of
which the sensor part is similar to that of
Bentley and Leal's (1986 a) control system
for the four-roll mill. The first step of the
control cycle is the detection of the drop. An
image processor grabs an image from the
video camera and thresholds it yielding a
binary image of a black drop on a white
background. (Optimal illumination is cru-
cial to accomplish sufficient contrast in the
video image.) Next, a contour operation is
performed and the position of the drop cen-
ter is calculated as the mean position of the
contour pixels. Once the position of the drop
is known, and thus the displacement from
the origin, a computer calculates the newly
required position of the stagnation point and
the corresponding angular position of the
control valve. Finally, rotation of the valve
is carried out via a motor with a gear wheel
reduction. A sample rate of 25 control cycles
per second results in a stable position for the
deforming drop at the stagnation point: up
to G ~ 5 s"1, the variation in the drop posi-
tion is typically one pixel (the minimum
detection level).
Figure 3-49. (a) Principle of the
control system for the drop posi-
tion; the stagnation point is shifted
by varying the ratio of the exit
flows, (b) The control valve com-
bining the two exit flows to one
that leaves perpendicularly from
the center.

3.7.3 Characterization of the Model
Liquids
In all the experiments in this study, vis-
cous (Newtonian) liquids were used as the
continuous phase: different grades of sili-
cone oil (Rhodorsil, Rhone-Poulenc) were
blended homogeneously to cover a viscos-
ity range of 0.1 - 1 0 Pa s.
Both viscous and viscoelastic (non-New-
tonian) model liquids were used as the drop
phase. The viscous drops consisted of either
castor oil (Ashland Slid Chemie) or homo-
geneous blends of corn syrup (Globe, Cere-
star Benelux) and water. Castor oil has the
advantage of a big difference in refractive
index with respect to silicone oil, which
gives good contrast in the images. More-
over, it has almost the same density as sili-
cone oil, thus excluding buoyancy effects.
The corn syrup/water blends have the dis-
advantage of being rather more dense than
silicone oil, but their viscosity is easily
adjustable by variation of the water content.
The corn syrup/water liquids are coded by
the weight percentages of corn syrup and
water: e.g., cs 70/30 contains 30% (by
weight) water. These mixtures were pre-
pared by gently tumbling the containers for
several days. To avoid growth of bacteria
and mold, a trace of NaN3 was initally added
to the water.
Table 3-1 lists the relevant properties of
all the viscous model liquids. The viscos-
ities were measured both in oscillatory and
steady simple shear on a Rheometrics
RFS-II equipped with a cone and plate
Table 3-1. Properties of the viscous model liquids at room temperature .
Property Silicone oil
Viscosity, ?](Pa s) 0.1-10
Interfacial tension, a (N/m)
Density, p (kg/m3) 976
a
Interfacial tensions are given with respect to silicone oil.
3.7 Appendices 181
geometry. In the range of deformation rates
applied (10 - 2 -10 2 s"1) the viscosities were
indeed constant, while no first normal stress
difference could be measured. The densities
were determined using a pycnometer and a
balance. The interfacial tensions were meas-
ured using different techniques: (i) spinning
drop (Vonnegut, 1942; Elmendorp, 1986),
(ii) breaking thread (Chappelear, 1964;
Elemans et al., 1990), and (iii) small defor-
mation theory. The last technique is based
on Taylor's (1934) linear theory for the
deformation of a dispersed drop, which
predicts a proportionality between the cap-
illary number applied and the induced
steady extent of drop deformation, i.e.,
D = Ca(\9p+\6)/(16p+\6) for small D,
both in simple shear and plane hyperbolic
flow. From a steady drop deformation
experiment in the opposed jets device, all
the parameters in this equation are known
except the interfacial tension (din Ca). For
the system castor oil versus silicone oil, all
three techniques give the same value for a
(10%). For the corn syrup/water versus sil-
icone oil systems, the values may deviate by
almost a factor of 2, small deformation the-
ory yielding the lower values. In all cases
the small deformation technique was cho-
sen as the most representative for later
experiments under similar dynamic condi-
tions. The values of crlisted in Table 3-1 are
valid with respect to all grades of silicone
oil used.
For the viscoelastic drop phases, some
polyacrylamide (Separan AP30, DOW
Chemicals) with a molecular mass (Mw) of
Castor oil cs 70/30 cs 80/20 cs 90/10
0.74 0.073 0.35 3.4
0.0041 0.018 0.018 0.021
963 1273 1322 1373
182 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
about 4 x 106 g/mol was added to the corn
syrup/water mixtures; in fact, the polymer
was first dissolved in the water at an elevat-
ed temperature before the corn syrup was
added. Four different fluids were prepared:
cs 70/30/0.1, cs 80/20/0.1, cs 80/20/0.01,
and cs 90/10/0.01, with the last number indi-
cating the weight percentage of polymer. It
was found that both the density and the inter-
facial tension with respect to silicone oil
were the same as without the polymer.
The rheological characterization of the
viscoelastic drop phases was performed in
simple shear using a cone and plate geome-
try. The measured data were fitted to the
Phan-Thien Tanner model [Eqs. (3-39) to
(3-41)1. Small amplitude oscillatory shear
measurements were performed to determine
the linear viscoelastic parameters (77,, #,,
and 7]s). Next, from steady simple shear
experiments, the nonlinearity parameter
(,) was estimated. Start up experiments
(from zero to a steady shear rate), necessary
to indicate after what time the steady
state is reached (e.g., 10-60 s), provided
a control of the determined material param-
eters, i.e., the build up of the viscosity
and the first normal stress difference with
time.
10-2 10-1 100 101
co [rad/s]
Figure 3-50 gives the experimental
results of model liquid cs 80/20/0.01 in
oscillatory shear and the best fit using five
modes. Figure 3-51 gives the results in
steady shear. Predicted values of the elon-
gational viscosity are also included; meas-
ured data in steady uniaxial extension are
not available except from the thread break-
up experiments (Sec. 3.3.2.1) that indicate
Trouton ratios (7?^7?r) of 10 2 -10 3 . The
material parameters for all four viscoelastic
model liquids are given in Table 3-2. Note
that the values of the so-called solvent
visocsity r/s determined using the Phan-
Thien Tanner model agree reasonably well
with the viscosities of the actual solvents,
as given in Table 3-1.
3.7.4 Viscous Thread Breakup During
Stretching
The analysis of the breakup of an extend-
ing liquid cylinder surrounded by another
immiscible liquid was first carried out by
Tomotika in 1936. He considered an infi-
nitely long axisymmetric liquid thread in a
3-D elongational flow. Both thread and
matrix liquid are incompressible, Newton-
Figure 3-50. Model liquid
cs 80/20/0.01 in oscillatory
shear: dynamic viscosity r\\
rigidity 77", and phase angle
<S(tan 8= 77777") vs. fre-
quency co. Symbols give
experimental results, curves
the five-mode Phan-Thien
75 Tanner fit.
102 103
 3.7 Appendices 183

Figure 3-51. Model liquid

cs 80/20/0.01 in steady sim-
ple shear and uniaxial
extension: shear viscosity
r\y and first normal stress
difference Nl vs. shear rate
/and elongational viscosity
r] vs. elongation rate .
Symbols give experimental
results, curves the five-
mode Phan-Thien Tanner
fit.

Table 3-2. Material parameters of the viscoelastic model liquids fitted to the five-mode Phan-Thien Tanner
model.

Parameter cs 70/30/0.1 cs 80/20/0.1 cs 80/20/0.01 cs 90/10/0.01

Solvent viscosity, rjs (Pas) 0.11 0.54 0.43 4.1

Relaxation time, #i(s) 0.01 0.01 0.01 0.0251
#2(s) 0.1 0.1 0.0891 0.200
tMs) 1 1 0.794 1.59
#4(s) 10 10 7.08 12.6
^s(s) 100 100 63.1 100
Viscosity, ?], (Pa s) 0.0633 0.130 0.0041 0.0174
7]2(Pas) 0.183 0.460 0.0466 0.198
773 (Pas) 0.572 1.21 0.102 0.404
^4 (Pas) 2.00 3.80 0.254 1.12
f75 (Pas) 4.17 13.7 0.324 2.49
Nonlinearity, 1-5 H 0.1 0.05 0.02 0.02

ian, and of equal density; the Reynolds num-
ber is small. A small sinusoidal disturbance
is imposed at the interface and the appropri-
ate boundary conditions are prescribed with
a normal stress jump across the interface due
to the interfacial tension, the driving force
for capillary instabilities. Solving the bal-
ance equations gives the evolution of the
initial disturbances with time. Unfortunate-
ly, Tomotika's results are quite complex, so
that, at the time, only a few computations
could be done.
In 1975 Mikami et al. improved the anal-
ysis and clarified it by further numerical
elaboration. Khakhar and Ottino (1987)
extended the theory for 3-D elongational
flow to general linear flows. The analysis is
illustrated for a constant positive stretching
rate e. For time-dependent the basic equa-
tions are similar; only a time-dependent
has to be integrated or differentiated where
appropriate. One parameter differs from
Khakhar and Ottino's paper (1987), i.e., the
shear rate 7 to which time is made dimen-
184 3 Emulsions: The Dynamics of Liquid-Liquid Mixing
sionless: here A/(2D:D) is used instead of
V(D:D).
An infinitely long liquid thread is
assumed to extend affinely with the stretch-
ing rate . The initial wavelength Xo of a dis-
turbance is stretched accordingly
X- (3-80)
The cross section of the exending thread
is assumed to remain circular, thus the
thread radius R decays as
= R0Qxp(-et/2) (3-81)
and the dimensionless wave number
X[=2KR/XJ containing the current radius R
instead of Ro, as in Eq. (3-17)] also decreas-
es exponentially with time
x = x0 exp (-3 t/2) (3-82)
As indicated in Sec. 3.3.3.1, the efficien-
cy parameter ef(= v 2 //) appears in the
analysis upon making the time dimension-
less with respect to the shear rate y. In order
to find the evolution of the amplitude of a
disturbance having a specific initial wave
number xo(=2nRo/Ao), the balance equa-
tions of mass and motion with Newtonian
behavior and prescribed boundary condi-
tions are solved. The resulting growth rate
of a small sinusoidal disturbance amplitude
a can be written in terms of the material
properties (ric,p, a), flow conditions (ef, ),
and current geometry (R, x)
d\na (3-83)
if x <x c (i.e., t*>t*)
\n(a/a0) = Eq. (3-84) integrated
The functions <X>{x, p) and &(x, p) are
taken from Mikami et al. (1975); they are
given in Sec. 3.7.5. It is convenient to use
the wave number x as the current variable otherwise
instead of time [t = 2/(3e) ln(xo/x) or
t* = 23/2/(3ef) ln(jco/jc)]. Note that in the
case of e = 0, Eq. (3-83) reduces to
dlna/dt= a(l-x2) &/(2ricR0) (with time
not dimensionless): After replacing
(l-x2)0 by Q, this corresponds to Eqs.
(3-18) and (3-19).
Upon integrating Eq. (3-83) (from t = 0
to f*, or rather from x0 to x), the magnifica-
tion of an initial amplitude a0 of a distur-
bance with initial wave number x0 is
obtained as a function of x
&(x,p) +
3x
(3-84)
Generally, the development of the initial
disturbance amplitude consists of three
stages (Fig. 3-52): first the amplitude is
damped, then it grows for a while, and final-
ly it continues to be damped.
Since the amplitude cannot damp below
the initial 'noise' level a 0 , the first damping
stage is omitted, i.e., the amplitude remains
equal to a0. The second stage starts at the
critical time denoted tf, the amplitude is
magnified from a0, and the dashed horizon-
tal line in Fig. 3-52 becomes the baseline
where ln(a/a o ) = O. The magnification at
time t*(>t*) is calculated by integration
from t* up to t* (or rather from xc down
to x). In the third stage the amplitude damps
again, but can, once more, not decrease
below 0CQ. The magnification of ao during
the three stages can be summarized as fol-
lows
fromxc to x provided
that l n ( a / a o ) > O

Disturbances of all initial wave numbers
xOi evolve according to Eq. (3-85). Mean-
while, the (undisturbed) thread thins
according to Eq. (3-81), which can be tran-
scribed as
\n(R/a0) = ln(R0/a0) - (3-86)
Upon plotting ln(a/a0) and ln(R/a0) ver-
sus time (Fig. 3-20) the point of intersec-
tion, if present, corresponds to breakup, i.e.,
a(t) = R(t). For small values of x0 the initial
amplitude a0 is not magnified sufficiently
to cause breakup. With increasing x0 the
stage of amplitude growth starts later and
the magnification reaches a higher level. If
x0 is large enough, intersection occurs, giv-
ing a possible point of breakup. There is
only one disturbance with the optimum
initial wave number x0opt, which corre-
sponds to the shortest breakup time and
actually leads to breakup. The critical time
at which this fatal disturbance starts grow-
ing is denoted f*rit; at this time the thread
radius and the wave number have decreased
to Rcdt and xcrit, respectively. The actual
growth time of the fatal disturbance, *,
spans from f*rit to t%.
3.7 Appendices 185
Figure 3-52. Typical mag-
nification curve of an initial
disturbance amplitude a 0 as
a function of time t* (linear
scale) or wave number x
(logarithmic scale).
Different strategies are possible to deter-
mine the fatal disturbance characterized by
the initial wave number x0opt, e.g., a func-
tion t$(x0) can be constructed so that x0opt
simply corresponds to the minimum func-
tion value. The procedure for this function
is as follows: For a given x0 the value of xc
(Fig. 3-52) is determined by evaluating
dln(a/a o )/dj:[= the integrand of Eq. (3-84)
with a minus sign]. Next, the \n(a/a0) and
\n(R/a0) versus x(or *) curves are calculat-
ed using Eqs. (3-85) and (3-86). An eventu-
al intersection point gives the breakup time
t% for the disturbance wave number x0 con-
sidered; if the curves do not intersect, t%
is infinite. For too small values of x0 the
stage of amplitude growth is absent and xc
does not exist; these values of x0 are irrele-
vant.
From the shape of the ln(a/a0) curves in
Fig. 3-20, it can be seen that the smallest
breakup time does not just correspond to the
smallest x0 that gives intersection. There-
fore a procedure is adopted that encloses the
minimum of the function t$ (x0) between two
limits. First, a value of x0 is chosen that is
small enough not to have an intersection
186 3 Emulsions: The Dynamics of Liquid-Liquid Mixing

point (t% =); in this case x0opt is definitely

Ix Xlx xKx
larger. Next, x0 is increased stepwise until
an intersection is obtained (7g finite); the h h + xh -Ko+xKx
previous x0 value (not quite yielding inter- Ph pxlo -xK0
section) is the lower limit for x 0opt . Then,
x0 is increased further until a larger break- h xl[ Kx
up time is found; this provides the upper h k+xlx -Ko
limit for x0opV In this way, the minimum of Ph pxlo Kx
t$(x0) is enclosed and the interval can be
decreased down to the desired accuracy for
p[(x2 I,-xI0] xKt (x2 +\)Kl+xK0
xK{
3.7.5 The Functions & and & A) + xh -K0+xK]
The functions <2> and & appear in the anal-
ysis of thread breakup in viscous systems pxlx xKx (x2 +l)K\+ xK0
(Tomotika, 1935, 1936; Mikami et al., Ix Kx xK[
1975; Palierne and Lequeux, 1991). In the IQ -KO -KO + xKx
breakup of a stretching thread both <2>and 0
are used (Sec. 3.7.4). In the case of thread where Iox and Kox are functions of x only;
breakup in a quiescent matrix only 0 is Iox are modified Bessel functions of the first
required; the growth rate of disturbances kind (of order 0,1) and Kox are modified
is then given by Q = (l-x2)0 (Sec. Bessel functions of the second kind (of order
3.3.1.1). 0,1). Using Matlab (1993) these are standard
Both 0 and 0 depend on the wave num- functions. /[ and K[ are the derivatives of Ix
ber x and the viscosity ratio p (=Tid/ric) and Kx with respect to x and can be calcu-
lated as
0 = ~(IXAX-XI[A2) and
A = Io - - and Kx =-K0-^-
x x
0 ( I l A l x

where
A = pxIxAx -p[(x2 +1)/! -xI0]A2
3.8 References
Abid, S. (1993), Ph.D. Thesis, Institute of Fluid
+jtKXA3 -[(x2 +1)Kx + xKo] A4 Mechanics, Toulouse, France.
Abid, S., Chesters, A. K. (1994), Int. J. Multiphase
and the determinants Flow 20, 613.
Acrivos, A. (1983), Ann. NY Ac ad. Sci. 404, 1.
xlx Al *A", Aref, H. (1991), Phys. Fluids A 3, 1009.
lo+xl\ -1^o Avalosse, T., Crochet, M., Fobelets, A. Dehennau, C.
*1 - -Aro+jc/:, (1992), in: Proc. 11th Int. Congr. on Rheology,
pxlo A\ ~xK0 Brussels, Belgium. Amsterdam: Elsevier, p. 318.
Avalosse, T., Crochet, M., Fobelets, A., Dehennau, C.
(1993), PPS Meeting for the Americas, Morgan-
h Kx xK'x town, WV, U.S.A.
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4 Flow-Induced Orientation and Structure Formation
Andrew Keller

H. H. Wills Physics Laboratory, University of Bristol, Bristol, U.K.

Hans W. H. Kolnaar

DSM Research BV, Geleen, The Netherlands

List of Symbols and Abbreviations 191

4.1 Introduction 192
4.1.1 Objective of this Chapter 192
4.1.2 Scope of this Chapter 194
4.2 The Fundamentals of Chain Extension 195
4.2.1 The Extension of Isolated Chains as Explored in Solutions 195
4.2.1.1 Preliminaries and Methodology 195
4.2.1.2 Molecular Characterization by the Elongational Flow Methodology 197
4.2.1.3 Flow-Induced Scission 199
4.2.2 Chain Extension in Permanent Networks 199
4.2.3 Transiently Interacting Chains 200
4.2.3.1 General Considerations 200
4.2.3.2 The Elongational Flow Approach to Transiently Interacting Chains 201
4.3 Structure Formation in Flowing Solutions 203
4.3.1 The Origin of Shish-Kebabs 203
4.3.2 The Structure of Shish-Kebabs 207
4.3.3 On the Mechanism of Shish-Kebab Formation 209
4.4 Structure Formation in Flowing Melts 211
4.4.1 General Considerations 211
4.4.2 Structural Analogies - Overall Morphology 212
4.4.3 Chain Extension - Fiber Generation 213
4.5 Relation Between Morphology and Orientation 217
4.5.1 The General Scheme 217
4.5.2 Examples of Fibrous and Parallel Lamellar Columnar Structures 221
4.5.3 A Special Case of Fiber-Platelet Structures: Interlocking Shish-Kebabs . . . 225
4.5.4 'Row Structures' 226
4.5.5 Interpretation of Orientation Effects 227
4.5.5.1 General 227
4.5.5.2 Orientation in Terms of Fiber-Platelet Morphologies 229
4.6 Orientation and Structure Formation in Simple Shear Flow 232
4.6.1 General Considerations 232
4.6.2 On the Role of Entanglements in Simple Shear Flow 233

Materials Science and Technology

Copyright WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
190 4 Flow-Induced Orientation and Structure Formation

4.7 Oriented Crystallization in Stretched Networks 235

4.7.1 Cross-Linked Polyethylenes 235
4.7.2 Crystallization of Traditional Elastomers 236
4.8 Discussion 239
4.8.1 General Considerations 239
4.8.2 On the Circumstances of Shish-Kebab Formation and Its Implications . . . . 240
4.8.3 A Special Case of Chain Extension: Adsorbed Molecules 243
4.9 Orientation Due to the Alignment of Supramolecular
Structure Entities 244
4.9.1 Orientation in Weak Flows 244
4.9.2 Orientation in the Absence of Flow 246
4.10 The Effect of Structure on Rheology:
The 'Extrusion Window' in Polyethylene 248
4.10.1 Introduction and Basic Features of the Window Effect 248
4.10.2 The Significance of the Window Effect for Melt Flow Rheology 255
4.10.3 Wider Implications 257
4.11 Some Practical Applications of the Concepts Developed 259
4.11.1 Structure Formation Relying on Elongational Flow 259
4.11.1.1 'Hard-Elastic' Fibers 259
4.11.1.2 Extrusion and Molding Processes 261
4.11.2 Structure Formation Relying on Controlled Solidification and Shear Flow:
The SCOREX and SCORIM Processes 262
4.12 Concluding Remarks 263
4.13 Note Added in Proof 265
4.14 References 266
 List of Symbols and Abbreviations 1 91

List of Symbols and Abbreviations

c concentration
c+ critical concentration
c* concentration for chain overlap
/ intensity
/ fold length
M molecular weight
Mn number-average molecular weight
Mw weight-average molecular weight
p extrusion pressure
pc critical pressure
t time
fdis disentanglement time
tnow flow time
T temperature
Tc crystallization temperature
Tm melting point
T^ theoretical melting point of infinite crystal
(T m ) h melting point of metastable modification (hexagonal phase)
(rm)o melting point of stable modification (orthorhombic phase)
v piston velocity
vm mean velocity
crystal growth velocity

7 shear
7 shear rate
7A apparent wall shear rate
7A,C apparent critical wall shear rate
7C critical shear rate
e strain, elongational
e strain rate, elongational
c critical strain rate, elongational
ef critical fracture strain rate, elongational
n critical strain rate for transient, mechanically effective network formation,
elongational
a stress
ac critical shear stress

PE polyethylene
PEEK polyphenylene-ether-ether-ketone
192 4 Flow-Induced Orientation and Structure Formation
4.1 Introduction
4.1.1 Objective of this Chapter
The present chapter aims to provide a sur-
vey of orientation phenomena in polymers
and their consequence for structure forma-
tion, along with the potential connection and
relevance to processing and products. It
hardly needs stating these days that long
chain molecules lend themselves to the
attainment of oriented products with asso-
ciated advantageous properties. There are
principally two different routes towards this
goal: (1) drawing (or otherwise orienting)
an initially random crystalline solid, and (2)
to orient chains in their random state (solu-
tion or melt) first and 'set' this orientation
by subsequent crystallization. In this respect
a distinction needs to be made between rigid
rod molecules and flexible chains. To
achieve orientation, rigid rods only need to
be aligned, while flexible chains need both
extending and aligning, the two occurring
simultaneously in the course of a normal
orientation process. Having stated this, we
shall only be concerned with flexible chains
and hence the stretching out of chains, in
what follows. We shall also only be con-
cerned with route (2), leaving the issue of
orientation from the solid state unaddressed.
[Solid-state orientation will be dealt with in
part by Ward in Chapter 16 of this Volume.]
Surveys with the above-defined content
have been presented repeatedly before (Kel-
ler, 1977, 1979; Keller and Mackley, 1974;
Keller and Kolnaar, 1993). However, in the
present paper the pertinent material will be
presented with a specific underlying theme.
In aid of this we shall first invoke some work
on the fundamentals of chain extension, per-
formed on solutions. Again, the latter has
been presented before, but in the context of
solution behavior; its reinvoking in connec-
tion with crystallization may therefore not
be an inopportune repetition in view of the
context of this section.
For the case of the orientation of chains
in their random state (solution or melt) and
their subsequent crystallization [subject
area (2) above], the theme is as follows: in
terms of flexible chain conformations there
are only two stages of orientation, i.e., the
essentially fully stretched out and the essen-
tially unoriented, random chain, with no
intermediate stages that are of consequence
here; in addition, all we observe in the final
products are the consequences of these two
extremes. Intermediate orientations such as
are seen in partially or not fully oriented
products are due to the different combina-
tions of the two extremes just stated, and not
to intermediate chain orientations as such.
We consider these assertions as basic, with
a vast and diverse amount of observational
evidence and also some fundamental back-
ground to support them, which we shall
attempt to convey here.
There are two stages to be considered: (i)
the primary chain orientation itself, and (ii)
the fixation of the chain orientation, which
occurs mainly by crystallization. Our theme
of two extremes with no intermediate stage
applies to both stages, but in different inter-
related contexts. Thus when a single chain
within an assembly, which is mechanically
unconnected to others, is exposed to exter-
nal orienting influences (in our case flow),
it either extends almost completely or stays
as a random coil. This is of course a bold,
generalizing statement, not intended to
imply that departures from the fully
stretched towards the contracted state do not
exist. Clearly they do, but we maintain that
within steady state conditions such depar-
tures are small, and as a first approximation
do not invalidate our main theme. We shall
'lump' such departures together within the
random or fully oriented categories accord-
ing to which they are closest. Of course there

Figure 4-1. Lamellar single crystal of polyethylene
grown from solution. Electron micrograph (Keller.
1985).
Figure 4-2. Lamellar crystal of polyethylene grown
from the melt and extracted subsequently from the
solidified material (scale bar = 1 urn). Electron micro-
graph (Toda and Keller, 1993).
must be intermediate states as transients (as
opposed to the steady state) on the way to
full chain extension, but we have yet to note
their influence in the wide ranging effects
to be referred to here; so far we have found
no need to take note of them. In what fol-
lows we shall first place these effects on the
map.
4.1 Introduction 193
Figure 4-3. Extruded film of polyoxymethylene
showing fibrous crystals (NW-SE) in addition to the
oriented crystal lamellae (NE-SW) seen largely from
an edge-on view. The fibrils are aligned along the
extrusion direction (arrow) and act as nuclei onto
which the lamellae crystallize (Garber and Clark
1970, 1971).
In the above we referred to the primary
chain extension. With crystallization two
distinct categories again arise from the
above two extremes: the random chain leads
to chain-folded lamellae and the extended
chain to fibrous crystals, with the chains
essentially (including all kinds of defect)
extended within them. Examples of folded-
chain lamellae from solution are shown in
Fig. 4-1 and from the melt in Fig. 4-2, the
latter being obtained by specially low under-
cooling (for a comprehensive review see,
e.g., Keller, 1985; see also Chapters 3 and
4 in Volume 12 of this series). A more gen-
eral situation representing the lamellar com-
ponent arising in a certain type of oriented
crystallization from the melt (Sec. 4.11.1.1)
is depicted in Fig. 4-3, which also displays
194 4 Flow-Induced Orientation and Structure Formation
the second kind of crystal, namely the
fibrous species. These two morphologies
are again distinct, with, to our knowledge,
nothing intermediate in between.
Having introduced the principal morpho-
logical players, namely the lamella and the
fiber, the question that remains is the degree
of chain extension that is needed to 'switch'
from the lamellar to the fibrillar morpholo-
gy. In situations where the chain orientation
prior to crystallization can be diagnosed
(such as in solutions, Sec. 4.2.1) the ques-
tion does not arise because no intermediate
state of chain extension, i.e., no 'halfway
house', could be found, at least as a steady
state. In cases where a similar diagnosis
could not be carried out with the same con-
clusiveness (as, e.g., in melts) the question
remains as to the degree of chain extension
required for the morphology to switch from
lamellae to fibers within a continuous spec-
trum of chain extensions. Nevertheless, as
will be seen, the situation as regards
'on-off' (or 'yes-no') effects so closely par-
allels the solution case that a direct transfer
of experience from solutions to melts is
clearly invited: more specifically, the exis-
tence of a coil > stretch transition and the
exclusive (to a first approximation) duality
of the random and fully extended chains.
This is in spite of difficulties to envisage
such a situation in the molten state, be it for
intuitive or preconceived reasons.
At this point an important injection has to
be made as regards crystal formation from
preextended chains. Chain extension pro-
motes crystallization both for thermody-
namic and kinetic reasons: thermodynami-
cally, because it increases the melting point
(the entropy of the melt or solution is low-
ered, hence the free energy is raised) and
kinetically, since an extended chain is clos-
er to its state in the crystal and has less of a
kinetic barrier to overcome than a chain in
the random state. It follows therefore that
orientation-induced crystallization and
hence the formation of fibrous crystals will
always proceed faster and can also take
place at a higher temperature than the crys-
tallization from the random state yielding
the lamellar crystals.
In what follows we shall try to combine
the works on flow-induced crystal morphol-
ogy with those on flow-induced chain exten-
sion, the latter irrespective of crystallization
or preceding crystallization. Historically, at
least as far as we are concerned in Bristol,
the elucidation of the crystallization effects
was the first objective which then, for great-
er understanding, prompted a separate pro-
gram on chain extension itself. The latter
line, pursued for the simpler case of dilute
solutions, has become a pursuit of its own,
providing an improved insight into the
extensibility of long chain molecules. The
present article aims to bring these two sub-
ject areas, stemming from the same roots but
pursued separately, together again in the
service of the theme stated. The main point
is that there is a two-way connection
between chain extension and the crystal
morphology resulting therefrom: the chain
extension determines the morphology on
subsequent crystallization, while the mor-
phology, as observed after crystallization,
can serve as a pointer to the preexisting state
of chain extension, provided we can read the
message it conveys.
4.1.2 Scope of this Chapter
Having declared the guiding theme, the
article itself is to cover the following mate-
rial, and this in the following sequence.
First, the fundamentals of chain extension
will be briefly reviewed as achievable
through elongational flow, together with the
relevant underlying experimental material,
first for isolated and then for interacting
chains, touching briefly on the issue of net-
 4.2 The Fundamentals of Chain Extension
works. By its very nature such material will
be confined to solutions. This will be fol-
lowed by a very brief survey of the crystal-
lization of chain-extended material, still in
solutions, providing the morphological
basis for the more general case of melts,
which will form the core of the article.
The discussion of structure formation
from the melt will start by drawing parallels
with the more readily observable and con-
trollable effects in solutions, specifically
with the description of common morpholog-
ical features and the generation of fibers.
From here the discussion will proceed to the
various macroscopic orientation effects to
which the microscopic morphology can give
rise, still based on elongational flow-gener-
ated chain extension. After this, the effect
of simple shear flow will be considered, the
subject of much of conventional melt rheol-
ogy, to be followed by a brief section on net-
works. In the last connection some totally
open-ended issues regarding the strain
required for orientation-induced structure
formation will be placed on the map, as a
concluding and at the same time forward-
looking section.
Other topics will also be touched upon in
the course of the above, such as macroscop-
ic orientation effects only attributable to
very weak flow (or no flow at all) with no
stretching out of the chains, some cases
relating to technological practice, and the
all-important feature of the influence of
structures reacting back onto the flow which
has initially generated the structures them-
selves.
4.2 The Fundamentals
of Chain Extension
First we need to distinguish between the
extension of chains (i) as in isolation and
(ii) as permanently, i.e., chemically, cross-
195
linked, hence forming part of a network, as
the two extremes. Between (i) and (ii) lies
(iii) the whole spectrum of physical con-
nectedness, which by its very nature is tran-
sient, its effectiveness being determined by
the time scale of the chain-extending influ-
ence. In what follows we shall take (i), (ii),
and (iii) in turn.
First we must state that reasonably pre-
cise information is available on (i) and (ii),
with the situation under (i) having been
(amongst others) our own working area and
that under (ii) being the well-grounded sub-
ject of the stretching of rubber networks.
The situation under (iii), however, is much
more elusive, we shall only be able to con-
tribute to this by setting some pointers.
4.2.1 The Extension of Isolated Chains
as Explored in Solutions
4.2.1.1 Preliminaries and Methodology
The situation of isolated chains can only
be realized in solution, and this only in high
dilution, which is the subject of the present
section. Special as such systems may
appear, they serve to establish basic knowl-
edge, which (as it will become apparent)
can, to a surprising extent, be transferred to
more general situations where by a priori
geometric considerations the chains can no
longer be regarded as isolated.
As will be familiar, extending a long
chain substantially is not as straightforward
as it may first appear. For uncross-linked
chains, stretching forces can only be trans-
mitted by means of flow through frictional
contact between a given chain and its sur-
rounding medium, which in the case of
dilute solutions is of course the solvent.
The customary simple shear flow is inad-
equate in this respect because of its rotation-
al component. To achieve full, or nearly full,
chain extension the flow has to be
196 4 Flow-Induced Orientation and Structure Formation
'elongational', i.e., the dominant compo-
nent of the velocity gradient has to be par-
allel to the flow direction, the simplest case
of the latter being unidirectional accelerat-
ing flow. The effect of elongational flow on
an isolated random coil macromolecule, as
found in dilute solutions, was worked out
theoretically by de Gennes (1974) [follow-
ing preceding works by Peterlin (1966)],
leading to the prediction of a sharp coil >
stretch transition at a specific strain rate ().
This means that as the elongational flow rate
is gradually increased through increasing
the velocity gradient along the flow direc-
tion, there will only be small changes in the
conformation of the random coil at first up
to a critical strain rate (c) beyond which the
coil will stretch out almost completely. It
follows that there is no steady intermediate
state: below c there is practically no chain
extension, while above c the chain becomes
practically fully extended. In addition to
reaching the critical strain rate, the exten-
sional influence must also be maintained for
a long enough time (t) for the high strain (e)
corresponding to final steady state exten-
sion to be reached. The latter can be
achieved through appropriate flow field
geometries. Thus, if there is a stagnation
point present, the high strain condition will
automatically be satisfied. In simple words,
the origin of the coil stretch transition lies
in the fact that once the resistance of the ran-
dom coil to substantial extension is over-
come on reaching c, its frictional contact
with the surrounding fluid (solvent) medi-
um is increased, which in turn increases the
resulting chain extension, and so on. Thus
the extension of the chain becomes a run-
away effect until close to near complete
chain extension; continuing extension is
opposed by the intrinsic resistance to
stretching of the valence bonds themselves.
It is apparent that the above considera-
tions are of salient significance for the
response of macromolecules to flow, and
vice versa, i.e., for the effect of macromol-
ecules on the flow itself. This is the subject
area which the Bristol program set out to
explore over the last decade (Mackley and
Keller, 1975; Pope and Keller, 1978; Odell
etal., 1985, 1992a, b; Keller and Odell,
1985; Miles and Keller, 1980; Keller et al.,
1985; Chow et al., 1988), some landmarks
of which will be recalled in what follows.
The first requirement was the creation of
well-characterized elongational flow fields,
and secondly a diagnostic tool to follow
chain extension when this occurred. For the
former several methods were designed
and/or used. Foremost amongst them was
the flow cell consisting of two opposed jets.
The two jets were immersed in the solution
that was being sucked out simultaneously
through both jet orifices. This created a
purely elongational flow field between the
two jet orifices along the center line. Here
the velocity is zero at the center (stagnation
point) and increases linearly in both direc-
tions towards the jet orifices (Fig. 4-4).
Chain orientation was registered by observ-
ing the resulting birefringence between
crossed polarizers. This became apparent as
a sharply defined bright line against a dark
background along the central jet axis
0.08 cm
Symmetry
Fluid flow
lines
Figure 4-4. The principle of the opposed jet tech-
nique for the study of molecular extension by elonga-
tional flow showing flow lines (Keller and Odell,
1985).
 4.2 The Fundamentals of Chain Extension 197

achieved. It will become apparent that we

acquired a powerful visual method for prob-
ing the influence of flow on macromole-
cules, and vice versa, i.e., the influence of
macromolecules on the flow itself, which
was exploited in the works that followed.
[See "Note Added in Proof at the end of the
chapter.]

4.2.1.2 Molecular Characterization

by the Elongational Flow Methodology
One of the follow ups of the above-men-
tioned recognitions was the relation be-
Figure 4-5. Chain extension by elongational flow tween the critical strain rate (c) and the
between two opposed jets seen as a birefringent line molecular weight (M). First the basic quan-
between crossed polars, in this case in a polyethylene
solution above the crystallization temperature (Mack- titative aspect of the experiment will be
ley and Keller, 1975). recalled. For this the transmitted light inten-
sity, / (which for low optical retardations is
proportional to the square of the retarda-
(Mackley and Keller, 1975) (Fig. 4-5).
tion), along the central axis of the jet is plot-
When closely monodisperse [sharp molec-
ted as a function of . As seen, e.g., from the
ular weight (M) distribution] polymer was
curve for Mj in Fig. 4-6, /is practically zero
used, this bright line appeared discontinu-
till (ec)i where it suddenly rises to a plateau
ously at a critical strain rate (c) as was
value. Here (c)l is the critical of the coil
increased. The degree of chain stretching
stretch transition for material of molec-
could be determined from the magnitude of
the birefringence which, within the latitude
of known polarizability values, was found
to correspond closely to full chain extension
(Pope and Keller, 1978). These findings thus
confirmed the reality of a coil > stretch
transition in elongational flow in support of
theory; conversely it established the meth-
od, possibly the only method, by which a
long-chain flexible molecule can be
stretched out nearly completely in a con-
trolled and registrable way. The sharpness
of the lines could be satisfactorily attribut-
ed to the fact that they corresponded to flow (U
paths going through or near the stagnation strain rate
point where the deforming fluid element Figure 4-6. Schematic plots of transmitted intensity
spent the longest time; hence where for a vs. strain rate for three different molecular weights
M{>M2 > M3, showing the coil > stretch transition at
given strain rate (>c) the required strain the critical strain rates (ec)u (c)2, and (c)3, respec-
(= t) for full chain extension could be tively.
198 4 Flow-Induced Orientation and Structure Formation
ular weight Ml9 and the plateau value of /
corresponds to that due to the practically
fully stretched out chain. Now, taking close-
ly monodisperse polymers of different M
(M2 and M3 in Fig. 4-6), different curves
with different c values are obtained. The
schematic plots in Fig. 4-6 illustrate the
trend: the lower M, the higher c, and vice
versa. This means that longer chains can be
extended using lower strain rates and hence
less strong flows, and vice versa; in simple
words the long chains are more readily
extensible. Quantitatively this is expressed
by the relation
8cooM-p (4-1)
where /3 was found to be 1.5 by our experi-
ments, rather remarkably, independent of
the solvent quality (Odell et al., 1992 a).
It will be readily apparent that this newly
found relation [Eq. (4-1)] and the method to
determine c experimentally provide a new
route toward the determination of molecular
weights, with certain advantages over con-
ventional methods (Keller and Odell, 1985;
Miles and Keller, 1980). First, it is most sen-
sitive at the highest M (where c is lowest),
where most other methods are either too
insensitive or difficult to apply. Secondly,
when there is a continuous distribution of
molecular weights (as is usually the case),
then the resultant / vs. trace will be a sum
of components such as Mx, M2, M3, etc. in Fig.
4-6; this can be readily dissected into its com-
ponents by differentiation. This then provides
a method for obtaining the actual molecular
weight distribution from the highest M end
down to a low end cut-off, which, in accor-
dance with Eq. (4-1), is determined by the
highest that can be achieved in a given appa-
ratus. Thus we see that a flow-induced effect
can provide a tool for basic molecular weight
characterization by utilizing chain extensibil-
ity, possibly the most intrinsic characteristic
of a flexible filamentous molecule.
It can thus be seen that the coil > stretch
transition, as assessed by the single parame-
ter c, has a two-fold criticality: for a given
M there is a critical and for a given there
is a critical M. The latter acquires particular
significance in the usual situation of a molec-
ular weight distribution when subjected to an
elongational flow field of a particular . Here
only the longest chains will be extended, with
a low end cut-off at a specific M, correspond-
ing to the appropriate c from Eq. (4-1),
while the rest of the molecules remain
unstretched. Thus we have a bimodal distri-
bution of chain extension constituted of prac-
tically fully stretched out and essentially
unstretched chains with no intermediate
stage in between, a result of salient impor-
tance for what follows. Increasing will not
substantially increase the degree of chain
extension (i.e., in terms of end-to-end dis-
tance), but will increase the amount of mate-
rial that becomes extended within a bimod-
al distribution of extended and unextended
chains by increasingly 'cutting into' the dis-
tribution from the high molecular tail down-
wards. This situation is illustrated by Fig.
4-7 with reference to three strain rates (c) of
increasing magnitude, which are meant to
correspond to the three M values in Fig. 4-6.
molecular weight >
Figure 4-7. Schematic plot of molecular weight dis-
tribution showing the three different cut-offs for the
molecular weights corresponding to Fig. 4-6.
 4.2 The Fundamentals of Chain Extension
4.2.1.3 Flow-Induced Scission
We now turn to a further notable aspect of
the present type of chain stretching experi-
mentation in elongational flow fields, name-
ly flow-induced chain fracture. Consider a
given molecular weight, say Mx in Fig. 4-6,
and continue to increase e beyond (c)\, i.e.,
proceed along the plateau of the /vs. e curve.
Here, at some stage, the fully stretched out
chain will break as a result of increasing
stretching forces along its length, transmit-
ted by frictional contact from solvent to
chain. It is the salient result of this experi-
ment that the chains were shown to break
exactly at the center. The latter was estab-
lished using the same experimental setup by
which the chains had been broken initially
to determine the molecular weight of the
scission fragments by the elongational flow
method described in the previous paragraph.
[For a recent review of the Bristol works on
chain scission, seeOdellet al. (1992b).] The
halving of this chain through flow-induced
scission, exact within the accuracy of avail-
able methods for molecular weight determi-
nations, is perfectly accountable theoretical-
ly and is presently one of the cornerstones of
our understanding of mechanically induced
chain degradation in flowing systems. As is
derivable by simple application of Stoke's
law, the critical fracture strain rate (f) obeys
the relation
1 system, the cross-links are never distribut-
1 (4-2)
M
It follows that not only does this fracture
behavior set a limit on the flow strength that
can be applied without permanently altering
the molecular characteristics of the materi-
al, but it also sets a limit on the length of
chain (hence M) that can be stretched out
without the chain breaking first (as a conse-
quence of the fact that the c vs. M [Eq.
(4-1)] and f vs. M [Eq. (4-2)] curves cross
over).
199
4.2.2 Chain Extension
in Permanent Networks
In relation to the extension of chains with-
in permanent networks, it is best to refer to
the extensive literature on the molecular
aspects of network deformation and rubber
elasticity. Nevertheless, in view of the fore-
going a few pertinent statements will be
added at this point.
First, a network and correspondingly the
chains constituting it, can be deformed stat-
ically: forces applied externally will be
transmitted throughout the whole system by
means of the network junctions 1 . Under,
e.g., uniaxial, stretching forces the macro-
scopic sample will extend uniformly in an
affine manner, as will the underlying net-
work elements, and this extension will be
maintained for as long as the forces are
applied. For a given macroscopic strain, the
molecular strain will be determined by the
length of the network (chain) element
which, in turn, is in inverse relationship to
the number of cross-links per unit volume
(cross-link density): the higher the cross-
link density, the shorter the chain in between
them and the higher the molecular strain.
The second point follows from the above.
Namely, in the event of a distribution of
chain lengths, it is the shortest one that, for
a given macroscopic strain, will become
most highly stretched out. As in a 'real life'
ed uniformly (even in the ideal simplest case
of cross-linking, the distribution of 'chain'
lengths will be statistical); there will be a
corresponding nonuniformity in the lengths
of the chains connecting these cross-link
points, where (as stated above) the shortest
1
Strictly speaking, in a rubber network besides per-
manent (chemical) cross-links, temporary (physical)
cross-links are also present. In the present context we
shall only be concerned with the former.
200 4 Flow-Induced Orientation and Structure Formation
ones will be the most highly stressed and
hence strained. It should be noted that this
is the opposite to what applies to the isolat-
ed chain in elongational flow (Sec. 4.2.1.2),
where it is the longest chains in a distribu-
tion that respond most (i.e., first) to the
externally imposed extensional influence
(i.e., strain rate).
There are also further major differences
which follow directly from the above.
Namely, in a network a chain element be-
tween two junction points is uniformly
stressed. This is in sharp contrast to an iso-
lated chain extended in an elongational flow
field where the stress distribution along a
chain is grossly nonuniform, the stress being
maximum at the geometric center of the
chain [the source of the central scission at
the appropriately high strain rate (f)].
As a consequence of all of the foregoing
there will be a fundamental difference be-
tween the response of a network and that of
an isolated chain to the imposed elongation-
al influence. At an increasing macroscopic
elongation, a given network chain will
extend progressively, each stage of exten-
sion corresponding to a state of equilibrium
with respect to the extensional forces (with
a corresponding distribution of extensions
in the normal situation of nonuniform cross-
link distribution). In contrast, in the exten-
sion of an isolated chain (as achievable by
the only possible means of elongational
flow) there is no steady (only a transient)
state between the two extremes of the unde-
formed random coil and the practically fully
stretched out chain (allowing for compara-
tively small gradations within the extremes,
as discussed in Sec. 4.1.1).
The above represents the a priori expec-
tations. In light of this, it will come as a sur-
prise to note that the actual observed mor-
phologies arising in stretched networks con-
form more closely to the elongational flow-
induced structures, as found in dilute
systems, than to what would be expected
from a network by the above a priori con-
siderations, an issue that (as will be dis-
cussed later - see Sec. 4.7) represents one
of the most open-ended aspects in the mate-
rial of the present review.
4.2.3 Transiently Interacting Chains
4.2.3.1 General Considerations
This situation arises when there is physi-
cal contact between different chains that can
act as network junctions, but only on an
appropriately limited time scale. Here then
a physical network arises where mechani-
cally active junctions keep forming and
breaking up in a kind of statistical equilib-
rium. Clearly, such systems cannot be
stressed statically through an externally
applied force field, as they will flow in the
form of a viscoelastic liquid. Here the chains
connecting the transient junctions are
expected to become temporarily extended as
in a network, but subject to the time-depen-
dence of the process. In this case the elon-
gational nature of the flow which provides
the extensional influence is no longer a pre-
requisite for a high degree of chain exten-
sion: simple shear flow should also be
capable of achieving it even if elongational
flows still remain the most effective.
The situation just described pertains to
the conventional Poiseuille flow of melts
and concentrated solutions. Its experimen-
tal investigation and theoretical treatment is
the mainstream subject of the hydrodynam-
ics and rheology of polymeric systems.
Nevertheless, extension of the previously
presented elongational flow approach, as
applied to isolated molecules, to more con-
centrated solutions where the overlapping
molecules start to interact provides a useful
and instructive entry into this complex sub-
ject, which will be pursued in the following.
 4.2 The Fundamentals of Chain Extension
4.2.3.2 The Elongational Flow Approach
to Transiently Interacting Chains
The opposed jets technique for creating
uniaxial extensional flows can readily be
extended to solutions of increasing concen-
tration where, by simple geometric consid-
erations, increasing coil overlap and conse-
quent entanglement is expected. Referring
to what was said for dilute systems contain-
ing chains in isolation, here, in the case of
more concentrated solutions, two stages
were found upon increasing the elongation-
al strain rate in the flow field between the
jet orifices: more explicitly, two critical
values occurred at a sharply defined critical
concentration. The first corresponds to the
coil stretch transition as before, i.e., as
is increased, at a certain a bright central
line appears between the jets, as in Fig.
4-5, signaling c and hence a coil stretch
transition. Increasing further, with new
solution containing still unstretched mole-
cules constantly entering the system, a sec-
ond distinct event occurs (following some
intermediate stages not to be enlarged upon
here). Instead of the steady, central bright
line, the birefringence pervades the whole
volume between the jets, the system becom-
ing unsteady and the birefringence flicker-
ing like a flame; a still picture of this is given
in Fig. 4-8. This 'flare' effect we consider
Figure 4-8. Optical micrograph observed between
crossed polars showing the 'flare' phenomenon; 0.1 %
atactic polystyrene solution; M = l.2xlO6 (Odell et
al., 1985).
201
as the manifestation of the formation of a
mechanically connected network (Odell
et al., 1985; Keller et al., 1985). At the strain
rate n, at which the flare shown in Fig.
4-8 occurs, the chains no longer extend indi-
vidually under the influence of the flow, but
in a cooperative fashion as a result of which
the flow becomes unstable.
There are two criticalities defining these
happenings: (1) a critical polymer concen-
tration 2 c+, at which (and beyond) the above
'flare', signaling network formation, can
occur, and (2) for a solution of concentra-
tion above c+, a critical strain rate n has to
be reached where n >c.
Figure 4-9 attempts to convey what is hap-
pening. It depicts an overlapping system of
chains. As the strain rate reaches c, the
chains disentangle and stretch out individu-
ally (Fig. 4-9 a). As is increased (while
fresh solution with overlapping molecules is
becoming exposed to the flow of increasing
strength) and the second critical strain rate n
is reached, the chains, now on the much short-
er time scale corresponding to n, 'grip each
other', so to speak, and will act like a mechan-
ically connected network (Fig. 4-9 b). Separ-
ate work also established that at this stage the
flow resistance (viscosity) is enormously
increased and flow-induced chain scission,
which now becomes increasingly random (as
opposed to being precisely central), is great-
ly enhanced (Odell et al., 1992b; Keller
et al., 1985; Chow et al., 1988). It can be seen
therefore that from simple visual criteria such
as Figs. 4-5 and 4-8, it is possible to explore
the effect of flow on molecules, and use these
effects to characterize them and diagnose the
interactions between them.
2
c+ is substantially smaller than the conventionally
defined concentration for chain overlap, i.e., c*. The
reason for this is that the elongational flow-induced
interchain interaction requires a smaller degree of
chain overlap than that in contact at the radius of gyra-
tion, the criterion used to define c*.
202 4 Flow-Induced Orientation and Structure Formation

Figure 4-9. Schematic drawing of the response of

dissolved molecules to an elongational flow field (at Concentration >
c > c+): (a) 4 < <n (extensibility within a strain rate Figure 4-10. Strain rate vs. concentration plot show-
window); (b) c < n < (mechanically effective net- ing the critical strain rate for the coil > stretch tran-
work formation giving rise to the flare phenomenon). sition (ec) and the critical strain rate for network for-
mation (n) in the case where a finite strain rate win-
dow (n-c, shaded area) exists up to c=\ (single
The relation between c, n, and concen- component melt).
tration (c) can be expressed by graphs, as
shown in Figs. 4-10 and 4-11. This is a sche-
matization of numerous results reported in
specific detail in individual works. They all
have the following features in common: (i)
c is a slowly decreasing function of c. This
is the consequence of the increasing solution
viscosity with increasing c, which in turn
increases the conformational relaxation time
T=l/ c (see Pope and Keller, 1978; Odell
etal., 1985, 1992a, b; Keller and Odell,
1985; Miles and Keller, 1980; Keller et al.,
1985; Chow et al., 1988). It is important to
note that the extending chain responds to the
frictional forces corresponding to the mean Concentration
viscosity of the medium surrounding it (i.e.,
Figure 4-11. Strain rate vs. concentration plots as in
the viscosity compounded by solvent and Fig. 4-10, but now for the case of crossover of the n
solute), (ii) n (where n >c) becomes oper- and c vs. concentration lines, in which case the strain
ative, i.e., the flare phenomenon results (see rate window ceases to exist with increasing concen-
tration.
Fig. 4-8), at and beyond a particular c=c+.
This means that for c>c+ there is an upper
limit to , up to which the chain is individu- than c, the strain rate window n - c nar-
ally extensible, and hence there is a strain rows with increasing c (Fig. 4-10). (iv) n
rate 'window' n - c for such chain exten- seems to approach c asymptotically, with
sion (shaded area in Figs. 4-10 and 4-11). n - c narrowing accordingly, but with no
(iii) As n is found to decrease more steeply evidence of a crossover of n with c as a
 4.3 Structure Formation in Flowing Solutions
function of c. This is highly significant as the
existence of a crossover (Fig. 4-11) would
signify that a given molecule can no longer
be extended in its entirely, because it would
have become part of a mechanically active
network as was increased. It follows that
as long as condition (iv) holds, a chain will
remain extensible within its appropriately
narrowed down n - c strain rate window at
the correspondingly lowered strain rate.
The question that arises at this point is
how far the condition in Fig. 4-10, i.e., the
existence of a finite strain rate window of
chain extensibility, holds with increasing c,
and specifically, whether it still holds for
c- 1, i.e., for the single component melt. As
will be seen below, the evidence in our work
on the melt is consistent with the conditions
embodied by Fig. 4-10, i.e., that the exten-
sibility of the full chain pertains even there.
Even so, situations will be quoted (cross-
linked melts) where this cannot be so a pri-
ori and where n<c must pertain, i.e., where
we must have a crossover at the high c side,
such as in Fig. 4-11, but where nevertheless
morphological effects equally attributable
to the fully extended chain (but now be-
tween fixed entanglement points) can be
seen. The existence or nonexistence of a
crossing over of n with c, and its depen-
dence (if and when it exists) on c and on pre-
existing cross-links is clearly crucial for the
attainment of full chain extension, and
beyond, for the understanding of entangle-
ments and melt behavior in general, and will
remain the open-ended issue in this chapter,
to be referred to again in Sec. 4.8.
4.3 Structure Formation
in Flowing Solutions
4.3.1 The Origin of Shish-Kebabs
Shish-kebabs are crystalline assemblies
consisting of two components: a central
203
core fiber (the 'shish') and lamellae (the
'kebabs') as if strung along this core. Such
composite entities (as shown in Fig. 4-12)
are the most conspicuous consequence of
the on-off effect of chain stretching by elon-
gational flow. Historically, shish-kebabs
were observed ubiquitously in solutions
very soon after the recognition of lamellar
single crystals and feature under various
names throughout the early literature on the
subject. It was gradually recognized that
orientation and flow are instrumental in
their formation (e.g., Kawai et al., 1968),
but their true origin was first incisively
grasped by Pennings (Pennings, 1977; Pen-
nings and Kiel, 1965; Pennings et al., 1970)
in his pioneering studies on crystal forma-
tion in solutions under the influence of stir-
ring. The structures observed and their par-
ticular attribution to flow-induced crystal-
lization, as emerged from the seminal works
of Pennings and coauthors, have remained
the basis of our understanding of flow- and
stress-induced structure formation and will
therefore have a prominent place in the
present article. In the tradition of the study
of polymer morphology, the clearest mani-
festations are the structural entities that arise
from solutions, to which we shall turn first.
However, from the earliest days onwards,
once recognized for what they are, shish-
kebabs and related structures were also
identified, either directly or through their
effect on orientation and certain physical
properties, in single component systems.
Amongst the latter were melts of polyethy-
lene in the form of hauled-off or blown
films, through the underlying studies on
slightly cross-linked, stretched melts (Kel-
ler and Machin, 1967) and stretched natural
rubber (Andrews, 1964, 1966), both of
which we shall return to later in this article.
Historically, the focus of Pennings's stud-
ies was the recognition of, and the account-
ing for, the dual fiber-platelet morphology
 o
QL

CD
Z3

0)
Q.

(f)
: <
&'-?$^i,Z :

c
CD
Tl
O

<$$?-'

1 um
Figure 4-12. Various versions of shish-kebab crystals as obtained from flowing (stirred) solutions. Electron micrographs [from Hill et al. (1980, 1983)]:
(a) micro shish-kebab; (b) enlarged view of a micro shish-kebab as shown in (a) (the black dots originate from decoration with gold); (c) micro shish-kebab
showing connecting veil (lcm represents 0.3 um); and (d) macro shish-kebab.
 4.3 Structure Formation in Flowing Solutions
constituting the curious, profusely occurr-
ing effects observed at the time, and their
origin. The latter was done through visual-
izing the coexistence of highly stretched and
essentially unstretched chains, where the
former crystallize first giving rise to fibers
of which the unstretched chains avail them-
selves as nucleating templates for their dep-
osition in the form of chain-folded lamellae
afterwards, usually on subsequent cooling
of the system. Figure 4-13 should serve as
a highly schematic illustration of the pro-
cess [originating from a later date based on
Bristol work (Keller and Mackley, 1974)].
The molecules that stretch out to form fibers
are the longest ones in an average broad dis-
tribution with the rest remaining unextend-
ed, giving rise to platelet overgrowth at a
later stage. Shish-kebab formation was seen
to be highly fractionating, the fiber portion
precipitating first and containing the long-
est molecules. [In fact originally Pennings's
work was concerned with fractionation
(Pennings and Kiel, 1965).]
For our present purpose we will now use
this original argument and invoke the ubi-
quitously documented shish-kebabs as evi-
a researches, essentially focusing on the
b.
Figure 4-13. Schematic representation of orienta-
tion-induced crystallization, (a) Formation of smooth
extended-chain fibers: (i) random coils; (ii) the chains
have become oriented by extensional influences; and
(iii) the preoriented chains have crystallized, (b) For-
mation of fiber-platelet composites (shish-kebabs).
Here not all the chains have been aligned and at stage
(iii) only the oriented chains crystallize; the unorient-
ed chains are left in their random conformation. The
latter use the crystalline fibers already formed as
nuclei for subsequent crystallization in the form of
chain-folded platelets (iv).
205
dence for the preexisting duality of extend-
ed and unextended chains prior to crystal-
lization, through our basic studies on elon-
gational flow-induced chain extension in
closely monodisperse material of noncrys-
tallizable polymers, as detailed in Sec. 4.2.
In Pennings's original works, the source of
elongational flow was identified as conver-
gent and divergent flow field regions be-
tween Taylor vortices created by stirring
(Pennings et al. 1970). In subsequent stud-
ies by ourselves on elongational flow-
induced chain extension, such flow fields
were created purposefully in the appropri-
ately constructed apparatus (jets, slots, roll-
ers, etc.) as explained in Sec. 4.2. Figure
4-14 should provide the link between the
two areas of work where, using the crystal-
lizable polymer polyethylene, flow-induced
chain extension was created and registered
first, with fibrous crystallization induced
subsequently at an appropriately lower tem-
perature (Keller and Mackley, 1974). Elec-
tron microscopic examination of fibers,
such as seen optically in Fig. 4-14, indeed
confirmed the shish-kebab character of the
underlying crystals.
In subsequent works the emphasis of
Pennings' and collaborators' and that of the
Bristol workers diverged. Pennings's
attainment of high modulus fibers, contin-
ued to concentrate on shish-kebabs, but this
(as we see it) with the intention of prepar-
ing ultrahigh modulus fibers of which shish-
kebabs can be either constituents or stations
along the route of their preparation. Under
these conditions, in the hands of Pennings
and collaborators, the solutions pass
through a gel stage prior to, or concurrent-
ly with, the occurrence of crystallization.
Stretching of the gel by the particular meth-
ods of Pennings leads to macroscopic and
microscopic fibrillation, of which shish-
kebabs, or bundles of shish-kebabs, are the
206 4 Flow-Induced Orientation and Structure Formation
Figure 4-14. (a) The development of crystallization
observed during suction in the opposed jet apparatus
for a 3 wt.% polyethylene solution at 7=100C,
= 2.3xl0 3 s"1, M^2xlO5. Polars crossed at 45. (b)
Fibrous crystal deposit obtained during suction; it has
blocked one of the jets. Polars crossed at 45 (Keller
and Mackley, 1974).
ultimate structural elements. The interpre-
tation arising from these studies attributes a
macroscopic origin to the shish-kebabs, i.e.,
as originating through a kind of crazing or
through meniscus instability (Roukema,
1991), which happens when extending gels
or viscous liquids, effects carried over from
well-documented studies in other fields: the
inhomogeneous deformation of solids and
the dispersion of liquids, respectively. In
molecular terms these studies consider the
entanglement nature of the deforming and
concurrently crystallizing systems, and spe-
cifically, the role of preexisting entangle-
ment 'clusters' (Smook and Pennings,
1984). The common denominator in this
interpretation is thus the existence of entan-
gled chains, and hence of sufficiently high
concentrations to create mechanically effec-
tive chain overlap on the time scale of the
deformation to which the system is being
subjected in the course of fiber preparation.
We have no reason to query the pertinence
of the above view to the circumstances under
which those structures were obtained. Nev-
ertheless, we are disinclined to accept them
as the sole, or even the most basic mecha-
nism for shish-kebab formation. There is no
doubt that the stretching of gels (just as of
any mechanically connected system) will
produce shish-kebab type structures on
crystallization, of which more will be said
in Sec. 4.8.2. Also, we readily accept that
once the stretching effect becomes cooper-
ative and extends over macroscopic sample
volumes, macroscopic phenomena such as
invoked in Roukema (1991) and Smook and
Pennings (1984) will arise. Nevertheless,
we maintain that the mechanism, as repre-
sented by Fig. 4-13, remains valid in
systems that are below the concentration
required for interchain interactions and
where, accordingly, the chains are extend-
ing (under the appropriate elongational flow
conditions) in isolation. This issue has in
fact been explicitly addressed more recent-
ly in the light of knowledge acquired in pur-
posefully conducted elongational flow
experiments, through investigations in the
opposed jet apparatus such as underlie
Fig. 4-14. Specifically, the question was
asked as to whether or not shish-kebabs can
arise from initially nonoverlapping chains
when suitably extended, or whether chain
 4.3 Structure Formation in Flowing Solutions 207

overlap, i.e., network formation, is neces- is the attribute of elongational flow-induced

sary for their formation (Narh and Keller, extension of the isolated chain, supporting
1991c). This distinction has become pos- the argument that follows.
sible since recognition of the flare phenom-
enon (Fig. 4-8) as a criterion for chain over-
lap. For this purpose experiments were per- 4.3.2 The Structure of Shish-Kebabs
formed on polyethylene to determine the
effect of polymer concentration on c and en, The shish-kebab crystals are more com-
as laid out in Sec. 4.2.3 by the sharp bire- plex and intriguing than the schematic draw-
fringent line and flare criteria, respectively ings (Fig. 4-13) and the more elaborate ver-
(Figs. 4-5 and 4-8), first at a temperature sion (Fig. 4-15; Pennings, 1977) might sug-
sufficiently high to avoid crystallization and gest. In particular, the kebabs (i.e., platelets)
thus establish the value of c+. Subsequent- can be molecularly connected or unconnect-
ly, fibers such as in Fig. 4-14 b were pro- ed to the shish (core fiber). The unconnect-
duced by performing the same experiment ed platelets constitute the larger exterior por-
at appropriately lower temperatures. It was tions and can be removed by selective dis-
found that fibers with a shish-kebab charac- solution, leaving behind a core that is a shish-
ter did form, both above and below c+. kebab structure itself, but on a finer scale.
We assigned to the two structure types the
These unpublished experiments thus
terms macro and micro shish-kebabs,
attest to the fact that shish-kebab crystals
respectively (Keller and Willmouth, 1972),
can form from chains that become extend-
(schematic drawings in Fig. 4-16); the actu-
ed as if in isolation. (The question still
al shish-kebabs in Fig. 4-12a-c are micro
remains open as to how and when the
stretched out chains come together to form
fibers.) We shall take this model as the basis
of the presentation to follow. This is not to
say that we wish to bypass systems that are
extending in the form of networks. The dif-
ference between the extension of the two
systems (isolated and mechanically con-
nected chains) is a crucial one, as already
raised when juxtaposing Figs. 4-10 and
4-11, and will arise again when dealing with
the single component system of melts. At
this juncture it has arisen in connection with
the different modes of generating shish-
kebabs from solution. The fractionating
properties in particular are consistent with
either mode of formation, namely the long-
est chain molecules are the ones that extend
preferentially in an elongational flow field,
but they are also the ones that are more effec-
tive at forming a network. Nevertheless the Figure 4-15. Schematic representation of a micro
criticality in the strain rate leading to a cut- shish-kebab indicating the intimate connectedness of
the platelets with the central core [after Pennings
off in M in terms of extensibility (Fig. 4-7) (1977)].
208 4 Flow-Induced Orientation and Structure Formation
microns
macro
shish-kebab
micro
shish- kebab
Figure 4-17. A sketch illustrating a current view of
the structure of the central core of a shish-kebab. Elon-
gated bundle-like crystals are connected by fringe-like
amorphous regions. The chains ('hairs') emanating
(sideways) from these regions crystallize later to form
platelets. The ends of the crystals are shown tapered
to allow for the lower density of the amorphous
regions (Barham and Keller, 1985).
shish-kebabs and in Fig. 4-12 d macro shish-
kebabs (mostly too thick, hence opaque for
direct transmission electron microscopy). (It
should be noted that the distinction between
macro and micro shish-kebabs is not adhered
to in much of the literature, leaving some
Figure 4-16. A sketch illus-
trating the difference between
macro and micro shish-kebabs.
In the macro shish-kebabs the
large platelets can be removed
to reveal the central micro
shish-kebab whose platelets are
intrinsically attached to the
central thread (Keller and Will-
mouth, 1972).
uncertainty as regards the nature of the
objects in question in specific papers.)
Thus the platelets of the macro shish-
kebab are additions to, while those of the
micro shish-kebabs are intrinsic constitu-
ents of flow-induced crystallization. The
latter arise because the fibers, as initially
formed, are 'hairy' (Fig. 4-17), with loose
chains dangling off their outer surface.
These hairs may crystallize later when the
solution is cooled further, or even after flow
has stopped, when in a random conforma-
tion they will form chain-folded platelets,
but now intimately attached to the fibrous
core. Alternatively, they can give rise to
veils connecting the platelets (Fig. 4-12 c),
or they may add smoothly to the core itself.
In brief, such hairs can impart different
appearances to the central fiber according to
the conditions of their deposition in the final
precipitation. We called these appearances
'hairstyles'; they can be readily altered and
interconverted by subsequent heat and
solution treatments, which we termed
the 'hairdressing' of shish-kebabs, Fig.
4-12a-c being examples (Hill and Keller,
1981; Hill etal., 1980, 1983).
We now turn to the structure of the cen-
tral core, already invited by reference to Fig.
4-17 above. Historically, this was first
 4.3 Structure Formation in Flowing Solutions
envisaged as a more or less continuous,
extended-chain crystal. In the light of fur-
ther evidence it is now pictured as an assem-
bly of elongated, bundle-like crystals of
finite length with a broad length distribu-
tion, where the mean length is an increasing
function of the formation temperature. As
shown schematically in Fig. 4-17, the bun-
dle-like crystal regions themselves are con-
ceived as connected by fringe-like, partial-
ly oriented amorphous regions, the whole
fibrous entity being enveloped in a shroud
of loosely dangling cilia which, as described
above, give rise to the kebab component and
connecting veils (when such are present) of
the micro shish-kebab on subsequent crys-
tallization.
Evidence for the ciliated shroud has come
from the variability of the appearance of the
micro shish-kebab with treatment condi-
tions, i.e., from the hairdressing character-
istics referred to above. That for the seg-
mented structure of the core fiber emerged
from a study of the thermal behavior (Grubb
and Keller, 1978). More precisely, on heat-
ing close to the melting region the platelet
structure which forms the kebab melts first,
as to be expected. On heating further, a grad-
ual shrinkage is observed which is rever-
sible in the sense that the fiber unit extends
again on cooling (self extension!). This is
best interpreted as melting of the crystal
bundles within the fibrous entity. As long as
such a fibrous chain assembly remains in
existence, melting will produce shrinkage
and crystallization extension. The melting
itself is envisaged as progressive, the short-
er crystals melting first. From a detailed
study of the shrinkage-extension behavior
as a function of temperature, the crystal
length distribution could be calculated, also
as a function of the formation temperature
of the shish-kebab (Grubb and Keller,
1978). Subsequently, this segmented nature
of the core was confirmed by dark field elec-
209
tron microscopy in quantitative agreement
with the size distribution calculated from
the thermal shrinkage behavior (Grubb and
Hill, 1980).
The above is intended merely as a guide
through some of the salient structural fea-
tures of shish-kebab crystals. Much of the
literature on this subject is associated with
the development of high strength-high
modulus fibers, for which shish-kebab crys-
tals provide one of the routes; many further
structural features have therefore been dis-
cussed in this particular context, for which
we refer the reader to the Ph. D. thesis by
J. P. Pennings (1994), which contains most
of the relevant references.
4.3.3 On the Mechanism
of Shish-Kebab Formation
The present section is a more specific
extension of that on the origin of shish-
kebabs (Sec. 4.3.1). Again, we cannot be
comprehensive; the features selected have
some general principles to convey and are
at the same time of relevance to the present
article. Here, within the framework of the
scheme represented by Fig. 4-13 we shall
confine ourselves to the formation of the
innermost central fiber. There are two
aspects to consider: (i) the mode of chain
extension, and (ii) the formation of crystals
from preextended chains.
(i) Chain extension - We shall consider
here only the extension of isolated, or at
least mechanically noninteracting chains. In
addition to the previously discussed chain
extending effect of elongational flow, a fur-
ther interesting associated factor comes into
play, the lead into which was provided by
the Zwijnenburg-Pennings 'tip growth'
method (Zwijnenburg and Pennings, 1975)
for producing high modulus fibers. In this
method, a preexisting polyethylene fiber (at
a later stage even a cotton fiber) was
210 4 Flow-Induced Orientation and Structure Formation
immersed in a flowing solution of polyeth-
ylene held at a temperature slightly above
that for precipitation. As the fiber was with-
drawn counterstreamwise, it was observed
that it was growing at the tip, and by adjust-
ing the flow and withdrawal speed, a steady
state could be reached where the growing
fiber tip always stayed at the same position
while being wound up at the other end: a
stage where clearly the speed of winding up
matched that of the fiber growth. The above
procedure lends itself to continuous fiber
production (potentially at least), but for
the present purpose it illuminates a scientif-
ic principle, namely that of the chain ex-
tending effect behind the tip when tip and
fluid are in relative motion. In this case a
stagnation point arises behind the tip (or
behind any other solid obstacle), with an
associated elongational flow field at that
locality.
The above situation can be readily trans-
ferred to the growth of shish-kebab crystals.
Once a shish-kebab fiber has formed it will
modify the flow field around it. Specifical-
ly, it acts like the seed fiber in the fiber grow-
ing method outlined above: downstream the
tip acts as a kind of 'windbreaker' to the
flow, creating a stagnation point and a con-
sequent elongational flow region which
extends the chains, so enhancing the effect
of the overall flow field. In this way growth
of the shish-kebab fiber should be maintain-
able even outside the locality of the macro-
scopic elongational flow field, which
caused the shish-kebab to be formed in the
first instance. Mackley (1975 a) has shown
by calculation that such expectations are
indeed realistic, and in fact has put these
principles to use in the preparation of shish-
kebabs through the immersion of prede-
signed obstacles into the streaming solution
of otherwise straightforward, simple shear
flow (i.e., not elongational flow) character
(Mackley, 1975 b). Ths influence of obsta-
cles to create flow-induced structures will
be reinvoked again later (Sec. 4.4).
(ii) Crystallization from preextended
chains - As already stated in Sec. 4.1, it is
apparent that crystallization will be promot-
ed by chain extension both on thermody-
namic and kinetic grounds. To recapitulate,
the extension and concomitant orientation
of chains reduces the entropy of the solution
(or for that matter melts), thus raising the
melting point (Tm). Consequently, for any
temperature T<Tm this will increase the
amount of supercooling and hence the driv-
ing force for crystallization. In addition, as
the chains have become more or less par-
allel, the kinetic hindrances which prevail
in the random coil state will become large-
ly reduced.
Attempts to treat the situation theoretical-
ly have focused largely on the issue of the
orientation-enhanced nucleation rate. Even
though this topic might be of great impor-
tance for the present article, we shall not
embark on it in any detail besides giving
some references (Hay et al., 1976; Ander-
sen and Carr, 1984; Pucci and Carr, 1984).
The nucleation enhancement is enormous
by any a priori expectation, but the spread
in attempted numerical assignments is so
large (in keeping with general experiences
in the nucleation field) that explicit predic-
tions are fraught with problems. This par-
ticular subject will receive more specific
attention from Eder and Janeschitz-Kriegl
in Chapter 5 of this Volume. For a most
informative earlier review see Pucci and
Carr (1984).
Having stated the above, we shall confine
ourselves to a few specific theoretical con-
siderations on crystallization such as are rel-
evant to the structural features of the core
fiber mentioned in the foregoing. Amongst
these is the likelihood of near simultaneous
crystal nucleation at several points along a
stretch of preextended chains, a situation
 4.4 Structure Formation in Flowing Melts
envisaged by Pennings (1977) and by Hoff-
man (1979), amongst others. Irrespective of
the actual rate values, this type of nuclea-
tion will create a 'crossing over' of chains
in such a way that crystals growing out lon-
gitudinally from the different nucleation
sites along the chains will not be able to
match up in perfect register when they meet.
This will lead to defective regions along the
fibrous crystals and thus to a limited crystal
size along the chain direction, with a length
distribution corresponding to the distribu-
tion of nuclei and hence also to the nuclea-
tion density. Such a situation is consistent
with the schematic structure in Fig. 4-17 and
has in fact been invoked previously to
account for the observed thermal behavior
(Grubb and Keller, 1978).
In addition to the above, Hoffman's
approach (1979) also provides an explana-
tion for the small diameter of the central core
fiber, which using the available experimen-
tal evidence [see George and Tucker (1975)]
is in the range of 20-30 nm, a dimension it
seems incapable of exceeding. Hoffman
considers that in a model such as in Fig.
4-17 there must be strains at the interface
between the crystal and the disordered
regions at the crystal tips because of the larg-
er cross-sectional area requirement of the
latter. As the crystal diameter increases
through continuing lateral growth, this strain
will increase correspondingly in a cumula-
tive manner until further lateral growth is
brought to a halt. Invoking basic principles
of mechanics, a match between the observed,
apparently limiting diameter and its calcula-
tion is obtained. The ciliated shroud envel-
oping the fiber but not crystallizing on it (at
least at this stage) would be a natural conse-
quence of such a model, several additional
predictions arising from it inviting further
experimental investigations.
At this point and to end this section, a fur-
ther, totally different departure needs men-
211
tioning that is seemingly in conflict with the
mainstream view outlined above. In experi-
ments analogous to the Zwijnenburg-Pen-
nings tip-growth fiber production method
(1975), McHugh and collaborators (Riet-
veld and McHugh, 1983; Vrahopoulou-Gil-
bert and McHugh, 1984) observed a dark
zone forming behind the solid tip (i.e.,
downstream), as seen between crossed
polars, with the birefringent fibers emerg-
ing subsequently from whithin this dark
zone. This dark zone, obviously isotropic
(but why darker than the equally isotropic
environment is not clear), is attributed by
the above authors to a randomly oriented
amorphous gel-like liquid precursor phase,
which is the result of flow-induced liq-
uid-liquid phase separation, and is seen as
the primary product of the orientation and
as the source of all subsequent happenings,
in a way elaborated in a series of papers sub-
sequently. In these works the view is taken
that the observed increase in birefringence
is the consequence of the growth of orient-
ed crystals within the unoriented precursor
fiber, as opposed to the initial formation of
oriented amorphous regions which subse-
quently crystallize. To account for the
observations underlying the above model
and to reconcile them with the mainstream
view expounded by the present chapter
remains a task for future work. But until then
the possibility of a precursor phase result-
ing from orienting influences has left a mark
on the whole subject (see the next chapter
in this Volume).
4.4 Structure Formation
in Flowing Melts
4.4.1 General Considerations
The main concern of this chapter is flow-
induced structures formed under the condi-
212 4 Flow-Induced Orientation and Structure Formation
tions of processing, or the equivalent of pro-
cessing. For a large majority of cases this
means structure formation from the melt. As
solution processing is currently gaining
ground, e.g., gel processing, experiences
with solutions (as described in Sec. 4.3)
should become increasingly relevant in an
explicit fashion. Even so, the main signifi-
cance of the earlier described experiences
on chain orientation and the resultant struc-
tures formed in solutions lies in the fact that
such experiences provide a basis for the
understanding of analogous effects arising
in the melt which are not as amenable to such
experimentation, at least not in a similarly
definitive and controllable fashion. One rea-
son for this is the lack of similarly well-
defined crystallizable material in sufficient
quantities as needed for such experiments:
the high molecular weight polyethylene
available for such a purpose is inevitably
highly polydisperse (to recall, orientability
is an inverse power function of the chain
length). Further and more significantly, the
resulting structural entities cannot be as
readily identified and even less separated
from the remaining, still untransformed
material and thus examined in isolation, as
in the solution case. Even so, there are ade-
quate indications that some, if not all, of the
principal conclusions reached on solutions,
and set out above, can be carried over to melt
systems. This, with due qualifications,
applies to the structures as such, i.e., to the
morphology, to the underlying molecular
processes, and to some of the associated rhe-
ology. These we shall describe and discuss
in turn in the following.
First, however, the main qualification
needs stating. In a solution there can be both
isolated and overlapping chains according
to concentration. In melts there are no such
alternatives, the chains are always (neces-
sarily) overlapping. Nevertheless, we have
seen in the solution case that topological
overlap need not necessarily mean mechan-
ical interaction under the orienting influenc-
es: whether the overlapping chains extend
individually as in solution (Fig. 4-9 a) or as
parts of a mechanically connected network
[with entanglements as junction points (Fig.
4-9b)] depends on the time scale (i.e., strain
rate) of the orienting influence, a shorter
time scale (higher strain rate) tending to
activate the network mode. Whether one or
the other mode is operative in the case of
geometrically overlapping chains, or both if
each mode is active, is a crucial question, as
already raised when discussing the alterna-
tives of Figs. 4-10 and 4-11 (as appropriate
for high concentrations and ultimately to the
melt). If we cannot provide the final answer
here, we can at least put these, what we
believe to be the basic alternatives, on the
map. We can, however, draw close parallels
between solutions and melts irrespective of
whether they arise through the isolated
chain extension or the network alternative.
As will be apparent, there are, rather
remarkably, many analogies with the case
of the extension of noninteracting chains, as
ascertained in solution, suggesting that such
considerations may also not be out of place
for the melts.
4.4.2 Structural Analogies -
Overall Morphology
Just as in the solution case, the dominant
orientation-induced crystalline structure is
the shish-kebab. Its visibility and hence
detectability is usually obscured by the sur-
rounding material, but thanks to the diffe-
rential melting behavior and to the contrast
provided by the polarizing light microscope,
shish-kebab entities can under certain cir-
cumstances, be made conspicuously appar-
ent (Grubb etal., 1975) (Fig. 4-18). The
similarity to the solution case (Fig. 4-12) is
obvious: both the kebab (platelet) structure
 4.4 Structure Formation in Flowing Melts
Figure 4-18. Shish-kebab crystals in a film of poly-
propylene formed after the melt was sheared by press-
ing. Polarizing optical micrograph, crossed polars
(Grubbetal., 1975).
and the shish (the central thread) are mani-
fest. However, in contrast to the solution
case, it is not possible to tell whether it is
the macro or micro shish-kebab variety, as
the selective dissolution test for removing
the 'macro' portion of the platelets is not
applicable in this case. The main feature, the
dual platelet morphology, remains apparent
nevertheless, which according to the fore-
going is the 'signature', so to speak, of the
dual nature of the underlying chain align-
ment corresponding to essentially random
and essentially fully or at least highly
extended chains. As stated in Sec. 4.1, this
dual nature of the chain alignment, as
reflected by the resulting morphology (or on
the other hand, giving rise to this particular
morphology), is our principal theme in this
article. Significantly, the formation of shish-
kebabs is promoted by high molecular
weight (M) material: shish-kebabs occur
more profusely in material of higher M treat-
ed similarly otherwise, and their number can
be significantly increased by the subsequent
213
blending of such high M materials (Afw
~ 106) into standard M samples, even in very
small proportions (-1%) (see Bashir et al.,
1984), which suggests that the shish-kebab
entities represent the high M fraction in a
given distribution. This sensitivity to the
high M fraction present is consistent with
the preferential alignment of the longer
molecules with a sharp, low M cut-off in
elongational flow, as diagnosed in solutions
of noninteracting chains. On the other hand,
long chains will also promote network for-
mation, and hence a broad consistency also
exists with a network-based model, even if
the step from a stretched network to shish-
kebab crystals cannot be as readily envis-
aged as in the case of isolated (or at least
noninteracting) chains through schematic
drawings, as in Fig. 4-13. We shall return to
this point later.
4.4.3 Chain Extension -
Fiber Generation
Here we recall early applications of the
jet-based elongational flow experiments as
performed on melts, which have shown con-
spicuous analogies with their solution coun-
terparts (Mackley and Keller, 1973; Mack-
ley et al., 1975). For our present purpose we
shall confine ourselves to experiments per-
formed at or closely above the stationary
state solidification temperature where crys-
tallization can occur as a consequence of
preceding chain extension, i.e., to situations
analogous to those pertaining to Fig. 4-14 in
the solution case. In double-suck-jet experi-
ments such as shown in Fig. 4-19, sharply
defined fibers appear along the central line
between the jets; this is closely analogous
to fiber formation from solutions (Fig.
4-14). (In the melt case the fibers are most
clearly visible in unpolarized light, because
between crossed polars the effect is overlaid
by the brightness of the background. This is
214 4 Flow-Induced Orientation and Structure Formation
Figure 4-19. Bright field photograph taken during
flow of the region between the orifices of the opposed
jets apparatus, showing the formation of the central
fiber and additional fibrous crystallization induced by
a gauze upstream in the polymer melt supply. Poly-
ethylene, T= 140 C (Mackley and Keller, 1973).
due to the massive optical retardation
caused by the surrounding melt, which has
a small birefringence but a very large opti-
cal path. In other words, in the melt case the
effects cannot be seen as a bright line against
a dark background as with solutions.) The
resemblance to the corresponding solution
case, both before and after crystallization,
is evident (compare Figs. 4-19 and 4-14b).
From this, to us compelling, evidence it thus
appears that given the appropriate strain rate
and strain (ensured by the stagnation point
along the central axis), molecules in the melt
can align and stretch out just as they do in
solutions, which is made visible in Fig.
4-19 by fixation of the stretched out state
through crystallization.
Another feature of Fig. 4-19 deserves
pointing out, namely the fibers along the
parabolic streamlines entering the jets from
the top downwards. These, as recognized at
the time (Keller and Mackley, 1974; Mack-
ley and Keller, 1973), originate behind the
grid bars of a metal gauze placed there as a
filter, which in turn generates stagnation
points for flow downstream, as any station-
ary obstacle would do as a matter of course.
The last point is brought out most striking-
ly by Fig. 4-20. Here a solid needle is placed
in the flow field with the melt flowing into
a single orifice. As the flow velocity
increases, a fiber appears at the needle tip
spreading downstream into the orifice
(Fig. 4-20b). Clearly, the fibrous tip has
generated a stagnation point which in turn
gives rise to a longitudinal velocity gradi-
ent and hence elongational flow, which,
when of sufficient magnitude, leads to chain
extension and at the appropriate tempera-
ture to fibrous crystal entities. Note that the
fiber only appears beyond a certain veloc-
ity [when going from Fig. 4-20a to (b)],
which suggests that the critical strain rate
criterion for the coil > stretch transition is
likely to apply and hence that the extension
behavior of noninteracting chains may
apply. (Firming up on this point by perform-
ing such experiments in smaller velocity
increments using sharp M fractions is clear-
ly invited.) Further, the generation of fibers
by an external obstacle, a needle tip in
particular, is analogous to the Zwijnen-
burg-Pennings tip-growth method (Zwij-
nenburg and Pennings, 1975) of fiber pro-
duction from solution, and on the scale of
the individual shish-kebab fiber, to the
mechanism of shish-kebab growth due to
the perturbation of the flow field by the
newly formed shish-kebab (Mackley,
1975 a, b), as described in Sec. 4.3.
The reality of the above theme is corrob-
orated by additional features of Figs. 4-20
and 4-21. In Fig. 4-20 c, on increasing the
strain rate a further effect is seen, namely
fibers entering the single jet along the con-
verging flow lines across the full jet diam-
 4.4 Structure Formation in Flowing Melts 215

Figure 4-20. Photographs viewed between crossed polars showing the development of fibrous crystallization
for a polyethylene melt flowing (left to right) into an orifice with a stationary needle-like obstruction upstream;
T= 140C. (a) Mean velocity into orifice (vm) = 0.8 c m s " ' , ( b ) ^ m = 3.3 cm s"1, (c) z;m = 8.0 c m s 1 (Mackley et al.,
1975).

Figure 4-21. Photograph

viewed between crossed
polars showing four succes-
sive stages of the develop-
ment of crystallization with
time at a single entry ori-
fice. (As in Fig. 4-20 but
here without an obstacle.
In this case the flow direc-
tion is from right to left.
vm - 2.6 cm s (Mackley
etal., 1975).

eter. This corresponds to the generation of
fibers, as a result of underlying chain exten-
sion, by a single orifice where (as opposed
to the double jet) there is no stagnation
point. It follows that for the same overall
strain rate, the achievable strain here will be
smaller than behind the needle tip at the
locality of the stagnation point. Indeed, as
seen from Fig. 4-20 c, the strain rate had to
be increased (as compared with Fig. 4-20b)
for this type of fiber formation in a single
jet to result.
Fiber formation in flowing melts entering
a single jet has received additional attention
(Mackley etal., 1975), (Fig. 4-21). Here,
just as in Fig. 4-20 c, fibrous crystals
appeared at the jet entrance at and beyond a
particular melt-flow velocity (Fig. 4-21 b).
On increasing the velocity further, the fibers
'grow' away from the jet entrance into the
melt interior along the converging flow lines
(Fig. 4-21 c), finally 'settling' at a particu-
lar distance from the orifice as determined
by the flow velocity (Fig. 4-21 d).
216 4 Flow-Induced Orientation and Structure Formation

The behavior shown in Fig. 4-21 can be

described by a self-stabilizing, dynamic
equilibrium, which we consider both impor-
tant for practice and pertinent for our under-
standing of flow-induced structure forma-
tion. Fig. 4-22 should help to convey the
essential details. First, however, it is impor-
tant to realize that fibers as seen in Figs.
4-19 to 4-21 are not stationary: they are con-
stantly being swept into the orifice by the
surrounding melt, in fact they are moving
together with the melt. They are seen as sta-
tionary because they are in a state of con-
stant self-renewal, growing out from the spe-
cific localities where they are being gener-
ated. The site of fiber creation depends on
the nature of the flow field. In Fig. 4-19 this (b)

site is along the central jet axis at the stag-

nation point, which is the geometric center
of the system. In Fig. 4-20 there is also a
stagnation point, but in this case located
down-stream behind the tip of the solid nee-
dle, created by the needle itself, and similar-
ly for the fibers along the parabolic flow lines
in Fig. 4-19, where the obstacles creating the
/
stagnation point are outside the field of view.
In the single jet case of Fig. 4-21 and in
the relevant part of Fig. 4-20, there is no
stagnation point. The fibers first arise close
to the orifice at points along a surface where
the velocity gradient is at a maximum. This
surface is not as uniquely defined as in
the case of a stagnation point-containing (c)

system, and indeed strong fluctuations of the

loci of fiber initiation are seen (recorded on
a motion picture). Once a fiber is formed it
Stationary fiber
is swept into the orifice with a velocity cor-
responding to that of the flowing melt with-
in the capillary. Since the velocity in the cap-
illary is larger than at some distance outside
it (where the fibers arise), the fiber tip will Figure 4-22. Schematic representation of flow into a
move faster than the surrounding melt, thus single orifice (Mackley et al., 1975): (a) flow field
creating a local elongational flow field at the with flow unobstructed; (b) flow field as modified by
the fiber itself being swept into the orifice but grow-
tip, which then produces chain extension and ing upstream at the tip; and (c) local flow field around
consequent crystallization. In fact the situa- growing fiber, considering the fiber to be stationary.
 4.5 Relation Between Morphology and Orientation
tion is analogous to that envisaged for shish-
kebab growth, as described in the preceding
section, where the role of the local elonga-
tional flow field generated by the newly aris-
ing fiber tip was first recognized. In the
present instance we have the superposition
of simultaneous removal and growth of the
fiber, the former generating the flow condi-
tions giving rise to the latter. Here, by obser-
vation, growth is faster initially, until at a
specific distance from the orifice the two
processes become equal in a state of dynam-
ic equilibrium (Mackley et al., 1975). To be
more specific, consider two flow fields, a
general macroscopic one and a local one
created by the tip of the newly arising fiber
which is moving into the capillary and hence
is in relative motion with respect to the melt.
The situation is depicted diagrammatically
in Fig. 4-22. Here Fig. 4-22 a represents the
general flow field, Fig. 4-22b the field as
modified by the fiber, and Fig. 4-22 c the
local flow field around the fiber taking the
fiber as stationary. For the two flow fields in
Figs. 4-22 a and 4-22c the corresponding
strain rates will be deonted gen and loc.
These vary spatially with a different func-
tional dependence in terms of the spatial dis-
tance r (from the orifice entrance). The crys-
tal growth velocity, ^cryst, is a linear function
of both gen and loc with different coeffi-
cients of proportionality (A and B)
v AF\ + RF (A-V\
In view of the fact that the fiber movement
downstream conforms to the highest veloc-
ity in the system, hence the relative velocity
between the fiber tip and the melt with
increasing r, it follows that Aloc increases
as a function of r. On the other hand, as the
velocity gradient will be highest in the region
of greatest convergence near the orifice, fall-
ing off to zero further out towards the melt
interior, on the whole, Be will decrease as
a function of r. Thus Eq. (4-3) should have
217
a maximum with r, from which the existence
of a surface (at a distance rmax) of dynamic
equilibrium follows in agreement with the
observation even on such qualitative
grounds. In fact the r region where fcryst has
a maximum can be calculated analytically
and, with coefficients that are pertinent to the
situation under consideration, reasonable
quantitative agreement with experiment
could be established (Mackley et al., 1975).
(In reality the velocity gradient willl also be
zero within the capillary, and hence # gen
itself will need to have a maximum with r.
However, this maximum occurs close to the
capillary entrance at an r value comparable
to the orifice diameter - more precisely at
r=5a/3, where a is the orifice diameter - at
a distance that the fibers soon outgrow. Such
particulars are taken into account by the
quantitative treatment.)
The above demonstration of fiber gener-
ation, as seen under low powers of light opti-
cal viewing, fully conforms with expecta-
tions from chain stretching in elongational
flow fields, in close analogy with what has
been observed under the more readily defin-
able and explorable conditions of the solu-
tion experiments. In addition, the last-pre-
sented case of the converging single jet ori-
fice leads us into a system that is common
in the technological practice of melt char-
acterization and melt processing and which,
in addition, has been the reason for further
fundamental studies relevant to the subject
of this review. These are covered in the fol-
lowing sections.
4.5 Relation Between
Morphology and Orientation
4.5.1 The General Scheme
In what follows we revert again to our
initial theme, namely that in orientation
218 4 Flow-Induced Orientation and Structure Formation
induced by flow we have essentially two
types of entity: those that are virtually fully
extended and those that are virtually unex-
tended, with (to a first approximation) noth-
ing in between. The 'entity' can refer to two
different dimensional levels, namely to the
chains and to the crystals arising therefrom.
The common ground is that flow of the
appropriate kind and strength will extend
the chains in a limited portion of the mate-
rial giving rise to fibrous crystals aligned
along the flow field, with the remainder of
the material crystallizing into chain-folded
platelets just as it would in a state of rest.
Thus the flow-oriented, final crystalline
product is constituted of a combination of
these two morphological entities. In the fol-
lowing we shall look at the possible combi-
nations. In the first place this will be irre-
spective of how they originate on a molec-
ular level, merely restating the fact that, to
a first approximation, increasing the
strength of the flow creates more fibers, i.e.,
it orients and extends more chains, as
opposed to extending all the chains uniform-
ly to some higher degree in a progressive
manner.
Before proceeding, the spherulite, i.e., the
relevant structural element of melt crystal-
lization, which arises in the absence of flow,
needs explaining. Figure 4-23 shows its
familiar appearance under the polarizing
microscope. It shows a spherically (or cir-
cularly, in two dimensions) symmetrical
arrangement of birefringent structural ele-
ments. In this instance they are displayed in
consecutive stages of growth, illustrating
the evolution of structure with time. This is
a cornerstone in the major field of crystal-
lization kinetics, specifically as interpreted
in terms of structure development, a subject
to feature in the next chapter in this Volume,
and hence will not concern us further
here.
Figure 4-23. Spherulites,
an example of their optical
features and growth in the
case of polyethylene. This
figure shows six successive
stages of spherulite growth
from the melt at the (con-
stant) temperature of
123 C. The times of crys-
tallization are indicated in
each frame; polarizing opti-
cal micrograph; crossed
polars (Chivers et al.,
1982).
 4.5 Relation Between Morphology and Orientation
Figure 4-24. Schematic model of a spherulite incor-
porating the following main features: spherical sym-
metry, lamellar crystal constituents, and periodic
orientation variations of these constituents along the
spherulite radius.
In Fig. 4-23 the spherulites are seen to
have a concentrically banded structure,
which is due to the periodically varying
orientation of the birefringent structure ele-
ments along the radii (see reviews, e.g., Kel-
ler, 1985). In morphological terms this aris-
es from crystal lamellae growing radially
outwards from a common center (which is
normally the centre of the initial sheaf) with
a continuous periodic variation in the orien-
tation. The latter is normally envisaged as
some kind of helicoidal twisting. Even if the
morphological details are by no means clear,
for the purpose to follow it will be repre-
sented through the model of Fig. 4-24.
(Detailed study of the fine structure, and
specifically how the lamellae build up the
spherulite in three dimensions is not quite
straightforward, because rather drastic etch-
ing or extraction procedures are required to
make the pertinent features accessible. Nev-
ertheless, micrographs such as Fig. 4-25 are
at least broadly consistent with a model such
219
Figure 4-25. Lamellar structures in melt-crystallized
spherulitic polyethylene. The interior three-dimen-
sional structures are revealed thanks to solvent extrac-
tion of lower molecular weight material that had not
crystallized at the intended high crystallization tem-
perature of 128.8 C, only on subsequent cooling.
Scale bar = 1 um (for A and B see source reference).
Scanning electron micrograph (Winram et al., 1978).
as Fig. 4-24, in as far as they reveal the
lamellar structural elements also indicating
their twisting nature.)
In the following the overall pattern of
structure development as a function of flow
strength will be outlined in the light of the
dual fiber-platelet morphology scheme.
This will be followed by illustrations
through case histories with emphasis on his-
torical development. The subsequent sec-
tion (Sec. 4.5.5) will then treat the macro-
scopic orientation in terms of the morpho-
logical background established in the pre-
ceding sections.
For the overall pattern of structure-mor-
phology development, Fig. 4-26 should
serve as guidance. Starting at the high flow
strength end of the spectrum, the situation
here is as follows. A large majority of the
chains will be stretched out under the strong
orienting influence and, when crystallized,
will give rise to fibers. Thus the situation of
an entirely, or at least predominantly,
220 4 Flow-Induced Orientation and Structure Formation

XDOOO ooooc x x x o ooooc

X X X X ) OOOOC XXDOO ooooc
>oooo OOOOC X X X X ) ooooc

a) b) c)
Figure 4-26. Schematic representation of the crystal texture originating during orientation (flow)-induced crys-
tallization of polymeric melts, shown for polyethylene. Details (a), (b), and (c) show the effect of decreasing the
strength of the orientation influences. Orientation generates fibrous crystals as shown in (a). On weakening the
orientating influence, fewer and hence more widely spaced fibers form, and the intervening material subsequent-
ly crystallizes as platelet overgrowth. With a moderate fiber separation the platelets are all essentially parallel
(b), but with a large fiber separation, arising under a still weaker orienting influence, the platelets will twist (c)
(meant to be conveyed by the plaited lines) as they would in spherulitic growth under stationary conditions (see
Fig. 4-24), except here they are confined to planes normal to the fiber (hence flow) direction. [Scheme based on
Keller and Mackley (1974) and Keller and Machin (1967)].

may be an intrinsic limitation on the fiber

Figure 4-27. X-ray diffraction pattern of a highly
oriented polyethylene filament showing oaxis orien-
tation (by courtesy of A.W.M. Braam).
fibrous morphology will arise giving rise to
the characteristic c-axis X-ray fiber diffrac-
tion pattern of Fig. 4-27. This is the case that
we attempt to illustrate schematically in Fig.
4-26 a. We have no a priori knowledge of a
specific fiber diameter, but by experience
(see Sec. 4.3), and by analogy with the solu-
tion case, the fibrils are likely to be in the
10-100 nm region. It is possible that there
diameter, as observed in solutions (George
and Tucker, 1975) and accounted for theo-
retically by Hoffman (1979) as discussed in
Sec. 4.3.3, conditions which may well also
be applicable to the melt. Also in reality a
small amount of unextended chains is like-
ly to be left, giving rise to some stunted
platelet overgrowth, not represented in the
sketch of Fig. 4-26 a.
With diminishing flow strength, fewer
chains will become extended because the
cut-off of chain extension will move
increasingly towards higher molecular
weights in a given molecular weight distri-
bution for a given strain rate (see Fig. 4-7),
which leaves an increasingly larger portion
of the chains unextended. Thus there will be
fewer fibrils where the space between them
will become filled with lamellar overgrowth
analogously to solution grown shish-kebabs
(Fig. 4-26b).
As, with a decreasing flow strength the
number of fibers decreases, with a concom-
itant increase of the spaces in between, there
will be a corresponding increase in the lat-
eral extension of the chain-folded over-
growth layer. However, based on extensive
long-standing experience, as the distance
 4.5 Relation Between Morphology and Orientation
between the fibers increases a further, new
factor comes into play. The growing lamel-
lae will not stay parallel but will progres-
sively randomize as they would in a sphe-
rulite. In spherulites this randomization is
usually achieved through regularly alternat-
ing orientation variations, giving rise to
periodic banding as in Fig. 4-23. This ran-
domization is represented in terms of peri-
odic helicoidal winding, as visualized in the
model of Fig. 4-24 in our schematization
(Fig. 4-26 c). The columnar object in Fig.
4-26 c can thus be regarded as a parallel
stack of two-dimensional spherulites, which
can be best appreciated through the three-
dimensional representation in Fig. 4-37 (see
Sec. 4.5.5.2). Note that in the case of very
weak flows very few fibers form. These, in
themselves, would be inadequate to influ-
ence the final sample characteristics if it
were not for setting the pattern of the ensu-
ing lamellar overgrowth for the overwhelm-
ingly major portion of the material, which
has remained unextended. This will impart
a characteristic texture, on a morphological
level, and a characteristic orientation pat-
tern, on the level of X-ray diffraction diag-
nosis, to the sample as a whole; these will
be taken in turn in the following.
On a morphological level the scheme of
Fig. 4-26 has the following to convey: the
characteristic effect is a fibrosity along two
mutually orthogonal directions, one parallel
and the other perpendicular to the initial
orienting influence (flow), but on different
scales. At low magnification it will be the
parallel fibrosity that is apparent, represent-
ed by the original flow-induced fibrils plus
the surrounding envelope of transverse
lamellae, where the latter may not be indi-
vidually resolvable. The impression of par-
allel fibrosity is thus created by the parallel
columns consisting of core fibers and over-
growth platelets. At high magnifications, on
the other hand, the transversely growing
221
lamellae will appear prominent giving the
overall impression of a fibrosity that is per-
pendicular to the flow direction. Under still
higher magnification a further distinction
may become possible within the transverse
fibrosity, namely straight fibers (lamellae
seen edge-on, see Fig. 4-26 b) or further
structural features along the transverse
fibrosity due to orientation variations along
the lamellae (Fig. 4-26 c). Irrespective of
the last-mentioned distinction, fibrosity
transverse to the orienting influence is
seemingly contrary to a priori expectations.
Clearly the borderline between the two
cases, as perceived at a given magnification,
will be much affected by the width of the
columns, which is determined by the num-
ber of fibers, in turn determined by the
strength of the flow.
4.5.2 Examples of Fibrous and
Parallel Lamellar Columnar Structures
The first examples used in developing the
theme just stated relate to experiences with
a capillary rheometer (Fig. 4-28). Here, the
portion effective in producing orientation is
the entrance orifice, which is equivalent to
the single jet case discussed in Sec. 4.4.3
(Fig. 4-21 there), thus forming a natural link
between the subject matter of the two sec-
tions.
We start with the high flow strength
end of the spectrum, which was also the
starting point of the seminal works of van
der Vegt and Smit (1967). These authors
performed standard rheological measure-
ments using a capillary rheometer (Fig.
4-28) on polyolefins (polypropylene, poly-
ethylene, and ethylene propylene copolym-
ers) and also on natural rubber, but in con-
trast to usual practice, not only at conven-
tional processing temperatures (i.e., far
above the melting point where the viscosity
is lower), but also closer to temperatures
222 4 Flow-Induced Orientation and Structure Formation
^ 10
PISTON
HEATING
ELEMENT
PRESSURE
TRANSDUCER
DIE
Figure 4-28. Schematic representation of a capillary
rheometer used in many of the experiments referred
to throughout the review.
where the respective materials solidify
under stationary conditions in practice.
Here they made the observation, unexpect-
ed at the time, that for sufficiently high
strain rates (as calculated from the plunger
speed) the viscosity increased (instead of
decreasing, as for the usually expected shear
thinning behavior) with increasing rate, this
rise proceeding to infinity, i.e., until com-
plete cessation of flow, meaning blockage
of the capillary at a critical shear rate (yc).
(A pressure vs. plunger velocity curve of our
own illustrating this phenomenon is shown
in Fig. 4-29.) The solidified polymer
blocking the flow in the form of a plug
showed a very high degree of orientation by
X-ray diffraction, corresponding to c-axis
orientation in a normal drawn fiber (see
Fig. 4-27).
10 101
Apparent wall shear rate (s l)
Figure 4-29. Apparent flow curve (uncorrected
stress vs. apparent wall shear rate) for a linear poly-
ethylene (M=2.8x105) measured at 146C showing
the onset of elongational flow-induced crystallization
(Kolnaar and Keller, 1995) (indicated by yc). Our own
repeat of the effect discovered by van der Vegt and
Smit (1967) (but expressed differently there).
van der Vegt and Smit (1967) interpreted
the effect in question as the consequence of
elongational flow-induced chain extension
associated with converging flow into the
entry orifice, which then raises the melting
point, in turn leading to crystallization. The
latter being from preoriented chains leads to
the macroscopic orientation observed.
Attribution of the blocking effect to elon-
gational flow is substantiated by the depen-
dence of the (apparent) critical elongation-
al strain rate eAc on the entrance angle of
the conical orifice, in the sense that a larg-
er a (where a is half the cone angle), corre-
sponding to higher convergence and hence
to a larger elongational flow component,
required a lower critical throughput
(expressed in terms of an apparent wall
shear rate yAc) and hence a lower piston
 4.5 Relation Between Morphology and Orientation
velocity for the blockage effect to occur. In
fact the anticipated relation of van der Vegt
and Smit (1967)
A c = K yAc tan 2a (4-4)
(expressed here in our own notation; K is a
constant3) was found to be closely obeyed.
The van der Vegt-Smit line of experimen-
tation was pursued further in numerous
studies by Porter and collaborators (e.g.,
Southern and Porter, 1970; Porter et al.,
1975). The emphasis here was on the prod-
uct (plug) arising through the blockage,
which showed advantageous properties,
specifically a high modulus (70 GPa) and
breaking strength ( 3 GPa), placing the
plug thus obtained in the ultrastiff and ultra-
strong material category. The latter arises
from the very high chain extension making
the C-C valence bonds along the almost
fully stretched out chain the stiffness and
strength determining element. Most essen-
tially for the present discussion, the materi-
al is highly fibrous and, as far as can be
assessed from the published scanning elec-
tron micrographs, consists largely, if not
entirely, of fibrous structural elements. The
macroscopic plug readily fibrillates, as is to
be expected from a predominantly fibrous
morphology, nevertheless it is highly homo-
geneous in its undisturbed state, at least on
the light optical scale, as testified by its
transparency (Fig. 4-30).
While the above-mentioned, highly chain
extended, essentially fibrous plugs are
obtainable by merely extracting the solidi-
fied material from the capillary after the
blockage has occurred, most of the so-called
'Porter plugs' referred to in the literature,
including the work in Bristol (Farrell and
Keller, 1977), have been obtained by
3 concerned (Keller and Odell, 1978), the
Following rheological practice we use here the sym-
bol 7 to denote shear rates as rheologically defined,
while retaining the symbol as the elongational strain
rate experienced by the individual chain molecule.
223
Figure 4-30. Two strands of the same high density
polyethylene. The opaque strand (bottom) is conven-
tionally extruded. The translucent strand (top) has
been prepared under special conditions involving
solidification in the capillary (Porter et al., 1975).
squeezing the solidified material out
through a further increase in the pressure.
From a practical point of view this was con-
venient as it enabled the continuous produc-
tion of filaments. Nevertheless, from the
scientific point of view, it gave the resulting
product a hybrid origin. Namely, these prod-
ucts are the combined outcome of flow-
induced crystallization and subsequent
'solid-state extrusion'. The latter is a solid-
state deformation process (even if per-
formed at high temperatures close to the
melting point), a subject outside the scope
of the present chapter (see Chapter 16, by
Ward, in this Volume). In the following we
shall focus on experiments involving flow-
induced crystallization alone, without any
subsequent deforming influence.
While keeping to a capillary rheometer as
in Fig. 4-28, we shall now consider struc-
ture formation at lower strain rates, i.e.,
before the onset of blockage yet still while
in the course of flow. In the particular work
temperature and plunger velocity were
adjusted so as to create fibrous crystal
entities that are solely flow induced but
224 4 Flow-Induced Orientation and Structure Formation
insufficient in number to produce blockage.
The fiber formation was monitored by
polarizing light optical methods. These
were of two kinds: (i) Viewing the melt dur-
ing flow in situ in an apparatus equipped
with a glass capillary (Keller and Odell,
1978). Here the appearance of birefringent
lines at a low magnification could be regis-
tered directly, (ii) After complete solidifica-
tion in the stationary state within the result-
ing product. Here the initially formed fibers
could be made apparent on the hot stage
under a polarizing microscope when, at a
sufficiently high temperature within the
melting range, only the fibrous entity
remained visible in high birefringence con-
trast (Grubb et al., 1975).
Having ensured that the conditions for
fibrous crystal generation were established
without blockage occurring, the resulting
final morphology could be purposefully
controlled and designed. In this way, over a
wide range of conditions, columnar struc-
tures with parallel lamellar overgrowth
could be created conforming to stage (b) of
Fig. 4-26 in the general scheme, which
could be made apparent through special
sample preparation methods under the elec-
tron microscope (Fig. 4-31).
The formation of parallel lamellar tex-
tures with the lamellae having grown trans-
verse to the initial orienting influence is
widespread and not confined to the special
conditions just described; the example
given should serve merely as an illustration
of how they can be controlled and purpose-
fully designed. Such structures can appear
under a range of conditions involving solid-
ification during flow and are a common
occurrence in, e.g., injection molding. Fig-
ure 4-32 illustrates such a case where it was
a coincidental consequence of the process-
ing conditions adopted and only understood
after the above-described morphological
framework had been established (Davis,
1966; Clark, 1967). In full knowledge of the
principles involved such structures can now
be purposefully created. This can be for
scientific studies or for technological appli-
cations. Amongst the former is a special
thin-film preparation method (Petermann
and Gleiter, 1973; Gohil and Petermann,
1979) involving hauling off molten films
from glass slides, extensively used as mod-
els of parallel lamellar structures, as seen in
edgewise projection. Examples with tech-
nological purpose or potential will be out-
lined in Sec. 4-11.
Figure 4-31. Columnar struc-
ture containing lamellae per-
pendicular to the column and
hence the flow direction in a
sample of polyethylene crystal-
lized under the influence of
flow (SW -> NE). (The lamel-
lae from adjacent columns in
fact interlock - see in detail in
Fig. 4-33 below.) Transmission
micrograph of a section, heavi-
ly stained in order to show up
the columns (Odell et al.,
1978).
 4.5 Relation Between Morphology and Orientation
Figure 4-32. Surface of an injection-molded bar of
polyoxymethylene showing edge-on lamellae trans-
verse to the injection direction. Electron micrograph
replica [Davis (1966) based on Clark (1967)].
4.5.3 A Special Case of Fiber-Platelet
Structures: Interlocking Shish-Kebabs
Within the topic of fiber-platelet struc-
tures in melt-crystallized material, a special
situation deserves a separate mention. This
is still in the category of Fig. 4-26 b with the
columnar structures and the lamellae all par-
allel. Here, by appropriate control of the
flow rate in a capillary rheometer and the
cooling rate of the emerging extrudate, the
lamellae can be obtained in a tapered form
where the wedge-shaped lamellae from
adjacent columns interlock. Figure 4-31 in
fact falls into that category, with the taper-
ing apparent at the higher magnification of
Fig. 4-33 (Odell et al., 1978), together with
the underlying computer-generated model
shown in Fig. 4-34. The origin of the taper-
ing lies in the well-known relation between
the lamellar thickness, i.e., the fold length
(/), and the crystallization temperature (r c ),
namely / <*> D/AT, where AT=T^-TC with
T^ being the equilibrium melting point and
D is a constant containing the material
parameters [see, e.g., review by Keller
(1985)]. It follows that when the tempera-
225
Figure 4-33. Enlargement of the interlocking, zip-
fastener type, lamellar structure as shown in Fig.
4-31. The section has only been lightly stained in order
to show up better the lamellar detail (Odell et al.,
1978).
ture decreases in the course of crystal
growth, the lamellar thickness will decrease
continuously according to the above rela-
tion, leading to tapered overgrowths. Inter-
locking is achieved by suitable control of
this taper and of the fibril separation. The
latter is governed by the combined effects
of strain rate (flow strength) and molecular
weight according to the foregoing, the for-
mer by the conditions of cooling of the
extrudate. The model in Fig. 4-34 was com-
puter-generated from the actual experimen-
tal input parameters and from the appropri-
ate relations determining layer thickness
and growth rates as a function of AT.
The interlocking shish-kebab structures,
having the appearance of a zip-fastener, in
Figs. 4-33 and 4-34 are of interest from sev-
eral points of view. They represent a special
manifestation of the fiber-platelet duality
theme of this paper: they show the potential
226 4 Flow-Induced Orientation and Structure Formation
Figure 4-34. Columnar-lamellar interlock model,
computer-generated from the input parameters of the
experiments underlying Figs. 4-31 and 4-33 (Odell
etal., 1978).
of harnessing the morphology for specific
purposes, and chiefly, that the extrudates
themselves thus prepared can have special,
advantageous properties (Bashir et al.,
1986). We shall return to this in Sec.
4.11.1.2.
4.5.4 'Row Structures'
Structure elements corresponding to case
(c) in Fig. 4-26 arose before any of the other
variants of the scheme. Historically, such
structures were invoked to account for some
anomalous X-ray orientation effects, such
as in Fig. 4-35, in certain polyethylene sam-
ples. Such patterns were first noticed by one
of us for certain polyethylene tubes prepared
in the laboratory from standard insulating
covers (for purposes extraneous to the
present article) and were identified as being
identical to those given by commerical poly-
ethylene sheets, which at that time were
obtained through hauling off the melt from
rollers (Keller, 1955). It was recognized that
Figure 4-35. X-ray diffraction pattern of a hauled-off
polyethylene film possessing the 'row structure' (Kel-
ler, 1955).
the common feature was solidification dur-
ing flow, under rather mild orientation con-
ditions such as leave the primary product of
the flow-induced crystallization, once
formed, undeformed by the prevailing
orienting influence4.
Spherulite formation was already famil-
iar at the time (even if not receiving the gen-
eral attention given to it later), but lamellae
and shish-kebabs were yet to be discovered
and so was the consequent distinction be-
tween lamellar and fibrous crystals. Never-
theless, it was recognized even at that time
that if primary crystal growth, such as would
normally lead to three-dimensional spheru-
lites, were initiated from rows of closely
spaced nuclei, the rather unusual diffraction
pattern of Fig. 4-35 would result; the essen-
tial point, in widest generality, being that the
orientation displayed by a pattern such as in
Fig. 4-35 is not due to deformation, but to a
particular kind of oriented primary crystal
A ready and virtually foolproof way to achieve the
said orientation (Fig. 4-35) even manually is to hold
a film of polyethylene across a heated zone (e.g.,
above a small flame) until its central portion just about
melts. At this stage the film should be slowly extend-
ed while being removed from the heated zone. The
extension should be stopped as soon as the progress-
ing solidification offers noticeable resistance to fur-
ther drawing.
 4.5 Relation Between Morphology and Orientation
growth. The underlying model called the
'row structure' is in the light of later knowl-
edge (Keller and Machin, 1967) identical to
that in Fig. 4-26 c (and Fig. 4-37 c below).
Even if the term 'row' or 'row-nucleated'
structure is nowadays often applied collec-
tively to both variants (b) and (c) in the
scheme of Fig. 4-26, here we shall confine
it to that under (c) alone, as originally des-
ignated.
As is apparent from the foregoing, the
main evidence for structures as in Fig.
4-26 c, arising at the low end of the flow
strength spectrum, comes from diffraction
patterns. Therefore the class of structure
patterns will be treated in detail in the sec-
tions to follow, which are devoted specifi-
cally to orientation-related issues as regis-
tered by diffraction. Here just a few com-
ments will be made concerning the row
structure's morphology. At the time when
the row structure was originally postulated
and verified [against considerable scepti-
cism; for the historical controversies see
Keller and Mackley (1974); Keller and
Machin (1967) - the full story has not yet
been put down as a coherent record], elec-
tron microscopic techniques for the study of
the bulk interior were not yet available.
Morphological substantiation of structures
such as in Fig. 4-26 c was confined to thin
films amenable to direct transmission. Fig-
ure 4-36 is an example that, even if it was
obtained not by flow but by static orienta-
tion of the melt (see Sec. 4.7), illustrates the
reality of the morphological model pro-
posed, and particularly its relation to the dif-
fraction pattern (in the case of Fig. 4-36 the
electron diffraction pattern) given by such
morphologies. Analogous morphological
effects were also later verified in bulk, flow-
oriented, low density polyethylene samples
(Dlugosz and Ungar, 1979), which even if
involving rather drastic interference with
the structure, substantiated the model used
227
Figure 4-36. Transmission electron micrograph of a
thin film of polyethylene crystallized from a lightly
stretched melt snowing ribbons transverse to the draw
direction (vertical); these are either fully twisted or
are in varying stages of partial twist (1 cm represents
0.25 Jim).
to account for the characteristic diffraction
pattern of Fig. 4-35. Reverting to the pre-
ceding experimentation using the capillary
rheometer (Fig. 4-28), diffraction patterns
such as in Fig. 4-35 were the regular out-
come at the lowest end of the extrusion rate
spectrum. By that time the reality of the row
structure of Fig. 4-26 c was firmly estab-
lished, yet the underlying morphology has,
to our knowledge, not received further
attention involving the use of the more
advanced electron microscopic sample
preparation techniques which have become
available in the meantime.
4.5.5 Interpretation of Orientation
Effects
4.5.5.1 General
In general, flow-induced structure forma-
tion leads to an overall orientation of the
macroscopic product, irrespective of wheth-
er attainment of the orientation is the intend-
ed purpose or an associated by-product of
the underlying melt processing. In either
case the resulting orientation needs to be
characterized, which as far as the crystal
228 4 Flow-Induced Orientation and Structure Formation
orientation is concerned is most informa-
tively done by X-ray diffraction and inter-
preted in terms of the underlying structure
(unit cell) and morphology. In common
practice the characterization is carried out
in terms of a single reference, i.e., the chain
direction, which in crystallographic nota-
tion corresponds to the c-axis, and is done
by the quantification of such an orientation
in terms of a single parameter (i.e., the orien-
tation parameter). We maintain that without
an adequate appreciation of the morpholog-
ical background, such a procedure can be
grossly inadequate and even misleading.
In general, the nature of the orientation in
question has first to be assessed in qualita-
tive terms, i.e., what kind of orientation we
are dealing with in a specific case, before
quantification in the above sense acquires
any meaning. It happens that in common
fiber drawing practice it is the c-axis align-
ment alone that is pertinent and the descrip-
tion of the resultant orientation in terms of
a mean angle (or a term containing this
angle) with respect to the fiber axis is con-
sidered an adequate representation, particu-
larly at high levels of orientation (draw
ratios). But even in the case of normal fiber
practice, the above procedure often be-
comes manifestly inadequate at low levels
of overall orientation, such as encountered
at low draw ratios and particularly in the
spinning operation. Under more general
conditions of melt processing the above-
mentioned procedure may break down com-
pletely, a factor often not even recognized.
At this point an important injection needs
to be made. Orientation, even when fully
characterized, e.g., by an X-ray pole figure
mapping over full reciprocal space (never
completely achievable in practice and sel-
dom even approximated), can never be
uniquely interpreted in terms of the spatial
arrangement of the underlying structural
entities. Any attribution of macroscopically
registered orientation to the underlying
structure requires a model. Usually, this is
implied without being specifically spelled
out or even recognized. Such is the case for
a normal fiber, in, e.g., textile application,
where the model is a crystallite with c
inclined at specific angles to the fiber axis,
which is itself an axis of cylindrical symme-
try. Here all c-axes corresponding to a par-
ticular inclination (0) are represented by a
mantle of a cone, there being some specifi-
able distribution of 0 values peaking at 0= 0
(i.e., c-axis parallel to the fiber axis). It is
this distribution that is normally extracted
from X-ray diffraction patterns and often
expressed in terms of a single parameter. It
is to be noted that, even within the confines
of this simple model, the attribution of orien-
tation to the structure remains incomplete,
as it does not specify whether there is to be
rotational averaging around c first within the
relevant structure unit, e.g., the microfiber,
it being at a particular 0, before rotational
averaging around the macroscopic fiber
axis, or whether we have a range of separ-
ate crystal units with different orientations
around c for each inclination 0. In terms of
the X-ray patterns, the two alternatives will
be indistinguishable, yet the underlying
morphology could be grossly different. The
above example refers to the simplest con-
ceivable X-ray diffraction pattern of a uni-
axially oriented structure (c-axis oriented
fiber pattern); for more complex orientation
patterns the ambiguities regarding the pos-
sible underlying structure are increasingly
manifold. The above relates to the most
informative technique, namely X-ray dif-
fraction, which can provide full orientation-
al mapping of each crystallographic plane;
it goes without saying that techniques that
are only capable of giving some average in
terms of a single parameter will provide
incomparably less information with a corre-
sponding increase in ambiguities.
 4.5 Relation Between Morphology and Orientation 229

4.5.5.2 Orientation in Terms their corresponding schematic diffraction

of Fiber-Platelet Morphologies
In this section we consider the orientation
that is imparted to the macroscopic sample
by the underlying fiber-platelet morpholo-
gy. Once again we shall follow the scheme
of Fig. 4-26. First, however, it must be
remembered that for all except thin film
samples, Fig. 4-26 is a projection: in a bulk
sample there will be cylindrical averaging
around the flow direction (the vertical in
Fig. 4-26), which in the simplest case is that
of uniaxial orienting influence; we shall
take this as our starting point. In order to
convey this, cases (b) and (c) in Fig. 4-26
are represented in a three-dimensional per-
spective view in Fig. 4-37, together with
patterns for the discussion to follow.
As regards crystallographic orientation,
the fibrous crystals will always impart a c-
axis orientation parallel to the flow direc-
tion (Fig. 4-37 a). As long as the transverse
lamellae are all parallel to each other
(Fig. 4-37 b), they too will represent c-axis
orientation with respect to the flow direc-
tion, so imparting the usual fiber orientation
with the familiar c-axis diffraction pattern
(Fig. 4-38 a and sketch in Fig. 4-37 d) to the
sample as a whole. (This, amongst others, is
the case for a parallel assembly of solution-
grown shish-kebabs.) In such a structure, the
fiber and platelet components are indistin-
guishable by the usual wide angle X-ray dif-
fraction pattern. However, in situations

Bulk

Thin film

a) b)

020( f 020 r j ) O2o( r \

d) e) f)
Figure 4-37. Schematic diagrams such as in Fig. 4-26 showing, in addition, the influence of the various mor-
phologies generated by orientation-induced crystallization on the resulting macroscopic orientation, as revealed
by the respective X-ray diffraction patterns. The structures have rotational symmetry around the direction of the
orienting influence (vertical) such as they would in a three-dimensional bulk sample. The similarities to the two-
dimensional versions in Fig. 4-26 should be obvious [(a), (b), (c)]. The diffraction patterns [(d), (e), (f)] are
sketches representing the main features of the two principal reflections in polyethylene for each structure type
beneath which they are placed in the diagram. Pattern (d) refers to both structures (a) and (b). Note that (c) is
the row structure giving the pattern in Fig. 4-35 [(f) in the present figure]. There is no structure drawn for the
intermediate orientation pattern of (e). This is accounted for by the scheme in Fig. 4-40 (to follow). Both scheme
and interpretation are based on Keller (1955), Keller and Machin (1967), and Keller and Mackley (1974) (in
chronological order).
230 4 Flow-Induced Orientation and Structure Formation
where fibers are few and hence widely
spaced, as arises in weak flow, the trans-
verse lamellae can twist (and hence random-
ize around b in the case of polyethylene) as
they do in a spherulite but here confined to
planes perpendicular to the flow direction
(Fig. 4-37 c). This type of arrangement, the
originally termed row structure, gives rise
to a characteristic X-ray diffraction pattern
(Fig. 4-35), as sketched in Fig. 4-37 f and
readily derivable by pole figure construc-
tions from a structure such as Fig. 4-37 c
(Keller and Mackley 1974; Keller and
Machin 1967). (Note, it involves two rota-
tional averagings: the first around the b-
axis, the radial direction for a spherulite in
polyethylene, and the second around the
flow direction, which is orthogonal to it.)
Such a diffraction pattern, displayed by the
hauled off and blown polyethylene films, is
generally distinctly different from that of
either a normal drawn fiber, or from that of
a random bulk, yet it does not represent an
intermediate state between the two, either in
terms of the alignment of crystals or in terms
of molecular extension preceding crystal-
lization; it is in fact due to a particular super-
position of fully oriented fibers arising from
oriented, stretched out molecules and of an
essentially disoriented overgrowth, with a
directionality that is determined merely by
its expitaxial relation to the fiber but other-
wise arising from initially random chains.
In cases where the orienting influence is
Figure 4-38. X-ray diffraction pat-
terns of polyethylene films crystal-
lized under stress at three different
stress levels [decreasing in the
sequence (a) to (c)].
more complex, e.g., having a biaxial char-
acter, such as arises in the blow-molding
fabrication of films, the same consideration
will still hold, except that here, as shown by
Choi et al. (1982), the resulting multiaxial
orientation is now in terms of the rows
(Fig. 4-39) and not directly in terms of
molecules and crystals, as might be envis-
aged without recourse to the morphological
background. Thus even in such a complex
case, the 'oriented-unoriented' crystal tex-
ture or in molecular terms 'extended and
random' chain duality (our main theme
here) still applies.
However, even when confining ourselves
to purely uniaxial situations, orientations
that are intermediate between those in
Fig. 4-38 a and Fig. 4-35 can arise (Figs.
4-38 b, 4-38 c, and sketch in Fig. 4-37 e). In
the beginning such orientations were taken
as intermediate orientations of crystals be-
tween the c-axis and the a-axis orientations
(the latter by incorrect reading of diffraction
patterns such as in Fig. 4-35). However, it
has become apparent (Keller and Mackley,
1974; Keller and Machin, 1967) that such
orientations are intermediate only in the
morphological sense and not in the sense of
the initial orientation of molecules and of
the resulting crystals. Namely, the exclusive
fiber-lamella duality, together with the pre-
ceding extended and random chain duality,
(our principal theme here) remains opera-
tive; the disposition of the lamellae will
 4.5 Relation Between Morphology and Orientation
MD
Figure 4-39. Morphological model for a tubular
blown film with equal biaxial orientation. MD and TD
denote machine and transverse directions, respective-
ly (Chori et al., 1982).
merely be intermediate between those in
Figs. 4-37 b and 4-37 c, so giving rise to
'intermediate' diffraction patterns such as
Figs. 4-38 b and 4-38 c and sketch 4-37 e.
In morphological terms the above inter-
mediate situations are best rationalized
along the llines of Nagasawa et al. (1973),
as represented by Fig. 4-40 from their work.
Here, the lamellar overgrowth starts with an
epitaxial c-axis alignment along the c-axis
oriented core fiber. As the lamellae grow
outwards they gradually twist (or in gener-
al randomize) around b (in the case of poly-
ethylene). Full randomization (around b) in
terms of the resulting orientation is only
reached after a number of turns of the lamel-
lar crystal. As worked out quantitatively in
Nagasawa et al. (1973), by integrating the
orientation over cylinders of increasing
231
og
I
IIIO
3
Figure 4-40. Scheme (Nagasawa et al., 1973) to
account for orientations intermediate between c-axis
and 'row' orientation (such as in Fig. 4-38), also includ-
ing predominant a-axis orientation, in terms of increas-
ing row (columnar) diameter. A and B refer to two
stages in the lamellar growth - see reference quoted.
diameter, the intermediate cases between
pure c-axis orientation (core fiber plus c-
axis aligned lamellar overgrowth close to
the core) and the final row orientation [such
as in Figs. 4-35 and 4-37 f, corresponding to
full randomization around b (i.e., to the fully
developed two-dimensional spherulites)]
include the observed intermediate orienta-
tions such as in Figs. 4-38b, 4-38 c, and
4-37 e (including stages of predominant
<2-axis orientation). Here the variable deter-
mining the final overall orientation is the
cylinder diameter, which is determined by
the distance between the fibers, in turn
determined by the number of fibers them-
selves. That is, many closely spaced fibers
yield overall c-axis orientation (constituted
of fibers plus overgrowths), but few, wide-
ly spaced fibers yield the row structure, with
the orientation of the lamellae essentially
forming two-dimensional spherulites with
232 4 Flow-Induced Orientation and Structure Formation
the spherulite planes perpendicular to the
flow direction; an intermediate number of
fibers will allow only partial randomization
of the lamellar overgrowth so giving rise to
orientations in between. All the above is
again in full accord with our theme here,
namely that all observed orientations are
accountable in terms of a fiber-platelet
duality as arises from the two extremes of
extended and random molecules without
intermediate stages in terms of chain exten-
sion and resulting crystal orientation, such
as may be construed (mistakenly) from a
picture of the affine deformation of mole-
cules and the resulting gradual orientation
of crystals. For a given material the orient-
ing influence, namely the strength of the
flow, only affects the fiber-lamella ratio,
stronger flow creating more fibers, with the
consequences just given. For a given flow
strength the determining factor is the molec-
ular weight: as will be referred to below,
higher molecular weight yields more fibers.
In conclusion, it will have become appar-
ent that the whole family of apparently com-
plex orientations follows from a single mor-
phological scheme. Or conversely, that
without such a morphological scheme such
a series of diffraction patterns would evade
a meaningful interpretation.
4#6 Orientation and Structure
Formation in Simple Shear Flow
4.6.1 General Considerations
In the preceding sections attention was
focused on chain stretching as explored both
on isolated chains in solution and on chains
forming a mechanically effective network -
as is the case in concentrated solutions and
melts - and on subsequent crystallization.
For the case of isolated chains in dilute solu-
tion it was argued that in order to achieve
complete, or nearly complete, chain exten-
sion, uniaxial accelerating flow (i.e., elon-
gational flow) is prerequisite. Here the forc-
es required to stretch out the chains are trans-
mitted by the surrounding fluid. In simple
shear flow, as it contains a rotational besides
an extensional flow component, full chain
extension of individual chain molecules can-
not be accomplished (see, e.g., de Gennes,
1974). Here, in simple shear flow, the pres-
ence of mechanical connectedness of the
individual chain molecules, in the form of
entanglement points, is a prerequisite to
achieve chain extension, which then takes
place between these topological constraints.
Once stretched out at the appropriate tem-
perature, these molecules can crystallize in
the form of fibrous crystals, the morpholog-
ical particulars of which (shish-kebabs) have
been discussed in earlier sections.
Thus it is possible to generate fibrous cry-
stals in concentrated solutions and melts
employing flow fields that are of simple
shear character, but with some uncertainties
as to the nature of the flow on the local level.
For example, there could be turbulence (in
solutions), or chains anchored along walls
(Sec. 4.8.3) or in already solidified layers
(Sec. 4.11.2), etc.
When the flow is of truly simple shear
character down to the molecular level,
shish-kebab creation is still possible
through entanglements, yet less effective
compared with elongational flow fields. It
was demonstrated in the 1960s that the
application of a low level of shear to a super-
cooled melt significantly increases the rate
of crystallization, both in the course of flow
(Andersen and Carr, 1978; Pucci and Carr,
1984) and in the subsequent quiescent state
after flow has been stopped (Maxwell et al.,
1964; Maxwell, 1965). In comparison with
quiescent crystallization conditions, the
presence of simple shear flow thus affects
both the rate of polymer crystallization, as
 4.6 Orientation and Structure Formation in Simple Shear Flow
well as the resulting crystalline morpholo-
gy (Fritzche and Price, 1974; Krueger and
Yeh, 1972). In a steady state of flow there
is then a balance between shear flow-
induced structure formation and nucleation
(Lagasse and Maxwell, 1976; Wolkowicz,
1978) on the one hand, and material renew-
al on the other. Moreover, most melt-form-
ing operations of crystallizable polymers
involving shear flow, e.g., injection mold-
ing, are not conducted isothermally, but
involve cooling, which needs to be taken
note of when considering structure forma-
tion. Therefore for control of the underly-
ing nucleation and crystal growth process-
es, besides the flow, heat transfer should
also be taken into account (Janeschitz-
Kriegl and Eder, 1990; Eder et al., 1989).
The broad subject area of orientation and
texture formation in shear flow will be cov-
ered extensively by the following chapter in
this Volume. Here, in the light of the themes
underlying the present review, only some
brief remarks will be made, partly for com-
prehensive presentation and also as they
provides further material to strengthen our
main points. Like most of the literature on
shear flow-induced structure formation, we
shall confine ourselves to the case of poly-
mer melts.
4.6.2 On the Role of Entanglements
in Simple Shear Flow
It was pointed out above that topological
constraints are a prerequisite for the stretch-
ing out of chain molecules in simple shear
flow fields. In fact, the major factor govern-
ing the overall motion of polymer in a dense
system is the effect of entanglements. The
concept of entanglements forms much of the
basis for polymer melt rheology. Entangle-
ment points may be specified, or described
by mathematical models, in which case a
polymer molecule is envisaged as a seg-
233
mented chain. [The latter is, e.g., also the
case for the well-known molecularly based
Doi-Edwards theory (Doi and Edwards,
1979), which does not refer to specific
points of entanglement, i.e., the molecular
weight between entanglement points does
not appear as a parameter. Instead, the
model starts with a mathematical chain,
namely a molecule composed of a tube.]
In the quiescent state entanglement points
are created and removed through Brownian
motion. The rate of both processes is
enhanced by temperature. During the steady
flow of a polymer melt there is again a bal-
ance between entanglements forming and
disappearing. However, now the number of
topological constraints (i.e., the entangle-
ment density) will be determined not only
by temperature but also by the rate of de-
formation and the total strain imposed, i.e.,
the macroscopic response of the melt is time
dependent. Being non-Newtonian in nature,
under steady state flow conditions at low
rates a polymer melt will display high resis-
tance to flow, i.e., high viscosity, which
qualitatively reflects a high entanglement
content. At higher rates of deformation the
fluidity of the melt is enhanced, an effect
known as 'shear thinning'. Thus, here in
simple shear flow, qualitatively, with an
increasing rate of shear deformation the
entanglement density is gradually reduced.
Another effect related to the (de)coupling
of entanglements is noted during start-up of
the flow (Lagasse and Maxwell, 1976). With
short time scales relative to the rate of de-
formation, the melt will behave like a high-
ly entangled elastic solid. Accordingly, the
stress will increase in proportion to the total
strain (f) imposed, which at a constant rate
of flow (y) means the time elapsed (y= yt).
Eventually, with much longer times, steady
state conditions will take over, in which
state through the action of the flow itself the
number of entanglements will become sub-
234 4 Flow-Induced Orientation and Structure Formation
stantially lower compared to the state at
t 0. For the entanglement density to decay
to its steady state value, a finite time (fluid
strain) will be required. When the disentan-
glement process is slow relative to the rate
of flow, i.e., the disentanglement time tdls
exceeds the time scale of the flow
(/Lflow= I//), 'delayed disentanglement' will
occur accompanied by an overshoot in the
stress (apparent as viscosity) compared with
the steady state value. Thus, depending on
the balance of the time scale of straining and
the rate of decoupling of the temporary top-
ological constraints, the entanglement den-
sity may remain high for a sufficient time,
and during this period of delayed disentan-
glement the elastic chain extension between
entanglement points may overshoot its
steady state value. Some consequences of
this will be commented on next.
In start-up flow experiments, shear flow-
induced crystallization effects become man-
ifest as a sudden rise in the melt viscosity
(which can be diagnosed using rheological
characterization methods such as cone-and-
plate and sliding plate rheometers). Concur-
rently, a fine fibrillar-like morphology (row
structure) begins to develop, as revealed by
examination of the subsequently quenched
product. At a given temperature and shear
rate, the shear-accelerated crystallization
effects are found to be critical in relation to
the molecular weight (M) (Lagasse and
Maxwell, 1976), a higher M requiring a
lower induction time, hence fluid strain.
This would imply that a critical fluid strain
is a precondition for the effects to occur. On
the other hand, at a given temperature the
critical shear rate for accelerated crystal-
lization shifts to a lower value as the molec-
ular weight increases. This is indicative of
an underlying molecular relaxation process,
which could, in particular, be a coil >
stretch transition. The onset of crystalliza-
tion effects in polyethylene occurs shortly
after start-up of the shear flow, particularly
at large supercoolings where the nucleation
rate is high relative to the rate of the chain-
orienting influence. Lagasse and Maxwell
(1976) therefore suggested that the high
degree of extension of the chain segments
between entanglements, accomplished
when conditions of delayed disentangle-
ment are present (i.e., during transient start-
up of simple shear flow), governs the kinet-
ics of the crystallization rather than the
molecular extension created under steady
state simple shear flow conditions. This
would imply that a strain requirement for
the shear flow-induced crystallization effect
would hold rather than a shear rate criter-
ion. Very broadly, the same picture is emerg-
ing from the works of Andersen and Carr
(1978), but in their case relating to steady
shear conditions.
Whether a total strain or a strain rate
requirement exists at the onset of flow-
induced crystallization of polymer melts in
simple shear flow remains unanswered.
Neveretheless, it is clear that in order to be
able to crystallize at temperatures where oth-
erwise no crystallization would be expected
in the quiescent state, a certain degree of
molecular extension must be achieved. Also,
when the time scale of straining is long rel-
ative to the time scale of disentanglement,
orientation relaxation will occur prior to
achieving a sufficient degree of molecular
extension for nucleation to become possible.
It thus seems that both a certain strain and
strain rate have to be present for shear flow
to induce crystallization. Further, it will
depend on the balance between the rates of
chain extension and nucleation. While rap-
idly crystallizing materials, such as polyeth-
ylene, may crystallize under conditions of
delayed disentanglement, slower crystalliz-
ing polymers will show an increasing ten-
dency to crystallize only under steady state
shear flow conditions.
 4.7 Oriented Crystallization in Stretched Networks
As already stated, the present section on
the effect of simple shear flow should only
serve as a pointer to the much wider litera-
ture on this particular subject. The point of
emphasis for the present article is that flow-
induced crystallization in dense systems
shows both the characteristics of dilute solu-
tions in elongational flow and those of chem-
ically cross-linked networks under uniaxial
extension. The latter will be addressed more
specifically in the next section.
4.7 Oriented Crystallization
in Stretched Networks
The study of the crystallization of net-
works on stretching is nearly as old as X-ray
diffraction and older than polymer science;
in 1925 Katz recognized that rubber can pro-
duce crystal X-ray reflections on stretching.
The orientation associated with stretching
induced crystallization, corresponding to
c-axis orientation, was consistent with a pri-
ori expectations. The emphasis at that time
was not on the orientation (which was taken
for granted), but on the specific feature that
stretching could induce crystallization in
systems which would not otherwise be crys-
talline at that temperature. In the tempera-
ture range where this occurred, stress-
induced crystallization was reversible: on
the removal of stress, crystallization is also
removed, i.e., the crystals melt and the elas-
tomeric sample shrinks back to its original
length. Crystallization of this kind leads to a
length increase at a constant load, or to a
reduction of the load at a constant length,
effects consistent with a priori expectations
as the chain, or chain portion, within the
crystal has a larger end-to-end distance than
in the oriented yet noncrystalline state.
None of the traditional studies on the
above phenomena were concerned with the
morphological aspects of the crystalline
235
structural elements arising on stretching-
induced crystallization of a network, nor did
they consider the possibility of orientations
other than chain (c-axis) alignment. The
present sections will deal briefly with these
two last-mentioned aspects, as they bear
directly on what has been said on flow-
induced structure formation in the forego-
ing parts of this article. The relevant works
fall into two categories developed indepen-
dently, practically simultaneously. The first
was on lightly cross-linked polyethylene,
and as such readily connects with the mate-
rial and examples in the rest of this article,
with which it is also in close relation histor-
ically. The second category relates to a par-
ticular type of electron microscopic study
on the crystallization of traditional elasto-
meric polymers, including natural rubber,
forming a class of its own not integrated into
either the mainstream of polymer crystal-
lization or that of conventional elastomer
research even though, as we shall point out,
it is highly relevant to both, raising some
core issues in polymer science.
4.7.1 Cross-Linked Polyethylenes
The origin of this subject is linked to the
research concerning the row structure and
related effects in Sec. 4.5. Polyethylene
(PE) when cross-linked, most conveniently
by irradiation, becomes a rubber in the mol-
ten state where it can be stretched and held
in the stretched state and where, at the
appropriate temperature, crystallization
will occur. In this way stretching induced,
hence oriented, crystallization can be fol-
lowed statically5 by X-ray diffraction and
other techniques.
5
Here and in the following by 'static' as opposed to
'dynamic' deformation we mean that, to a first approx-
imation, the macroscopic deformation is time inde-
pendent.
236 4 Flow-Induced Orientation and Structure Formation
Such a study was first carried out by Stein
and Judge (1961) as a function of sample
extension. They obtained a series of orienta-
tion patterns which were like Fig. 4-35 and
the ones in the sequence (c), (b), (a) in Fig.
4-38 with increasing chain extension. Clear-
ly this is the sequence arising in flow-induced
crystallization with increasing flow rate,
which at the time was leading to the morpho-
logical scheme in Fig. 4-37 including the row
structure. In the light of this it then appeared
that the whole subject could be studied in the
more readily accessible static manner instead
of conducting such an investigation dynam-
ically in the course of flow.
The above recognition was followed by a
series of coordinated morphological and dif-
fraction studies (including electron diffrac-
tion on thin films) using PE specimens light-
ly cross-linked by radiation (Keller and
Machin, 1967; Hill and Keller, 1969, 1971;
Hill et al., 1970). In fact it was in the course
of these investigations that the row structure,
postulated previously from X-ray diffraction
patterns alone, as obtained from melt-
extruded and commercial hauled-off films,
was confirmed and the full scheme of
Figs. 4-26 and 4-37 established. Figure 4-36
is in fact taken from these works. As seen,
the findings on flow-induced and stretching-
induced crystallization were meshing close-
ly, in fact they seemed undistinguishable as
regards both morphology and orientation
effects. In view of this, the intrinsic differ-
ence between them, namely that the materi-
al in the former consists of unconnected
molecules which can become displaced with
respect to each other, and hence can flow,
while that in the latter is a chemically con-
nected system which can extend but not flow,
has not been given any attention up till now.
Shish-kebabs, together with the underlying
fibrous crystallization, were recognized at
about the same time as originating from
flowing solutions. The conclusion on the ori-
gin of the core fibers arising from stretched
out molecules could then be readily carried
over to the row structure scheme, being con-
solidated at the time by the static experi-
ments on lightly cross-linked films. In fact
the following details fell neatly into line.
The time-dependent in situ X-ray diffrac-
tion on stretched melts held isothermally
always recorded a oaxis orientation pattern
first (which was reversible with extension)
followed, at low extensions, by the appear-
ance of the other orientations, such as, e.g.,
(e) and (f) of Fig. 4-37 in the later stages of
crytallization. This is fully consistent with the
sequential formation of core fiber and lamel-
lar overgrowth (Keller and Machin, 1967;
Hill and Keller, 1971). Further, when the sam-
ple was held freely and stretched by a con-
stant load, the sample length was observed to
increase and subsequently decrease (Keller
and Machin, 1967; Hill and Keller, 1969; Hill
et al., 1970); these two successive stages were
observed to be associated with the formation
of the two successive kinds of orientation.
This again was fully consistent with the antic-
ipated length increase on initial chain-extend-
ed crystallization with a sharp change in
behavior, manifest by contraction, when the
overgrowth formation occurred. Neverthe-
less, from our present viewpoint there is a
basic difference between the stretching out of
chains that are independent and those that are
part of networks, which should lead to corre-
sponding differences in their crystallization
and resulting morphology. We shall return to
this still open-endd issue again in Sees. 4.7.2
and 4.8.2.
4.7.2 Crystallization
of Traditional Elastomers
As already indicated, this subject has devel-
oped along separate lines, seemingly having
a life on its own. Here we try to link it up with
the mainstream subject of this review.
 4.7 Oriented Crystallization in Stretched Networks 237

Traditional elastomers, i.e., rubbers, are

polyenes, and hence unsaturated, which
makes them suitable to a particular metho-
dology which characterizes the whole class
of work under the present heading. Name-
ly, they react with heavy metal stain, which
by leaving the crystals unstained differen-
tiates between the crystals and the noncrys-
talline parts of the morphology in very high
contrast. In addition, when the stain (in
vapor form) is introduced in the course of
crystallization, it also arrests the crystalliza-
tion so enabling the morphology to be inves-
tigated at any selected stage. All these inves-
tigations relate to thin films and to their
examination on crystallization in the
stretched state under the transmission elec-
tron microscope.
This class of study was introduced by
Andrews (1964, 1966) and Andrews and
Reeve (1971) who found that rubber, when
crystallized under stress, has an electron
microscopically identifiable morphology of
a kind and on a scale that was at that time
totally unsuspected, as shown in Figs. 4-41
and 4-42 [the latter is from a later date
(Davies and Long, 1977)]. The full devel-
opment of the structures with increasing
extension is displayed schematically by Fig.
4-43. As is apparent, there are columns of
transverse lines. At first these were desig-
nated as fibers, but subsequently, with the
lamellar nature of polymer crystals gaining Figure 4-41. Thin film of cross-linked polychloro-
recognition at that time, the transverse lines prene crystallized under 100% strain at -5 C: (a) par-
were identified as edgewise projections of tially crystallized, (b) fully crystallized. Transmission
electron micrographs, OsO4 stained (Andrews and
lamellae confined to within the thickness of Reeve, 1971).
the films (in fact when the orientation
departs from the edge-on view the lamellar
nature of the entity becomes directly appar- visibility is variable (Fig. 4-42), it can in
ent). Clearly, all of this conforms with the some instances appear in surprisingly high
scheme of columns of parallel lamellae orig- contrast (Davies and Long, 1977). At high-
inating from a central line of nuclei, and er extensions the columns gradually become
hence with the scheme in Figs. 4-26 and the dominant and eventually, when closely
4-37. The central line only appears beyond spaced, the only visible structural elements.
a certain extension (Fig. 4-43). Even if its Clearly, this is again in line with the scheme
238 4 Flow-Induced Orientation and Structure Formation

Figure 4-42. Thin film of

polytrans-1,4-isoprene
strained 150% and partially
crystallized at 45.5 C
showing central threads.
Electron micrograph
(Davies and Long, 1977).

-100% strain

Figure 4-43. Schematic

diagram illustrating the
effect of prestrain on nucle-
ation and growth patterns in
a high polymer. The arrow
represents the direction of
applied strain (Phillips,
-400% strain 1990).

in Figs. 4-26 and 4-37 (even if by Andrews's
nomenclature - he refers to the fibers, when
profusely visible, as /-filaments - the over-
lap between the two schemes in Figs. 4-43
and 4-26 may not be complete). As they
stand, the structures revealed in this class of
work correspond mostly to the (b) side of
the range in Fig. 4-26, i.e., to parallel lamel-
lae and hence to c-axis orientation, which
makes them more closely allied to the shish-
kebabs than to the row structures as such.
Nevertheless, there are also well-document-
ed cases of twisting (e.g., Davies and Long,
1977) where, however, in their more flat-on

view the contrast and hence visibility of the
lamellae can become much reduced.
There has also been work on the kinetics
of structure formation in such elastomers
(Andrews and Reeve, 1971). Significantly,
the columns themselves (Andrews's /-fila-
ments) establish themselves very rapidly.
Most of the crystallinity development that
can be followed kinetically is associated
with the much more slowly developing
lamellar overgrowth (see Fig. 4-41 b). The
latter is unaffected by the level of strain and
corresponds to that of the spherulite of the
same material. Rather significantly, this
indicates that the material forming the
lamellae is unstrained - see Sec. 4.8.2. Here
we cannot survey this large subject area in
any detail. The salient point appropriate to
the present review is the close resemblance
between structure formation in stretched
networks and flowing melts, the latter being
the main subject of this review. As seen, the
former even includes the traditional elasto-
mers (rubbers), raising issues more appro-
priate to the elastomeric field but neverthe-
less, through their close resemblance, perti-
nent also to the main subject of this chapter.
From the traditional viewpoint of stretching
induced crystallization of rubbers, the dual
fiber-platelet morphology and the underly-
ing implication of respective chain-extend-
ed and chain-folded crystallization should
be particularly surprising, and especially the
scale of the structures and the scale of their
distribution in the sample. All of this implies
pronounced inhomogeneity in the structure
and the preceding stress distribution, a point
to which we shall return in Sec. 4.8.2.
4.8 Discussion
4.8.1 General Considerations
Even though further experimental,
including some practical, aspects will fol-
4.8 Discussion 239
low in Sees. 4.9,4.10 and 4.11, a discussion
of the material featuring so far may be
opportune.
In the preceding sections an overview was
given of structure formation in polymer
systems, as ensuing from orienting chain
molecules in their random state followed by
crystallization. This survey was presented
with an underlying theme, namely, that in
terms of the preceding chain conformations
there are only two structural elements: the
one arising from nearly completely
stretched out chains and the one from essen-
tially unoriented, random chains, these two
structure elements usually arising sequen-
tially. The various combinations of structur-
al elements are referred to collectively as
shish-kebab morphologies. Here the
strength of the orientation will affect the
number of core fibers formed but not, to a
first approximation, their overall orienta-
tion.
Concerning the initial, unoriented
system, four different physical states have
to be distinguished: (i) Dilute solutions,
where according to the present definition the
polymer concentration is below the critical
overlap concentration, and hence individu-
al chains cannot 'sense' one another. Con-
sequently, entanglements are absent, (ii)
Concentrated solutions, i.e., solutions at
concentrations above the critical overlap
concenration, in which case physical con-
tact points are present which, for the appro-
priate topology and even then only on the
appropriate time scale, may act as physical
entanglements. Such entanglements appear
and disappear in steady state equilibrium,
their number being dependent on the poly-
mer concentration and temperature, (iii)
Melts, which are similar to concentrated
solutions, i.e., the entanglement points are
physical and temporary and hence are form-
ing and disappearing but are, within the
steady state, present in much larger num-
240 4 Flow-Induced Orientation and Structure Formation
bers. (iv) Cross-linked networks - in this
case both fixed chemical junction points and
temporary physical entanglements are
present, our emphasis here being on the for-
mer.
Concerning the mechanism of the under-
lying chain extension, the material is most
readily subdivided according to the method
by which the chains are extended. Depend-
ing on the consistency of the system, chain
extension can essentially be achieved in two
ways:
(1) Static extension - in this case the
material is stretched and kept in this state
until crystallization results. The prerequi-
site for crystallization is the retention of
orientation, which is normally associated
with the absence of stress relaxation on the
time scale of the crystallization process.
This is satisfied by the networks of cross-
linked systems where the ensuing crystal-
lization corresponds to the familiar stress-
induced crystallization effects of elasto-
mers. In the case of static deformation, we
shall confine ourselves to extensional de-
formation for the purposes of this discus-
sion.
(2) Dynamic extension - in this case chain
extension and ensuing crystallization is
induced by flow, a situation in which the
material response is time-dependent and
most importantly, where in a given flow
Table 4-1. Interchain relations and modes of deformation under which shish-kebab morphologies have been
observed.
Interchain relation
Dilute solution
Concentrated solution
Melt
Cross-linked network
a
By our definition, in concentrated solutions the chains interact; b n.a. = not applicable by our definition.
region continuous material renewal takes
place. In the discussion to follow, both elon-
gational and simple shear flow types will be
considered.
4.8.2 On the Circumstances
of Shish-Kebab Formation
and Its Implications
It is well known that depending on the
mode [(1) or (2) above] and on the strength
of the deformation, the systems [(i-iv)
above] may display rheological behavior
that is distinct for each mode and each
system. Yet in spite of these differences and
rather unexpectedly by any a priori consid-
erations, both dilute and concentrated solu-
tions, as well as melts and cross-linked net-
works, are observed to produce closely sim-
ilar morphologies which are all within the
shish-kebab family (see Table 4-1).
Table 4-1 also refers to cases not includ-
ed in the foregoing. Of these, mentioned
here separately is shish-kebab formation in
sheared isotactic polystyrene, which has
subsequently been vitrified (Petermann
et al., 1979; Dlugosz et al., 1972; Grubb and
Keller, 1974). In such cases central core
fibers can be conspicuously visible in high
contrast (Dlugosz et al., 1972). The forma-
tion of such structures in these cases is most
remarkable in view of the relatively low
Mode of deformation
Dynamic Static
Elongation Shear Extension
yes no
yes yes a
yes yes n.a.
n.a.1 n.a.b yes

(several hundred percent) macroscopic
strains involved.
In all cases in Table 4-1 for crystalliza-
tion to occur a certain molecular strain
requirement must be satisfied. In molecular
terms this means a level of chain extension,
parallel to the direction of principal defor-
mation, such as leads to the formation of
fibrous (as opposed to lamellar) crystals. In
most cases the actual molecular strain
involved is unknown and it cannot be mea-
sured directly. Possible attempts to calcu-
late the molecular strain from the macro-
scopic strain imposed would require either
exact mapping of the flow field present, or
assumptions as regards the homogeneity of
the deformation, specifically, that the de-
formation proceeds affinely down to the
molecular level.
Next, the particulars of the various com-
binations of system and modes of deforma-
tion depicted by Table 4-1 will be briefly
summarized. Attention will be focused on
the formation of the fibrous crystal and the
underlying mechanism of chain extension.
For this purpose the distinction between
static and dynamic extension in Sec. 4.7.1
will be taken up further and extended so as
to include physical entanglements.
With regards to the number and nature of
entanglements, two extreme cases can be
distinguished in Table 4-1, namely dynam-
ic extension in dilute solutions and static
extension in chemically cross-linked net-
works. As the chains cannot sense one
another, and hence entanglement points
must be absent, in the former, while they are
permanent in the latter, the mechanisms of
formation of shish-kebab crystals in these
two cases must necessarily be different.
For dilute solutions, formation of the cen-
tral core relies on the forces imposed by the
fluid, so causing the chains to stretch out
almost fully, thus forming the backbone
(shish) of the shish-kebab morphology.
4.8 Discussion 241
Here the strain requirement is met by the
presence of a stagnation point such as is the
case, e.g., in the opposed jet apparatus.
At the other extreme, with static exten-
sion in the cross-linked network, the forma-
tion of shish-kebab morphologies relies on
the straining of chain segments between
entanglement points that are regarded as
fixed, including, in addition to chemical,
also temporary physical cross-links on the
appropriately short time scale. According-
ly, it will be the shortest links between these
fixed entanglements that become loaded and
stretched out first. As the deformation of
elastomers can only be imposed in a static
fashion (i.e., to a first approximation rub-
bers do not flow), in this case only a strain
requirement exists (see Fig. 4-43). In this
respect it is important to note that in rubbers
the usually studied stretching induced crys-
tallization effects are reversible: on remov-
al of the external force the crystals 'melt'
and the network rearranges to the situation
present prior to loading. Most theoretical
approaches to calculate the molecular strain
presume proportionality between the mac-
roscopic deformation and the molecular
strain, i.e., affine deformation [see, e.g.,
Treloar (1958)]. If this is the case, on stress-
ing, nuclei would form randomly through-
out the sample. Morphological observations
(Sec. 4.7.2) show, however, that crystalliza-
tion propagates along specific, relatively
widely spaced and sharply defined path-
ways. It is difficult to envisage how such a
clearly delineated propagation would result
from a homogeneous stress distribution as
presumed by the traditional models. It
appears that an (initially) inhomogeneous
stress distribution is present. Further, the
stress-induced shish (i.e., fibrous) crystals,
once formed, would lead to stress relief
along the direction of propagation, thereby
dispersing the load over a larger area, and
hence this would terminate rather than pro-
242 4 Flow-Induced Orientation and Structure Formation
mote continuing crystal growth along the
same path. Thus the formation of long, line-
shaped nucleus crystals separated by micro-
scopic distances raises basic questions, not
only about stress-induced crystallization,
but also about the stress distribution preced-
ing crystallization. If we now add that, as
evidenced by subsequent lamellar kebab
formation, all the material in between the
shish must essentially be unstressed (recall-
ing Sec. 4.7.2, specifically Figs. 4-41 and
4-42), we note that the possibility of gross
stress inhomogeneities arises, an issue that
should also be of concern to the whole sub-
ject of rubber elasticity.
With regards to the mechanism of forma-
tion of a shish-kebab morphology, the
remaining systems in Table 4-1 must corre-
spond to behavior intermediate between the
two extremes of dilute solutions and cross-
linked networks. More specifically, depend-
ing on the solution concentration, the type
of flow (i.e., extensional or simple shear
flow), and the strain rate, a coil stretch
transition will or will not occur, the condi-
tions for which are exemplified by Figs.
4-10 and 4-11 in Sec. 4.2, and which will be
briefly recalled in the following.
The distinction between Figs. 4-10 and
4-11 is basic for our appreciation of what
happens in the melt. As stated at the end of
Sec. 4.2.3.2, if the conditions of Fig. 4-10
pertain the chains can, by a coil > stretch
transition, become practically fully extend-
ed for all concentrations up to and includ-
ing the melt within the strain rate interval
n - c , which even if narrowed down and
shifting to low strain rate values remains
finite and positive [case (1)]. On the other
hand, the conditions represented by Fig.
4-11 imply that the strain rate interval of full
chain stretchability becomes zero at the con-
centration corresponding to the crossover
[case (2)]. The situation beyond the cross-
over, which includes the single component
melt, will necessarily pertain to chemically
cross-linked systems, but whether it also
pertains to uncross-linked systems remains
an open-ended question. If so, it would mean
that, owing to entanglements, a highly vis-
cous melt can sustain sufficient stress to dis-
play the characteristics of a cross-linked
elastomer, while itself remaining in a con-
tinuing state of elongation, i.e., flow (until
flow ceases due to solidification in the case
where the conditions for crystallization
apply). The time-scale (hence strain rate)
dependence will still pertain, namely, that a
threshold strain rate will have to be reached
first, which in this case is n, i.e., the strain
rate at which the chains begin to 'grip' each
other and thus where the mechanically
active entanglements begin to arise. As
shown by Fig. 4-11 ate 1 (i.e., in the melt)
n < c; the critical strain rate (c) for a coil
> stretch transition cannot be reached
before the network response begins.
Relating to alternatives of cases (1) and
(2) to shish-kebab formation, the shish
could then be compounded either by chain
segments stretched out between entangle-
ment points as in case (2) (such should be
the situation for very concentrated solutions
and melts in shear flow - see below), or if
case (1) applies, it would consist of fully
stretched out chains.
There are a number of experimental
observations that make a strong point for a
coil stretch transition also occurring in
the melt: (i) Experiments carried out using
a single jet and solid obstacles demonstrat-
ed the effectiveness of elongational flow at
producing fibers, and specifically the role
of a stagnation point and a lower limit in the
effective strain rate (Sec. 4.4.3). (ii) A two-
fold criticality between the molecular
weight (A/) and the strain rate, which is char-
acteristic of the coil stretch transition in
dilute solutions, seems to also be present for
the formation of fibers in the melt, (iii) Cor-

roborating (ii), it has been observed that the
addition of only a minute amount of ultra-
high M material significantly promoted
fiber formation (Bashir et al., 1984), sug-
gesting that a cut-off in M is operative at the
high end tail, a feature previously found to
pertain also for the formation of fibrous
crystals in dilute solutions.
The above observations were all made
using some version of the jet flow metho-
dology. As the total strain and the strain rate
cannot be varied independently, these
experiments cannot be conclusive as to
whether a strain rate or a total strain require-
ment is pertinent to the onset of fibrous crys-
tallization in flowing concentrated solutions
and melts. Clearly, a strain requirement
would hold for both a coil stretch and a
cross-linked network-like mechanism of
shish-kebab formation, while a strain rate
criterion would only be present for a coil >
stretch transition. In order to decide which
mechanism is operative, experimental data
from a set-up where the strain rate and the
total strain can be varied independently are
clearly invited. This is a long recognized
need (Lagasse and Maxwell, 1976), which
to our knowledge is unrealized so far.
The formation of shish-kebab morpholo-
gies in shear flow should rely entirely on the
presence of entanglements to achieve the
chain extension required for the creation of
the core fiber. Therefore, in dilute solutions
under shear flow conditions, shish-kebab
crystals have never been observed. [In fact,
the formation of fibrous crystals in the
Couette apparatus by Pennings's original
experimentation technique did not rely on
shear flow (the laminar flow between two
concentric cylinders), but on elongational
flow between Taylor vortices occurring
beyond a certain flow velocity (Pennings
et al., 1970).] The number of entanglement
points (entanglement density) thus plays a
decisive role. As pointed out repeatedly in
4.8 Discussion 243
the present article, this entanglement den-
sity is not uniquely related to the topologi-
cal chain overlap per se, but also to the time
scale of the molecular contact and thus in
addition to the temperature (Brownian
motion) and the rate of deformation
imposed (including the differences between
the start-up of flow and steady state condi-
tions).
On coming to fiber formation, the above
deformation rate determined time-scale
dependence needs compounding with that
of the crystallization process. Depending on
the rate of nucleation, it has been hypothe-
sized that crystallization may occur both
under transient flow conditions, i.e., after
start-up an overshoot in the stress is
observed corresponding to a state of high
entanglement density, and under steady
state conditions (i.e., when the entangle-
ment density is constant in a kind of dynam-
ic equilibrium). More about crystallization
in shear flow will be said in the following
chapter in this Volume.
4.8.3 A Special Case of Chain Extension:
Adsorbed Molecules
As opposed to elongational flow, in sim-
ple shear flow there can be no sharp coil
stretch transition (de Gennes, 1974). Nev-
ertheless, a special situation arises, even in
the case of simple shear flow, when the
molecules are anchored (adsorbed) to a solid
wall. This situation can be treated mathe-
matically as a kind of 'quasi-elongational'
flow. As predicted by Brochard and de
Gennes (1992) and confirmed by experi-
ment (Migler et al., 1994), chains of equal
length constituting a so-called 'weak brush'
may undergo a sharp transition from an
entangled state to one in which the anchored
molecules become disentangled from the
bulk. This process, which takes place at a
critical value of stress, is accompanied by a
244 4 Flow-Induced Orientation and Structure Formation
sharp increase in the slippage velocity in a
boundary layer at a short distance from the
solid boundary [referred to as a 'marginal
state' in Brochard and de Gennes (1992)].
Within and beyond this marginal state fur-
ther chain extension can take place, but now
being disentangled from the bulk, not
through the action of entanglements, but as
imposed by monomeric frictional forces.
The whole issue of the potential role of
molecules at or close to the surface will be
raised again in specific terms in Sees. 4.10.2
and 4.10.3.
The macroscopic orientation effects dis-
cussed so far all rely on the presence of com-
paratively strong flow fields or, in the case
of cross-linked networks, on relatively large
static extensions. Under certain circum-
stances macroscopic orientation effects can
also arise in weak flows or even in the
absence of flow. It is to the latter kinds of
orientation effects, which are related to the
alignment of supramolecular structural
entities (and not directly to that of chain
molecules), to which we turn next.
4.9 Orientation Due to the
Alignment of Supramolecular
Structure Entities
4.9.1 Orientation in Weak Flows
If the flow is too weak to extend the
chains, it may still lead to macroscopic
orientation by aligning larger scale structur-
al entities, themselves resulting from the
crystallization of unextended, random
chains, also influencing the direction of
their continuing growth. The entities
involved are of course the lamellae and still
larger scale units arising therefrom. Lamel-
lar reorientation is known to be one feature
in the early stages of solid state deformation
of the already solidified material under
some specific circumstances (e.g., Keller
and Pope, 1971). However, we shall restrict
ourselves here to cases that are associated
with the primary crystallization process tak-
ing place in deforming or flowing melts.
Lamellae growing in a flowing (deform-
ing) melt will tend to align with their lamel-
lar planes parallel to the flow (deformation)
direction. In view of the fact that in chain-
folded lamellae the chain direction is per-
pendicular, or at a specific large angle to the
lamellar surfaces, the sample (as a whole)
will display an orientation in which the
chains are perpendicular, or at a specific
large inclination, with respect to the flow
direction. Such, by conventional expecta-
tions, highly anomalous orientations feature
frequently in the literature. They may also
be due to other causes (see below), but in
many instances they are attributable to flow-
induced lamellar alignment. In addition to
the alignment of the basal planes, it will be
the most elongated and hence fastest grow-
ing lateral crystal direction that, in general,
will become parallel to the flow, i.e., the
direction that is normally radial in a spher-
ulite (e.g., b in polyethylene - see Fig.
4-24). It follows that the macroscopic orien-
tation displayed by such a sample will be
equivalent to that along the radius of a
spherulite. A corresponding X-ray diffrac-
tion pattern (in this case from a nylon) is
shown in Fig. 4-44. This situation was real-
ized early on by one of us, even before the
lamellar nature of the basic crystal entity
was recognized (Keller, 1956). Identifica-
tion of the effect with preferential lamellar
alignment in the flow direction soon fol-
lowed (Keller and O'Connor, 1957) after the
discovery of chain-folded lamellar crystals
from solution. In fact the latter was the first
(at that time debated) inference that the
novel findings for crystallization in solu-
tions have counterparts in the less readily
accessible crystallization from the melt.
 4.9 Orientation Due to the Alignment of Supramolecular Structure Entities
Figure 4-44. X-ray diffraction pattern of a nylon 6.6
filament solidified during weak flow while exuding
unconstrained from an extruder (Keller, 1956). Flow
direction vertical.
This line of reasoning was well substantiat-
ed by later events and is pursued further in
this chapter (Sec. 4.9).
The pattern of alignment of growing
lamellae and that of the resulting larger
entities is best illustrated by the compara-
tively recent case of polyphenylene-ether-
ether-ketone (PEEK) polymer. Here a
sequence of X-ray orientation patterns, both
wide and low angle, and the development of
birefringence could be successfully
accounted for by the scheme in Fig. 4-45, as
briefly described in Waddon et al. (1988)
and Blundell et al. (1989), and given in
detail by Waddon (1988). Figure 4-45 (i)
represents the lamella with both basal planes
and the long and hence fastest growing
direction, b, parallel to the orienting influ-
ence (vertical). With random orientation
around the flow direction, the macroscopic
orientation (as indeed observed) corre-
sponds to a /?-axis fiber pattern (with the
chains, i.e., the c-axis, perpendicular),
which is similar to the orientation along a
spherulite radius (Waddon et al., 1987). In
245
ii)
iii)
Figure 4-45. Structure formation under very weak
flow where the influence of the flow is only to orient
the lamellae in various stages of branching/sheaving
in the course of their development towards a spher-
ulite, and does not otherwise affect the formation of
the lamellae themselves (which is the same as in the
stationary state). The present figure shows the scheme
as established for the polymer PEEK (which, amongst
others, displays a characteristic 'cartwheel'-like
morphology intermediate between the sheaf and the
spherulite). Development of a lamella (i), into a sheaf
(ii), then into a cartwheel (iii), where the 'axle' is the
crystallographic a axis. [Out of plane sheaving beyond
(iii) would then lead to a spherulite.] Flow direction
vertical (Waddon et al., 1988).
the course of continuing growth, the lamel-
lae will branch as in (ii) leading to the
'cartwheel'-like structure as in (iii), which
corresponds to randomization around a. The
randomization of this carthwheel around the
flow direction (vertical) - the cartwheels are
present in all orientations with their axles
(i.e., a) normal to the flow direction - results
in the overall orientation actually observed
at that stage of crystal development, as is
deducible by pole figures analysis (Waddon
246 4 Flow-Induced Orientation and Structure Formation
et al., 1988; Blundell et al., 1989; Waddon,
1988). Full development of the final spher-
ulite leads to total overall randomness.
However, as PEEK can be quenched into the
glassy state, any of the intermediate stages
of crystal development can be preserved
within the final sample, and with it the mark
they leave on the macroscopic sample orien-
tation. Further, the range of structure units
can be preserved in the fully crystallized
sample even without any intervening pre-
mature quenching pending on the nucleation
density. Namely, if there are many nuclei,
and hence the growing entities are closely
spaced, this development will be arrested by
mutual impingement, and, depending on the
stage at which this impingement occurs in
the sequence (i) - (iii) (and beyond towards
a full spherulite), the corresponding orien-
tation will remain imprinted on the macro-
scopic sample. Indeed, upon increasing the
nucleation density (by self-seeding), the
opposite orientation sequence (iii)-(i) (i.e.,
the reverse to the crystal development pur-
sued above) was obtained in agreement with
expectations (Waddon et al., 1988; Blundell
etal., 1989; Waddon, 1988).
Thus we have essentially two levels of
morphological entity that can become
aligned, the lamella and the cartwheel6,
with all intermediate splay stages in be-
6
The 'cartwheel' needs some comment. Such entities
have been identified by Lovinger and Davis (1985) as
specific to PEEK. We regard them as a form of the
familiar sheaves, leading to spherulite formation in
which the branching of the lamellae is more confined
to a plane than usual. Or rather, that the randomiza-
tion around the sheaf axis (vertical b in Fig. 4-45),
which normally occurs before the sheaf closes up on
itself, is here delayed until after sheaf closure, i.e.,
until after the randomization around the normal to the
sheaf axis, here a, is complete. Accordingly, there
should be no difference in the overall pattern from
what is normal, but merely in the relative degree of
sheaving in different directions for reasons that must
lie in the specific nature of this particular polymer.
tween. The above example on PEEK there-
fore illustrates the orientability of large
scale morphological entities in different
stages of their own structural hierarchy.
4.9.2 Orientation in the Absence of Flow
Macroscopic orientation can arise even
without any flow, due to the selection of the
primary crystal growth direction being
brought about by other causes. This can lead
to orientations that are indistinguishable
from some of those mentioned above.
Therefore their appreciation is essential for
any attribution of orientation effects of the
kind under discussion to flow or deforma-
tion, in addition to the fact th^t such spon-
taneous, purely growth-generated orienta-
tion effects are of interest in their own
right.
One way such oriented growth without an
externally imposed orienting influence can
arise is through a thermal gradient coupled
with movement of the sample in a direction
opposite to that of the crystal growth, with
a velocity matching that of the growth of the
crystal. In the case of polymers, this meth-
od, which is equivalent to that of growing
single crystals of simple substances in zone-
refining experiments, leads to unidirection-
al spherulite-type growth along the moving
temperature gradient. The resulting macro-
scopic orientation corresponds to that along
a spherulite radius. The method was intro-
duced by Seto and coworkers (Tanaka et al.,
1963) and has been followed up by numer-
ous workers since. Figure 4-46 is one exam-
ple of an attempt to prepare such a unidirec-
tional spherulite sample in a controlled man-
ner (Lovinger and Davis, 1985). The result-
ing macroscopic orientation is clearly iden-
tical to that arising from lamellar alignment
due to weak flow, i.e., corresponding to
stage (i) in the scheme of Fig. 4-45, leading
to X-ray diffraction patterns such as in
 4.9 Orientation Due to the Alignment of Supramolecular Structure Entities
Figure 4-46. Oriented banded spherulites in nylon
6.12 directionally solidified. Polarizing micrograph,
crossed polars (Lovinger and Gryte, 1976).
Fig. 4-44 for the appropriate polymer, even
if the ultimate underlying cause is basical-
ly different.
Another source of oriented growth arises
from nucleating surfaces (transcrystalliza-
tion) and from alien fibrous inclusions that
nucleate crystallization (the nucleating abil-
ity of which could involve epitaxial
growth). An example, a common occur-
rence in fibrous polymer composites with
thermoplastic matrices, is shown in Fig.
4-47 (Waddon, 1988; see also Chapter 8 in
Volume 13 of this Series). Here and in many
similar other cases [e.g., for polypropylene
in Varga (1992) to quote a salient recent
work], closely spaced nuclei confine spher-
ulitic growth to directions normal to the
nucleating fiber, so leading to the equiva-
lent of two-dimensional spherulites with the
spherulite planes normal to the nucleating
fiber direction. Such an assembly is clearly
equivalent to the flow orientation-induced
row structure of Fig. 4-37 c (discussed in
length in Sec. 4.5.5.2), except that here the
nucleating entity is not a polymer but an
alien body, and no chain stretching is
involved in its formation. Orientation may
nevertheless play a prominent part, not by
stretching chains but by aligning the fiber
component of the fibrous composite. In such
247
Figure 4-47. PEEK-C fiber composite with transcry s-
talline structure arising through spherulite nucleation
along the C fiber. In this instance cleavage along the
columnar interfaces is also displayed. Polarizing opti-
cal micrograph, crossed polars (Waddon et al., 1987).
an oriented fiber composite, a macroscopic
orientation will arise that is indistinguish-
able from the row structure of the corre-
sponding polymer (e.g., polyethylene will
give an X-ray diffraction pattern as in
Fig. 4-35). In addition to the effect of the
morphology on the orientation, Fig. 4-47
also contains an instructive demonstration
of fracture along the column boundary, and
hence of the influence of the morphological
hierarchy on the macroscopic properties.
Finally, orientation by directional growth
can arise due to special constraints (as in the
familiar capillary method of single crystal
production in the crystal growing practice
of simple substances). A particularly
instructive and potentially significant situ-
248 4 Flow-Induced Orientation and Structure Formation

carbon fibres

x nucleation site

(a) (b)
Figure 4-48. Diagrammatic representation of two possible spherulite morphologies resulting from constrained
growth in thermoplastic composites. Depending on the nucleation density along the fibers and on the fiber sep-
aration distance, two different, mutually orthogonal growth directions may arise, imparting the corresponding
orientations to the macroscopic sample (Waddon et al., 1987).

ation can arise in fibrous composites, again
exemplified by experience with PEEK. Fig-
ure 4-48 should serve to convey the princi-
ples involved. In (a) we have carbon fibers
that nucleate the crystallization leading to
two-dimensional spherulite development,
i.e., the row structure analog discussed in
the preceding paragraph. If the carbon fibers
are not strongly nucleating (a factor depen-
dent on the preceding surface treatment),
they will merely act as a confinement to nor-
mal spherulite growth occurring in the spac-
es between them (as in Fig. 4-48 b), sporad-
ically along the fiber surface or also within
the confined melt interior. If, in addition,
they are closely spaced, the overall spher-
ulite growth direction will tend to be par-
allel to the fiber constituent of the compos-
ite. If the fibers are all parallel, as they usu-
ally become under the weak orienting influ-
ence of the technological processing
involved, there will be an overall orienta-
tion in the macroscopic sample. Note that
this orientation is different, in fact exactly
opposite as regards the dominant crystallo-
graphic growth direction for the two alter-
natives (a) and (b) in Fig. 4-48. The deter-
mining factors are the nucleating ability and
the separation of the fibers (hence the load-
ing of the composite). The above situations
have in fact become pertinent for technolog-
ical situations (Blundell et al., 1989) where,
in addition, a combination of weak flow-
induced crystal orientation (in the sense of
Fig. 4-45) and directional crystal growth, as
influenced by nucleation and confinement
(Fig. 4-48), were found to be operative.
4.10 The Effect of Structure
on Rheology: The 'Extrusion
Window' in Polyethylene
4.10.1 Introduction and Basic Features
of the Window Effect
So far we have been concerned with the
consequences of flow-induced chain exten-
 4.10 The Effect of Structure on Rheology: The 'Extrusion Window' in Polyethylene
sion on the crystal morphology of the solid-
ified sample, and through them, the type and
strength of orientation in the final product.
Now we turn to a further aspect of the inter-
play between flow and structure formation,
namely modification of the flow pattern
through the presence of structures previous-
ly created within the flow field.
A situation where flow-induced struc-
tures can give rise to a change of the flow
field was introduced earlier in the discus-
sion on flow-induced crystallization effects
in the opposed jet apparatus and in connec-
tion with shish-kebab formation (Sees. 4.3.3
and 4.4.3). To recapitulate, the presence of
fibrous crystals within the orifice could lead
to a change of the local velocity gradient at
the solid growing tip of the fiber (Keller and
Mackley, 1974; Machley, 1975 a, b), there-
by generating an accelerating elongational
flow component which, in turn, could give
rise to further stretching out of the chain
molecules.
In the following we shall describe
another, recently discovered example of
how flow-generated structures can react
back on the flow itself, in this case creating
a major, macroscopically registered rheo-
logical effect in the capillary flow of high
molecular weight (M) polyethylenes (PEs).
This anomalous effect is part of the broad-
er subject area discussed in the foregoing
(Sec. 4.4), namely, melt flow not too far
above the solidification point of the poly-
mer - in this case polyethylene. This has
been reported in several publications (Wad-
don and Keller, 1990, 1992; Narh and Kel-
ler, 1991a, b; Kolnaar and Keller, 1994,
1995; Kolnaar, 1993) [it also features in a
publication from a different source but is not
followed up there (Titomanlio and Marruc-
ci, 1990)], and involves a specific singular-
ity in the extrusion behavior occurring with-
in a narrow temperature interval of 1 - 3 C
around 150 C, which does not follow in any
249
predictable way from conventional rheolo-
gy. It involves reduced flow resistance cou-
pled with the absence of extrudate distor-
tions, and utilization of the effect may offer
practical advantages in processing. The
anomaly itself we attribute to chain exten-
sion and chain extension-induced phase
transitions.
In the case of linear polyethylene, solid-
ification (crystallization) occurs between
120 and 130 C on cooling, depending on
the cooling rate, while on heating a solidi-
fied product melting occurs at 132-136 C
(practical melting point) with the maximum
(theoretical) melting point generally held to
be 145 C (see, e.g., Flory and Vrij, 1963).
Conventional melt processing is usually
conducted at much higher temperatures, i.e.,
160 C and above, to avoid any possible
interference of the solid state with the melt
flow (for this and the foregoing see the anno-
tated temperature scale of Fig. 4-49). In
contrast, the subject matter of present con-
cern is melt flow within the range at which
such an interaction can occur, not only
because of its intrinsic scientific interest,
but also because processing at these lower
temperatures can be advantageous, either by
virtue of the melt properties or by that of the
properties of the resulting solidified prod-
uct. This is the temperature region of the
pioneering works by van der Vegt and Smit
(1967) on elongational flow-induced crys-
tallization. The central point of these works
was essentially rheological. In subsequent
works, taking up the above theme, the
emphasis shifted to the structure and prop-
erties the extrudate (Southern and Porter,
1970; Porter et al., 1975). Subsequent
works (Bashir et al. 1984, 1986; Keller
and Odell, 1978; Odell et al., 1978) contin-
ued to focus on the resulting extrudate,
'fine tuning' the morphology by what may
be termed 'micro-morphological engineer-
ing'.
250 4 Flow-Induced Orientation and Structure Formation
QUIESCENT FLOW
k
* NORMAL *
160C | PROCESSING {
FLOW
INSTABILITIES
152C
EXTRUSION WINDOW
150C
145C
SOLIDIFICATION
MELT
T -~132C
CRYSTAL
Figure 4-49. Temperature scale for melt flow of lin-
ear polyethylene in a capillary extruder. The scale on
the left relates to the quiescent state (Tm = practical
melting temperature; T^ = theoretical melting point of
an infinite crystal). The scale on the right applies to
the melt flow, which leads to solidification, and dis-
plays the 'extrusion window' (Kolnaar and Keller,
1995).
More recent works reverted to the reex-
amination of melt flow properties, that is to
rheology, at or just before the stage at which
the above-mentioned structures started
forming. A new, unexpected phenomenon
(Waddon and Keller, 1990, 1992; Narh and
Keller, 1991 a, b; Kolnaar and Keller, 1994,
1995; Kolnaar, 1993) arose in the course of
these investigations, to be described and
pursued in what follows. The experiments
quoted again involved a capillary rheome-
ter consisting of a converging die entry (see
Fig. 4-28) followed by a capillary, used
either as a viscometer to measure the melt
flow properties or as an extruder for obtain-
ing an extrudate.
For the effects to be observed, the capil-
lary rheometer is operated at a constant pis-
ton velocity (v), measuring the extrusion
pressure (p) as a function of temperature (I).
Here v relates to the shear rate at the capil-
lary wall, most readily expressed as an
'apparent wall shear rate' yA, where
7A = (4-5)
nR'
with Q being the material throughput per
unit time, which is proportional to v. R is the
capillary radius and the ratio ply A relates to
the apparent flow resistance, and hence the
apparent melt viscosity7.
The key effect, the basis of what follows,
is shown in Fig. 4-50. Here, just as in the
first experiments leading to the discovery
of the effect in question (Waddon and
Keller, 1990,1992; Narh and Keller, 1991 a,
b), comparatively high M material
(M=10 5 -10 6 ) was used, such as may dis-
play several kinds of extrudate distortion
and unsteady flow at the usual processing
temperatures (i.e., at 160 C and above).
However, rather surprisingly, at lower
extrusion temperatures, between the tem-
perature at which solidification of the flow-
ing polymer leads to blockage and roughly
152 C, the flow becomes steady. The pres-
sure displays a pronounced minimum with-
in a narrow temperature interval of
150-152C (Fig. 4-50). The singularity of
the 'window effect' is even more strikingly
apparent from the appearance of the extru-
date. For the high Ms in question, and for
practicable values of v (i.e., yA), the extru-
dates display nonuniformities and gross dis-
tortions of various kinds under the usual
processing conditions (see, e.g., Vinogra-
7
As we shall be concerned with anomalous flow con-
ditions at which rheological correction schemes such
as the Rabinowitsch-Weissenberg correction lose
their validity, the apparent yA values will not be cor-
rected to obtain the real shear rates (y). Qualitatively,
it follows that an increase in v will have the result of
increasing fA, f, and hence e.
 4.10 The Effect of Structure on Rheology: The 'Extrusion Window' in Polyethylene
15
start
smooth
oscillations
10
CO
145 150 155
temperature (C)
Figure 4-50. Pressure vs. temperature trace recorded
during heating at a fixed extrusion rate showing the
pressure minimum associated with the extrusion win-
dow. The vertical arrows denote pressure oscillations
[v= 1.25 mm min"1 (yA= 1.89 s"1), heating rate= 1 C
min"1, M=4.4xlO5] (Kolnaar and Keller, 1995).
dov et al., 1972). Several of these are absent
within the T window where the extrudate is
smooth. Figure 4-51 illustrates the effect in
terms of a photograph of an extrudate where
the temperature was raised during extrusion.
The smooth region corresponding to the
extrusion temperature of -150 C, in con-
trast to the gross distortions of various kinds
both below and above this temperature
should be strikingly apparent. The effect is
reversible with temperature (Narh and Kel-
ler, 1991 a); it takes place both on heating
and on cooling. Nevertheless, this rever-
sibility is not quite unconditional (Narh
and Keller, 1991a): the p minimum at
150-152 C always appears on heating, but
not always, and not always in the same
strength (i.e., the same magnitude of the p
drop) on cooling. Namely, if on completion
of a given heating run cooling starts imme-
diately after the highest T (~180C) is
251
Figure 4-51. Photograph of extrudate obtained dur-
ing a heating run corresponding to the pressure vs.
temperature trace of Fig. 4-50. Barrel wall tempera-
tures are indicated (Kolnaar and Keller, 1995).
reached, the window effect usually reap-
pears with the same strength on cooling. In
contrast, if the system is held at that high-
est temperature (e.g., 180 C) for some time
and the pressure is allowed to decay to zero,
the window effect may not reappear after-
wards. Similarly, if a cooling run is started
from the high Tend (e.g., 180C), without
a preceding heating run, depending on the
extrusion rate the window may or may not
appear. As recognized in Narh and Keller
(1991 a), this 'conditional' reversibility has
all the hallmarks of a memory effect, name-
ly, that a particular structure ('phase' - see
below) is created by the flow which is
responsible for the window effect. This
always happens on heating, but needs to be
nucleated on cooling, a process much aided
if some memory of the structure still exists.
Accordingly, storage at an elevated temper-
ature before cooling starts could erase this
memory effect, and of course in the absence
of any previous heating run such memory
would be altogether nonexistent. In either
case, renucleation of the structure in ques-
tion would be required. This view has been
confirmed by ongoing works since, where it
was found that even when considering heat-
ing runs only, the 'strength' of the effect
(i.e., the depth of the p minimum) increas-
252 4 Flow-Induced Orientation and Structure Formation
es on repeated heating runs (Kolnaar and
Keller, 1994).
To sum up (at this stage), we have the rath-
er surprising effect that material that would
conventionally be unprocessible at such low
extrusion temperatures becomes potentially
processible at temperatures below those
used in conventional technological practice,
with a narrow temperature window of min-
imum flow resistance ('extrusion window').
Thus, in the heating experiment, the oscil-
lations are absent up to the upper edge of the
window, at which stage they first appear (see
Fig. 4-50). In the reverse experiment on
cooling they are present to begin with but
disappear when the upper edge of the win-
dow is reached. Cooling through the T
region of the window approaches the con-
ditions for solidification. This is the region
leading to the various fiber-platelet mor-
phologies and eventual blockage of the flow
through massive solidification into a pre-
dominantly fibrous, crystalline structure.
When this occurs the pressure is rising, as
is to be expected (the increase in p with
decreasing T eventually swinging up
towards infinity when the flow stops; this is
seen best in Fig. 4-52 to feature below). In
spite of this increase in p with decreasing T
on crystallization, the p vs. T trace remains
smooth compared to the oscillations at the
high T side of the window. This would also
apply to the appearance of the extrudate if
it were hauled off at sufficient speed. If this
is not done, there is pronounced die swell
on exit, particularly at Tbelow the window;
hence the extrudate again becomes grossly
nonuniform, as is conspicuously apparent
from Fig. 4-51. In the window itself die
swell is again at a minimum, displaying the
special advantage of the window condition
(Wadden and Keller, 1990; Kolnaar and
Keller, 1994). Die swell reappears at T
above the window minimum (Kolnaar and
Keller, 1994), but compounded there by var-
OH
en
w
145
temperature (C)
Figure 4-52. Pressure vs. temperature traces for
increasing apparent wall shear rates showing the onset
of the extrusion window. From bottom to top:
j A = 2.21, 2.65, 3.02, 3.78 s'] (M=2.8xlO5) (Kolnaar
and Keller, 1995).
ious other kinds of distortion, and so it is not
as easy to recognize and even less easy to
quantify.
The above window effect (such as in
Fig. 4-50) was found to occur discontinu-
ously above a certain piston velocity (hence
apparent shear rate, yAc) for a given molec-
ular weight (M) (Waddon and Keller, 1990;
Narh and Keller, 1991 a; Kolnaar and Kel-
ler, 1994). This is shown in Fig. 4-52. Here,
for the lower values of yA, p is a slowly
decreasing function of T without any sign of
a minimum, as is expected from a steady
decrease of the melt viscosity with temper-
ature (yA and the associated extrusion out-
put here are very low, such that flow
instabilities that would characterize the
extrusion at more practical speeds do not yet
appear). However, the onset of a minimum
in p at 150-152C appears sharply on a
small increment increase of yA beyond a cer-
tain yA. Increasing yA further does not affect
 4.10 The Effect of Structure on Rheology: The 'Extrusion Window' in Polyethylene
the location of the minimum along the tem-
perature axis, but it makes the window more
pronounced (Kolnaar and Keller, 1994).
Therefore onset of the flow effect is critical
in yA, hence a critical apparent wall strain
rate y Ac .
Analogous criticality also applies to the
molecular weights (Waddon and Keller,
1990, 1992; Kolnaar and Keller, 1994). We
found that yA c was strongly dependent on
M: a lower M requiring a much enhanced yA
for the minimum to appear, and vice versa.
In spite of the fact that we did not have sharp
fractions for this purpose, but only materi-
als with comparatively broad, but neverthe-
less in a given series, comparable M distri-
butions (Mw/Mn ~ 5), we could establish an
apparently very well defined relation be-
tween Mw (= M) and the critical wall shear
rate yA c for the creation of a minimum in
thep vs. Tcurve (Kolnaar and Keller, 1994).
Accordingly, we found that
f-4.00.1
7A,C ~ (4-6)
as derived from the double logarithmic yA
vs. M plot Fig. 4-53).
At this stage we may remark that, bear-
ing in mind the intrinsic complexity of the
effect in question and the polydispersity of
the materials used, the emergence of such a
clear cut effect is remarkable and indicative
of some basic underlying cause. Even the
exact meaning of the - 4 functional depen-
dence apart, the message of Figs. 4-52 and
4-53 is clear: The appearance of this effect
(i.e., the minimum in the p vs. T curve) is
critical in both yA and M, the double criti-
cality that is the hallmark of a flow-induced
coil > stretch transition.
The same criticality is strikingly con-
firmed by extrusion experiments carried out
at constant p (Kolnaar and Keller, 1994).
Here, the pressure p was kept fixed while
lowering the temperature with the piston
displacement rate (v) being measured. The
253
molecular weight
Figure 4-53. Critical onset apparent wall shear rate
at the inception of the extrusion window vs. weight
average molecular weight as obtained from heating
runs (Kolnaar and Keller, 1995).
experimental results are displayed by the yA
vs. Tcurves of Figs. 4-54 and 4-55 obtained
at increasing values of constant p. In Fig.
4-54 yA is an increasing function of T, as is
to be expected from the increasing fluidity
(or decreasing viscosity) of the melt with T.
As can be observed, the yA (or v) values are
higher for higher values of p (the curves lie
above each other in order of increasing p)
in line with the expectation of higher shear
rates in response to higher applied stresses.
(The steep drop at the low T end of the T
range corresponds to solification and to ulti-
mate flow blockage, the counterpart of the
rise of the p vs. T curves in Figs. 4-50 and
4-52). So far it is all normal rheological
behavior. However, as shown in Fig. 4-55,
the situation changes dramatically on a fur-
ther increase of p: at a specific p the yA vs.
T curve shows a sharp maximum at
150- 151 C. On a further increase in p the
position of this maximum in yA remains
unaltered but increases in size.
As will be apparent, the above experi-
ment, as represented by Figs. 4-54 and 4-55,
is the precise complement of that in Fig.
254 4 Flow-Induced Orientation and Structure Formation

7.7 MPa
n D a
7.0 MPa
A A A A
_2 3
A
5.6 MPa
CO
o o o oo oooo
o oooo
10

Molecular weight (g/mol)

Figure 4-56. Critical pressure (pc) vs. weight aver-
140 145 150 155 160 165 age molecular weight as obtained from heating runs
such as in Fig. 4-50 (Kolnaar and Keller, 1995).
temperature (C)
Figure 4-54. Apparent wall shear rate (yA) vs. tem-
perature plots recorded during extrusion at a constant
pressure. Pressure values increasing from bottom to 4-52, both registering the same effect. The
top are indicated (Kolnaar and Keller, 1995). first in the form of p as a function of T at
constant v (hence yA), the latter in the form
50 of v (hence yA) as a function of Tat constant
p. In the first case the effect is manifest in
8.4 MPa
the form of a minimum and in the latter as
v
40
V V
a maximum in the respective curves vs. T.
We interpret the opposite, mutually comple-
menting effects displayed by Figs. 4-52 and
.2 30 4-55 as manifestations of the criticality inp,
in Fig. 4-55 directly and in Fig. 4-52 indi-
CO
rectly via yA, where, by our interpretation,
20 p increases with yA until its critical value pc.
8.0 MPa
Additional results (Kolnaar, 1993) indicate
that the criticality in M is also mirrored by
10 both types of experiment with constant rand
also with constant p.
j% o o o o o o o o o o o o ooA As a next step we consider the pressure
value (pc) for each yA in Fig. 4-53. A plot of
140 145 150 155 160 165
pc vs. M shows that the pc values were all
temperature (C) closely in the same range, around 7.0 MPa
Figure 4-55. As in Fig. 4-54 but extending to the (Fig. 4-56). The points broadly define a hor-
higher pressure values where a sharp maximum in yA izontal line: even if there is some scatter
appears at 150 C; this develops rapidly with a further about this line, the deviations are negligible
increase in pressure (Kolnaar and Keller, 1995). The
three curves in Fig. 4-54 are also included. (Note the compared to the huge variations in yA over
contracted abscissa scale compared to Fig. 4-54.) the same M range. We can assert therefore
 4.10 The Effect of Structure on Rheology: The 'Extrusion Window' in Polyethylene
that while yA varies steeply (to the power of
minus four) with M, pc is to a good approx-
imation constant over the same M range.
4.10.2 The Significance of the Window
Effect for Melt Flow Rheology
The existence of the window effect may
offer a potentially significant advantage for
processing that involves melt flow through
orifices. The advantages include: less ener-
gy for a given throughput, uniform pressure,
and chiefly, a uniform extrudate under con-
ditions where nonuniformity would other-
wise prevail, and could in fact make the
manufacture of unidirectional products such
as, e.g., monofilaments, rods, and pipes
impractical if not impossible. In addition to
the above practical considerations, an
understanding of the origin of the window
effect has posed a significant scientific chal-
lenge, to be addressed by much of the work
to follow.
It was recognized early on that the origin
of the window effect cannot be explained by
the continuum rheology of polymer melts
alone, and that the sharp singularity with
temperature points to a thermodynamic fac-
tor, in particular a phase transition. The
above results lend further support to this
contention: namely, the uniqueness and
sharpness of the effect, its clearly defined
temperature range, and the further evidence
that memory effects (conditional reversibil-
ity with heating and cooling, etc.) may be
operative.
With regards to the nature of the phase
involved in the proposed phase transition,
in analogy to the antecedents surveyed in
the previous sections of this chapter, a liq-
uid to crystal transformation would be con-
sidered likely. However, such a transforma-
tion would increase the flow resistance, as
opposed to decreasing it, which is the
present effect. In fact the upswing of/? at the
255
low T end of the p minimum (see, e.g.,
Figs. 4-50 and 4-52) and the downturn of yA
(v) at the low T end of the maximum in the
rate in Fig. 4.54, are in fact due to crystal-
lization, which can indeed lead to complete
cessation of the flow, the effect first
observed by van der Vegt and Smit (1967).
Based on such considerations, from the very
beginning, the hexagonal phase of PE was
suggested as responsible for the window
effect (Waddon and Keller, 1990, 1992;
Narh and Keller, 1991a). This hexagonal
phase is known to contain the chains in a
highly mobile form and has rather liquid
crystal-like characteristics. This, in princi-
ple at least, could account for the low flow
resistance and for the absence of features,
such as die swell, associated with the elas-
ticity of melts constituted by randomly
interpenetrating molecules. This hexagonal
phase is metastable at atmospheric pressure,
but there is evidence that it can be produced
as an apparently stable phase, e.g., by hold-
ing the chains stretched by appropriately
constraining ultra-drawn fibers or flow-
oriented shish-kebab crystals (Pennings and
Zwijnenburg, 1979; van Aerie et al., 1987;
Hikmet et al., 1987; Clough, 1970). In such
cases the melting points (Tm) of all modifi-
cations are increased, but that of the meta-
stable modification (Tm)h to a greater extent
than that of the stable one (Tm)o with the
result that a temperature range is created
where the previously metastable phase
becomes stable (subscripts o and h above
refer to orthorhombic and hexagonal phas-
es in PE, respectively). In most previous
experiments a temperature of 150 C, or
close, is recorded for an o h transition in
such a constrained system, in remarkable
coincidence with the present observation of
the p minimum.
It is implied by the above that the suggest-
ed phase transition is induced by the chains
becoming stretched out in the course of
256 4 Flow-Induced Orientation and Structure Formation
flow, modifying the free energy of the
system in such a way as to 'uncover' the
originally metastable, hexagonal phase
(Keller and Ungar, 1991). Or looking at it
in another way, we create a situation analo-
gous to that of the constrained fiber referred
to above. Having reached this stage of the
argumentation, the first works (Waddon and
Keller, 1990,1992; Narh and Keller, 1991 a,
b) envisaged chain extension as arising
through the effect of the elongational flow,
such as is necessarily present at the orifice
entry, already invoked to account for the
crystallization-solidification effects (at a
slightly lower temperature but still above
the practical solidification temperatures) by
van der Vegt and Smit, Porter, and previous
Bristol works (referred to in Sec. 4.5.2). The
present effect of reduced (instead of
increased) flow resistance would fall natu-
rally in this schema by invoking the mobile
hexagonal instead of the conventional
orthorhombic phase, as created at the par-
ticular temperature. As argued above, chain
extension by elongational flow is a rather
discontinuous process, corresponding to a
coil > stretch transition with no steady
intermediate stage in between, it being crit-
ical both in strain rate and molecular weight,
both criticalities pertaining to the creation
of the present window effect.
So far the argument seems self-consis-
tent, its different ingredients mutually sup-
porting each other. However, one item, the
last finding in Sec. 4.10.1., i.e., the constan-
cy of pc as a function of M (Fig. 4-56), does
not fall in line. Namely, it makes the win-
dow effect analogous to a 'yield' phenom-
enon, a runaway effect at a particular stress
(crc) rather than the direct consequence of a
critical rate. This suggested the yield as slip-
page of the material at or in close vicinity
to the solid boundary, converting a Poiseulle
type flow behavior into at least partial plug
flow within the capillary (Kolnaar and Kel-
ler, 1994, 1995). It is readily envisaged,
even in qualitative terms, that such a plug
flow component could have the characteris-
tics required by the newly found window
effect: namely, low flow resistance and an
absence of flow irregularities both in terms
of the p vs. T trace and in that of the extru-
date appearance. Further, it is to be noted
that, as regards the window effect at least,
the emphasis has shifted from the entry ori-
fice to the capillary as the likely site respon-
sible for the flow singularity under discus-
sion.
Plug flow (or wall slip) is of course a
familiar phenomenon in rheology. Howev-
er, this is by no means a downgrading of the
window effect to a known, somewhat trivi-
al precedent. Specifically, we see that a ther-
modynamical factor, a phase transition in
particular, is required, because without it
there is no reason why plug flow should
occur at a specific, sharply defined temper-
ature. Secondly, the phase responsible for
the window effect should be 'slippery', con-
sistent with it being 'mobile': as already
stated, proper crystals would block, not pro-
mote, flow, hence the invoking of the hex-
agonal phase. The transition to the new
phase at a particular temperature must be
chain extension-induced, otherwise there
would be no reason for a phase other than
the orthorhombic crystal. Recent in situ
experiments conducted at the synchrotron
radiation facility (DESY) in Hamburg have
indicated (Kolnaar et al., 1995) that a phase
with a single X-ray reflection, different
from both the orthorhombic phase and the
melt, indeed forms within the capillary
portion of the rheometer at temperatures
around 50 C. Within registration sensitiv-
ity, this single reflection could indeed be
attributed to the hexagonal phase. A subse-
quent study confirming the hexagonal
nature of this new phase has further shown
(van Bilsen et al., 1995) that this phase
 4.10 The Effect of Structure on Rheology: The 'Extrusion Window' in Polyethylene
also arises in the elongational flow field of
the constriction, as could have been envis-
aged from elongational flow considerations
such as in Sec. 4.5, but as just stated, will
only affect the rheology when it appears at
or near the boundary wall of the capillary
portion of the rheometer (Kolnaar and Kel-
ler, 1995).
The question therefore arises as to wheth-
er such chain extension could also be
expected at the walls, where the flow is of
simple shear character. It is apparent qual-
itatively that it could in the case of chains
that are adsorbed to the walls of the flow
channel. This issue has arisen previously in
connection with the formation of shish-
kebabs, in fact, of extended chain-type
fibers from solution by Pennings's surface
growth method (Pennings, 1977). Adsorbed
molecules anchored at the wall could pro-
vide the answer, as invoked in Sec. 4.8.3. In
fact the Brochard-de Gennes theoretical
considerations (1992) [together with corre-
sponding experimental observations of sur-
face layers (Migler et al., 1994)] quoted
there, envisaging disentanglement between
adsorbed molecules and the flowing bulk
with an associated criticality in the shear
stress, are likely to be applicable to our win-
dow effect, in which case a phase transition,
occurring at a specific temperature, would
still need to be superposed on the envisaged
chain extension.
We gave the rheological window effect
such detailed attention in the foregoing part-
ly because of its quite recent topicality, but
chiefly since it is a salient example of struc-
ture formation through flow with a striking
feedback effect of the structures arising on
the flow itself, with as yet unforeseeable
consequences for both basic knowledge and
practical exploitation. In addition, the par-
ticular structure formation in question
brings in a new element, namely, the role
and importance of the surface of the flow
257
channel. In specific terms, because the new
structure arises along the surface, and in
wider terms, because it raises the issue of
the role of surfaces in polymer melt flow in
broader generality, we shall return to it
below.
Even if the window phenomenon has
directed attention to the effects along the
wall of the capillary during flow in a rhe-
ometer (such as in Fig. 4-28), the possibil-
ity of elongational flow inducing chain
extension in the orifice remains unques-
tioned, as this has been the origin of all past
studies on solidification effects and of the
purposeful creation of specific micro-mor-
phologies by extrusion not too far above the
static melting point (see Sec. 4.5). The par-
ticular question that arises is the connection,
if any, between those past works on solid-
ification effects attributed to happenings in
elongational flow at the die entry and the
present window effect, which seems to be
associated with happenings along the capil-
lary wall in simple shear flow. At present
this question remains unanswered. The
commmon underyling feature is the
'on-off effect of chain extension with crit-
icality in both the strain rate and the molec-
ular weight, in turn leading to structure for-
mation even if in two different portions of
the flow system, with different consequenc-
es in the two cases.
4.10.3 Wider Implications
Interesting as it is in its own right, the
extrusion window effect may well be
regarded as a highly special phenomenon
with relevance limited to special systems
under rather circumscribed conditions. To
counteract such an impression here, we
draw attention to wider issues, of which
the present effect may be a special manifes-
tation, with pointers to future develop-
ments.
258 4 Flow-Induced Orientation and Structure Formation
First there is the influence of surfaces on
the polymer melt flow itself. Here the atten-
tion is focused on happenings at the wall,
which, as recognized by Brochard and
de Gennes (1992), can be important factors
in determining the nature of the flow itself.
Our present findings certainly fit into this
newly opened framework. While starting
from experimental observations on macro-
scopic flow behavior, it arrives at inferen-
ces that mesh with the new theoretical
approaches that start from molecular con-
siderations and focus on the nature and
behavior of the polymer chain at the
solid-liquid interface. From a more gener-
al standpoint, a special effect such as the
present phase transition may be regarded as
a useful aid. Namely, it serves to illuminate
the underlying generalities through enhanc-
ing these effects, resulting in conspicuous
consequences by which they can be readily
recognized, appreciated, and possibly even
utilized.
In connection with the influences of sur-
faces on flow and structure formation, we
recall two further, possibly relevant classes
of observational fact. Both involve a differ-
ent flow system, simple shear flow between
plates, and material, high-M polystyrene.
One concerns the formation of shish-kebabs
and row structures in simple shear flow, as
invoked previously in Sec. 4.8.2. In addi-
tion to the unresolved issues raised there,
those arising in Grubb and Keller (1974) are
specially pertinent to the discussion at this
point. Namely, here the resulting crystalline
'columns' were seen to be confined to layers
20 |im from both shearing surfaces, indicat-
ing stress concentration there. In addition,
the leading external edges of the film sam-
ples displayed 'lips' of about 20-|Ltm thick-
ness as seen in cross section, indicating that
sheets of such a thickness must be moving
together with the bounding solid surfaces
which are transmitting the shear on both
sides of the melt, fully consistent with the
concurrently observed structure formation.
The second surface-related effect was in
the field of melt rheology (Burton et al.,
1983). Namely, the torque measurement in
a parallel plate rheometer was found to be
flow gap-size dependent, specifically
decreasing below a gap size of 200 |im. The
torque reduction could become very pro-
nounced for a gap of 50 (Xm and below, and
increasingly so for increasing molecular
weights (5xl0 5 and above). This effect
requires the invoking of a boundary melt
layer of broadly 20 \xm attached to the solid
surface. The two alternative ways by which
this could then lead to the observed torque
reduction are laid out in Burton et al. (1983).
Here we merely remark that the rheological
effect in question could be consistent with
the structural effect in Grubb and Keller
(1974) (preceding paragraph) and could be
pertinent for the window effect, the main
subject of the present section, while of
course of note in its own right.
Also, the interaction between a polymer
and the solid surface of another material has
consequences beyond melt flow (or solution
flow). It is of direct consequence to the fric-
tion between two moving solids in contact,
where at least one is a polymer. The pos-
sibility of chain alignment arises, whether
cold or through the intermediary of local
melting. In the latter case the subsequent
formation of chain-aligned 'mobile' meso-
phases would have a potentially profound
influence on the frictional properties.
In addition to its own intrinsic interest,
the window effect is yet a further phenom-
enon contributing to the principal theme of
this chapter, namely, the 'on-off' effect of
chain extension with all its consequences for
the resulting structure and orientation, and
in the case of the window, also for melt rhe-
ology. This theme then raises issues about
melt flow in wider terms. Specifically, why
 4.11 Some Practical Applications of the Concepts Developed
and how could such an on-off effect exist
in the melt, and further, how is it that the
melt flow under the circumstances quoted
in this chapter 'senses' the presence of the
longest chains, even if present only in min-
ute proportions [e.g., see Bashir et al.
(1984)], far beyond their contribution to
conventional flow properties (e.g., simple
shear viscosity)? In principle at least, a coil
> stretch transition would provide the
answer, as established in dilute and semi-
concentrated solution (Sec. 4.5), but its
transference to the melt would test our tra-
ditional conceptions on melt flow. This
point has already been raised in Sec. 4.2.3.2
and 4.8.3 through Figs. 4-10 and 4-11; here
we bring it up again from yet another view-
point.
At this point an attractive, even if highly
speculative, possibility presents itself. In
the case of solutions the coil > stretch tran-
sition is conceptually clear. Namely, in the
non free-draining coil state the coil interior
is screened from the effect of flow in the sur-
rounding solvent, and the runaway effect of
the coil > stretch transition on increasing
the strain rate (with no intermediate stage as
a steady state, except as a transient) is the
consequence of the coil interior becoming
increasingly exposed to frictional contact
with the solvent, as it starts opening up
beyond a critical strain rate. We suggest that,
in the melt, the same effect may be due to
the same cause, namely that analogous
screening effects may be operative there as
well. This effect could be provided by a high
degree of polydispersity in normal polymer
melts. Accordingly, a molecule at the high
tail end of the distribution could be regard-
ed as a long molecule in a solution of its
shorter species, which provide a screening
effect analogous to that in a solvent. The
indicated response to elongational flow,
including the coil > stretch transition,
would then occur. Possibly the general
259
experience that polydispersity is favorable
to steady stretching flows, while the trend
towards monodispersity is inducive to flow
instabilities [network response (Vinogradov
et al., 1972)1 is supportive of the above
argument.
4.11 Some Practical Applications
of the Concepts Developed
In Sec. 4.5 a detailed description is given
of the various ways in which flow-induced
crystallization and the oriented crystalliza-
tion of chains can lead to a wealth of intri-
guing morphologies such as row-nucleated
structures and (interlocking) shish-kebabs.
In the next sections, attention will be direct-
ed briefly towards a few selected processes
and products of technological applicability,
realized or potential, that have been devised
relying on the formation of shish-kebab type
morphologies created in elongational flow
(fiber spinning, extrusion, and molding) and
shear flow (extrusion and molding), respec-
tively. As will be shown below, the presence
of shish-kebab type morphologies and par-
allel lamellar structures can lead to signifi-
cant enhancement of the mechanical, ther-
mal, dimensional, and various other proper-
ties in an advantageous manner.
4.11.1 Structure Formation Relying
on Elongational Flow
4.11.1.1 'Hard-Elastic' Fibers
'Hard-elastic' fibers display long range
elasticity (even if with a substantial time
delay in recovery) such as is more appropri-
ate to elastomers than to crystalline thermo-
plastics, yet retaining the high stiffness
(modulus) of a thermoplastic, i.e., high com-
pared to a rubber. This hard-elastic mechan-
ical behavior, as is apparent from Fig. 4-57,
260 4 Flow-Induced Orientation and Structure Formation
TEMPERATURE: -190 C
ELONGATION RATE: 100 %/min.
10 20 30 40
% ELONGATION
is not relatable to the molecular character-
istics alone (as, e.g., in rubbers), but arises
from the crystalline micro-morphology,
which has to be specially created for this
purpose, as described in the patent literature
[see Cannon et al. (1976), which is a
summarizing article on this whole field].
The essential feature of this micro-mor-
phology is the parallel lamellar arrange-
ment throughout the whole macroscopic
sample.
The special long range elasticity of these
materials arises from the lamellae being
pulled apart by the load applied and from
the resistance of the lamellae to such separ-
ation, which provides the comparatively
high modulus and the driving force for
reversibility. This type of high elasticity is
energy as opposed to entropy driven, as is
the case for traditional elastomers. In mod-
Figure 4-57. Tensile curves (tensile
stress in grams per denier versus per-
centage elongation) illustrating the
long range elasticity (coupled with
hysteresis) of hard-elastic ('springy')
fibers [from Park and Noether as
quoted in Cannon et al. (1976)].
50
els to account for them, the lamellae are vis-
ualized acting as leaf springs, somewhat as
sketched and modeled in Fig. 4-58. As seen
from Fig. 4-58, the model implies pro-
nounced void formation as the lamellae sep-
arate, a fact conspicuously apparent from
the whitening of the sample and the inhibi-
tion of wetting liquids and directly access-
ible by low angle X-ray scattering. In fact
such voids can be locked in (by overstretch-
ing and annealing), in which case appropri-
ate thin films with lamellae edge-on can
serve as filters (Celgard filters - Fig. 4-59).
In such a case the voids between the lamel-
lae become subdivided into still smaller
ones through fine fibrils spanning the gaps
that formed on preceding overstretching
(interlamellar fibers), where these subvoids
lead to the high filtering efficiency of the
product.
 4.11 Some Practical Applications of the Concepts Developed
life
X))
Figure 4-58. Row structure model for energy driven
elasticity in springy polymers: (a) Schematic diagram
of lamellae in deformed and undeformed states. Tie
points represent interlamellar tie molecules, (b) Paper
bell mechanical model [after Clark as quoted in Can-
non et al. (1976)].
Figure 4-59. The submicroscopic structure of a
'Celgard' filter, having arisen from overstretching and
subsequent setting of a film of hard-elastic polypro-
pylene. Electron micrograph. (From the prospectus of
Hoechst-Celanese.)
The origin of the crystal morphology
responsible for the hard-elastic properties
falls neatly within the subject of the present
article. The preparation details are in the
domain of patent rather than scientific liter-
ature. This much is clear, however, and com-
261
mon to all variants, in that the parallel lamel-
lar structure arises through row nucleation
created by stress/flow imposed on the melt
in the course of the spinning operation, in
some cases followed by slight additional
drawing and sometimes annealing [see, e.g.,
review by Cannon et al. (1976) and further
references there]. The desirable structural
element is the lamella, the fibers only serv-
ing as nucleating entities setting the pattern
of the lamellar texture: since they are few in
number, they make, little contribution to the
overall properties. It is desirable to keep the
lamellae straight, and hence to be on the par-
allel side of the scheme of Fig. 4-26. The
materials worked on so far are polymers
where the lamellae have comparatively lit-
tle tendency to twist, which allows for wider
columns of still straight lamellae to be
attained with fewer nucleating fibers. Poly-
propylene, polybutene, polypivalolactone,
and polyoxymethylene were found to be
appropriate in this respect, even if lamellar
twisting does occur even there (particularly
with polyoxymethylene). Figure 4-3 in Sec.
4.1.1 in fact originates from studies on such
hard-elastic fibers where, after some etch-
ing procedures, the fiber-platelet duality
(with some twisting of the platelets)
becomes clearly apparent, to the extent that
we selected it here as one of the introducto-
ry micrographs of this article.
4.11.1.2 Extrusion
and Molding Processes
The first publication of relevance for
present consideration was, as discussed in
Sec. 4.5.2, by van der Vegt and Smit (1967),
who observed that the flow through a cap-
illary die in a melt extruder became blocked
by crystals induced by the elongational flow
at the constriction. As already described in
Sec. 4.5, taking up the concept of elonga-
tional flow-induced crystallization further,
262 4 Flow-Induced Orientation and Structure Formation
Porter and coworkers (Southern and Porter,
1970; Porter et al., 1975) recognized that
such extrudates had advantageous proper-
ties. Subsequent works in the Bristol labor-
atory (Bashir et al., 1984, 1986; Keller and
Odell, 1978;Odellet al., 1978) continued to
focus on the resulting extrudate, 'fine
tuning' the morphology by what may be
termed 'micro-morphologicalengineering'.
This consisted of the purposeful variation of
the ratio of the two morphological compo-
nents (fibers and lamellae), leading to,
amongst others, the 'zip-fastener morphol-
ogy' of Figs. 4-31 and 4-33, which could
give rise to the advantageous properties
itemized in Sec. 4.5.3, such as high Young's
modulus - ranging from 100 GPa (discon-
tinuous process) to 20 GPa (continuous pro-
cess) - without, however, possessing the
fibrillating behavior and thermal shrinkage
that usually accompany the attainment of a
high modulus by a process such as fiber
drawing, with prospects of technical appli-
cability (Bashir et al., 1984). In the latter
continuous process the fibers were wound
taut on a drum so as to prevent relaxation of
the orientation created within the extrusion
die. The application of a subsequent hot-
drawing stage after winding up could
enhance the modulus even further (Bashir et
al., 1985).
By another approach, based on the same
theme, under high extrusion pressure and
controlled flow conditions at temperatures
slightly above the melting point, in conjunc-
tion with a longitudinal flow gradient in the
die, Pornnimit and Ehrenstein (1992) pro-
duced high-strength, rigid profiles from
high density polyethylene using a conven-
tional screw extruder. Here, again, enhance-
ment of the mechanical properties origi-
nates from the presence of a shish-kebab
morphology (which is sometimes also
termed 'self-reinforcement' or 'PE-PE
composite'). In comparison with conven-
tionally extruded profiles, here the profiles
produced exhibit a 10-fold increase in the
Young's modulus, homogeneous transpa-
rency, and improved thermal stability as
well as good dimensional stability. In addi-
tion, the presence of the shish-kebab mor-
phology was shown to result in better trans-
verse mechanical properties.
Besides extrusion, molding processes
have also been devised that introduce elon-
gational flow along the injection direction
to induce orientation and pressure in the
flow channel for the fixation of the result-
ing shish-kebab morphology with advanta-
geous properties (Rueda et al., 1989; Bayer
et al., 1989).
4.11.2 Structure Formation Relying
on Controlled Solidification
and Shear Flow: The SCOREX
and SCORIM Processes
This type of processing, developed at
Brunei University, UK (Allan and Bevis,
1991; Gibson et al., 1990), is based on the
principle that by applying a controlled
shearing action to the melt in the course of
solidification, the resulting microstructure
can be purposefully 'managed'. Designed
originally for the fabrication of fibrous com-
posites with thermoplastic matrices, it can
also be applied to single component crystal-
lizable thermoplastics where the micro-
structure to be managed is the crystalline
structure itself, explicitly, the fiber-platelet
morphology under discussion. In this way a
predesigned overall orientation, created by
alignment of the morphological entities
along desired directions, is produced with a
corresponding improvement in the mechan-
ical properties. The principle can be applied
to injection molding (SCORIM) and extru-
sion (SCOREX).
Technically, molten material is fed from
the extruder (or mold) through one or more
 4.12 Concluding Remarks 263

channels into the die block. The material

solidifies within the die block while being
sheared through the controlled, reciprocat-
ing displacement of two or more pistons
which are located within the die block. Typ-
ically, there are four pistons with the strokes
acting in different phases according to the
particular design and purpose of the opera-
tion. The process is complete when the
desired orientation is 'locked in' through
solidification. In the case of extrusion the
solidified extrudate is expelled in a contin-
uous manner. As the appropriate chambers
containing the polymer are cooled from out-
side, solidification starts at the outer surfac-
es of the sheared melt, spreading gradually
inwards. In this way there is constant rela- D
tive displacement of the melt with respect
to the already solidified portions, the strong
shearing effect near the interface producing
the orientation. Figure 4-60. Internal morphology of a polyethylene
plaque fabricated via the SCORIM process. The recip-
The oriented morphology as revealed by rocating shear direction is along the NE-SW diago-
electron microscopy is of the row-nucleat- nal. Solidification started at the outside walls of the
mold (i.e., from top left and from bottom right inwards)
ed type in accord with the scheme in Fig. where it gave rise to shish-kebab type structures while
4-26. Figure 4-60 gives an example. The under shear. In this case shearing was interrupted,
fiber-platelet shish-kebab type morphology leading to the central zone D being formed from the
still uncrystallized material. Here the lamellae are
is clearly apparent, aligned parallel at the more extended laterally, and have started to curve and
top left and bottom right portions of the twist, gradually going over to a random spherulitic
micrograph. In this instance the shearing type of arrangement (by courtesy of M. J. Bevis).
was stopped before solidification was com-
plete. This is reflected by the central portion ponent melts is the fabrication of pipes, even
where the material crystallized without any up to very large diameters (several tens of
orienting influence, thus giving rise to more centimeters), in which case orientation is in
or less unoriented lamellae indicating incip- the hoop direction, stiffening the pipe in lat-
ient spherulite development. It is instructive eral compression (e.g., against the weight of
to note how the row-nucleated columns soil in common water pipe applications).
widen towards the center, which is indica-
tive of the reduction in the number of nucle-
ating fibers as the shearing action gradual- 4.12 Concluding Remarks
ly came to a halt, a visually instructive illus-
tration of our basic theme throughout this It will have become clear that, within the
article, in this case purposefully utilized in existing space limitations, the present arti-
a technological application. cle cannot be a fully comprehensive survey
One of the most promising applications on flow-induced structure formation.
of the SCOREX technique with single com- Instead, a specific theme was chosen to
264 4 Flow-Induced Orientation and Structure Formation
serve as a guide for traversing an extensive
and varied territory. The theme, as spelled
out in (Sec. 4.1.1), is the dual nature of the
fiber-platelet crystal morphology, with
apparently nothing in between, which trans-
lates in molecular terms into the preceding
duality of essentially random and highly
extended chains, respectively. The above
two aspects, namely the structural features
and the preceding respective molecular con-
formations and processes, have in the past
been subjects of investigations along separ-
ate lines; the present survey is [following a
preliminary paper (Keller and Kolnaar,
1993)], to our knowledge, the first attempt
to combine the two in one and the same trea-
tise.
As will have become apparent, the par-
allel between the molecular processes and
the structural features has proved to be sur-
prisingly productive in accounting for a
wide range of experimental observations:
specifically, the parallel between the coil
stretch transition and the fiber-platelet
duality, as based on observations in dilute
systems. In fact, this parallel holds up only
too well, as it seems to be applicable even
when it should not, as based on existing
notions on the behavior of chain molecules
in mutual interaction. As will have been
noted, the conception of stretching out
chains as individual entities can be taken
quite far into the concentrated regimes, fur-
ther than might have been thought possible
in view of the anticipated intervention of
entanglements. While there may be a broad
latitude in the limits where such entangle-
ments can become effective, particularly in
view of the time-scale dependence of such
interactions emphasized throughout this
chapter, the 'isolated' chain approach
should certainly become inapplicable once
permanent chemical cross-links are intro-
duced. Nevertheless, there seems to be no
break in continuity regarding the observable
structures when going from dilute to con-
densed systems, and beyond to systems that
are lightly cross-linked: the fiber-platelet
duality, and this on a microscopic (optical
and low power electron) scale, persists as
the salient feature throughout, irrespective
of any interpretation in molecular terms.
Clearly, this must remain the experimental
basis for any interpretation of the resulting
orientation and properties.
As regards molecular interpretation we
have made, what we believe, a promising
start by building on the behavior of dilute
systems with the underlying conception of
the coil > stretch transition, as already stat-
ed. Its extension to condensed and lightly
cross-linked systems, so as to account for
the observed structures, with due regard to
feasibility considerations of molecular
behavior, remains a challenge for the future.
For this, at least some guidelines are provid-
ed in this paper together with highlighting
of the problems that arise.
As referred to repeatedly throughout the
text, the problems that arise come down to
the question as to which of the two alterna-
tives as expressed by Figs. 4-10 and 4-11
applies: Fig. 4-10 allowing for the coil >
stretch transition of individual molecules to
be taken up to the melt, or Fig. 4-11 with a
changeover to network behavior at a partic-
ular concentration through the agency of
transient entanglements arising beyond a
certain strain rate (n). The alternative of
Fig. 4-10 ensures full continuity between
dilute solutions and the melt, which is the
message of the structural observations,
while the alternative in Fig. 4-11 is more in
line with expectations from conventional
knowledge of macromolecular behavior.
Whatever weight is given to points of
agreement as compared to issues that create
difficulties in the respective alternatives, the
notion that identical (or at least closely sim-
ilar) structures in different systems are not

likely to be due to totally disparate causes
must remain a reasonable pointer for the
way ahead.
As regards orientation and properties, the
issues are clear. Only by taking note of the
full complexities of the structural hierarchy,
resulting from orientation-induced crystal-
lization, is there any chance for meaningful
interpretation and prediction. Complex as
the structures may appear in themselves,
they are in fact the straightforward conse-
quence of the fiber-platelet duality, the prin-
cipal theme of this article, even irrespective
of how and why they arise in molecular
terms.
4.13 Note Added in Proof
Since submission of this chapter, an issue
of potential consequence for the whole sub-
ject has come to the forefront. Namely, some
doubts have been voiced regarding the exis-
tence of a true criticality for the coil >
stretch transition and consequent attainment
of a high degree of chain extension in elon-
gational flow experiments such as reviewed
in Sec. 4.2. If such a critique is valid it would
clearly affect not only the content of Sec.
4.2 but also the conceptual scaffolding of
some other parts of the chapter, the reason
for the matter needing to be addressed at this
late stage of preparation of the book. A fully
reasoned argumentation of the issue is avail-
able [Carrington, S. P., Odell, J. A. (1996),
in the special issue of the Journal of Non-
Newtonian Fluid Mechanics edited by K.
Walters on the Workshop "Unresolved
Experimental Dilemmas in the Dynamics of
Complex Fluids", which was held at the
Isaac Newton Institute of Mathematical Sci-
ences, Cambridge, in January 1996]. In the
light of the analysis in this paper (with which
we fully concur), the validity of the critical
nature of the coil > stretch transition and
4.13 Note Added in Proof 265
the ensuing high degree of chain extension
is upheld. At this stage we confine ourselves
merely to a few essentials which should suf-
fice to safeguard the viewpoint that we
adopt in this chapter.
From the experimental point of view the
critique is based primarily on values of bire-
fringence obtained for the supposedly
extended-chain regions in the appropriate
flow field (e.g., in the region of the bright
line such as in Fig. 4-5), which are claimed
to be much lower than what is expected from
nearly full chain extension (Nguyen et al.,
1995). To this we reply that, not only did
values of the earliest work (Pope and Kel-
ler, 1978) conform to expectations from
nearly full chain extension, but so do the lat-
est values arising from the much more
sophisticated most recent measurements
(Carrington and Odell, 1996; also Leal,
1996, as presented at the above-mentioned
workshop and published in part previously
by Dunlap and Leal, 1987).
However, sharing the views of Carring-
ton and Odell (1996), we are sure that the
case for near full extension rests on much
firmer ground than reliance on numbers
arrived at by the combination of rather del-
icate measurements with evaluation of the
data obtained [raising, for example, ques-
tions about the precision of sampling of the
narrow birefringent line, such as in Fig.
4-5, or about the homogeneity or otherwise
of the orientation distribution within the
confines of such a line, etc., all points which
apply even more so to light-scattering data,
which are also claimed to be at variance with
near full chain extension (Menasveta and
Hoagland, 1991)]. Namely, there are two
uncontested facts - even qualitative trends
of general nature - that are in favor of near
full chain extension, and, in fact, could hard-
ly be explained otherwise, but which are not
given their due weight in the contrary argu-
ments.
266 4 Flow-Induced Orientation and Structure Formation
One is the saturation of birefringence
with , i.e., the existence of a final plateau
in the experimental intensity versus
curves as drawn schematically in Fig. 4-6.
It would be difficult to conceive of any (not
to say a very low intermediate level of) state
of chain extension that would correspond to
a well-defined final steady state in response
to the extensional influence, other than that
approaching full chain extension.
The second point of general character is
the precision with which the chains break
into what appears to be exactly equal halves
on flow-induced chain fracture (Sec.
4.2.1.3). How would the chain "know"
where its precise geometric center is locat-
ed unless it is already close to fully out-
stretched?
Finally, since quite recently there has
existed optical visualization of a chain actu-
ally stretching out in the case of fluorescent-
ly labeled DNA molecules. In this case the
DNA chain could actually be seen to stretch
out to up to 90 % of its contour length (Lar-
son et al., 1996, a follow-up to Perkins
et al., 1995) in an appropriate elongational
flow field in accord with theoretical expec-
tations and with the theme pursued through-
out our whole chapter.
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General Reading
Preparatory or background reading on some specific
aspects of this chapter:
Morphology
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Keller, A. (1968), Rep. Prog. Phys. 31, 623.
Keller, A. (1985), in: Polymers, Liquid Crystals and
Low-Dimensional Solids: March, N., Tosi, M.
(Eds.). New York: Plenum, p. 3.
Keller, A., Goldbeck-Wood, G. (1996), in: Compre-
hensive Polymer Science, 2nd SuppL: Aggarwal,
S. L., Russo, S. (Eds.). Oxford: Elsevier Science,
p. 241.
Rheology
Dealy, J.M., Wissbrun, K.M. (1990), Melt Rheology
and Its Role in Plastics. New York: Van Nostrand
Reinhold.
General Polymer Physics
Gedde,U.W. (1995), Polymer Physics. London: Chap-
man & Hall.
5 Crystallization
Gerhard Eder and Hermann Janeschitz-Kriegl

Institute of Chemistry, Linz University, Austria

Dedicated to Prof. em. Jan Koppelmann, Leoben.

List ofSymbols and Abbreviations 270

5.1 Fundamentals 273
5.1.1 Disposition 273
5.1.2 The General Theory 275
5.1.3 Some Special Cases 277
5.1.4 The Rate Equations 278
5.1.5 Nucleation Models 279
5.1.6 Influence of Temperature Gradients 280
5.1.7 Crystallization in Confined Samples 282
5.2. Experiments in Quiescent Melts 288
5.2.1 Differential Scanning Calorimetry (as Applied to Isotactic Polypropylene) . 288
5.2.2 Other Measurements Concerning the Growth Speed
of Isotactic Polypropylene (i-PP) 295
5.2.2.1 Dilatometry 295
5.2.2.2 Optical Measurements 296
5.2.2.3 Transcrystallization 296
5.2.2.4 Crystallization Zone 299
5.2.2.5 Quenching of Extremely Thin Samples 301
5.2.2.6 Compilation of Growth Data for the a-Modification of i-PP 302
5.2.3 Crystallization Kinetics Data for Some Other Polymers 304
5.2.3.1 Isotactic Polystyrene 304
5.2.3.2 Polyethylene terephthalate) 306
5.2.3.3 Linear Polyethylene 308
5.2.3.4 Some Complementary Measurements on i-PP 313
5.3 Flow-Induced Crystallization 314
5.3.1 Introduction 314
5.3.2 Apparatus 315
5.3.3 Results 317
5.3.4 Theoretical Considerations 320
5.3.5 Towards a Quantitative Evaluation 323
5.3.6 Further Evidence for the Correlation Between the Model and Reality 327
5.3.7 Towards the Recognition of Molecular Parameters 330
5.3.8 Chances for Numerical Simulation 333
5.4 Closing Remarks 338
5.5 Acknowledgements 340
5.6 References 340
Materials Science and Technology
Copyright WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
270 5 Crystallization

List of Symbols and Abbreviations

a heat diffusivity of the melt
A growth area/set
a(T) shift factor obtained from rheological measurements on melt
a (t, sy x) area
b constant
c, cp heat capacity of the melt
cp, cs heat capacity of the DSC pan and sample
C constant
D thickness of slab; average distance between threadlike precursors; dia-
meter
dA, dy characteristic distances between neighboring surface nuclei/bulk nuclei
Dw average distance between threads at the wall
/ function in Eqs. (5-39), (5-67)
Fo Fourier number
G growth rate
gh gn factors in Eqs. (5-97), (5-98)
Gw growth rate at wall temperature
g function in Eqs. (5-39), (5-67)
Go constant radial growth speed; growth speed factor in Eq. (5-94)
G growth rate as a function of the temperature
h latent heat of crystallization per unit mass
H duct height
/*_, h+ functions
/ intensity
k nonnegative integer
K(T) kinetic function
L length of precursors
La average length of threads
L tot total length of precursors/threads
M confined volume; molar mass
Mn number-average molecular weight
Mw weight-average molecular weight
Mz z-average molecular weight
rap, ras mass of DSC pan/sample
n number of nuclei; power-law index
n, neff (effective) Avrami index
n average number of points
An birefringence
N number of nuclei/spherulites/scatterers per unit volume
A^ A number of spherulites per unit of surface area
Afc, TVS number of existing spherulites per unit volume
Afv number of potential sites/nuclei per unit volume
A^v number of spherulites nucleated per unit volume in bulk of material
 List of Symbols and Abbreviations 271

N number of spherulites per unit surface

p fraction of crystallinity in the final product shortly after its manufac-
ture; relative growth rate gradient
r(t,s) radius of sphere
R ratio of time constants in Eq. (5-3)
R, Rs radius of spherulite
s, t0 time at which spherulite is nucleated
S intensity of light scattering
St Stefan number
t time
tc starting point of light scattering
tD thermal equilibration time
t{ an induction time
t0 time when actual crystallization temperature reached; nucleation time
ts shearing time
tT residence time in tunnel
f dimensionless time
t\/2 dimensionless time when mean degree of crystallinity is Vi
tl/2 time of half conversion
tx/2 time at which the retardation reaches half the wavelength
T temperature (in mid-plane of sample)
Th base line temperature
Tc crystallization temperature
Tf furnace temperature
Tf constant cooling rate of furnace
Tfr furnace starting temperature
Tg glass transition temperature
T{ initial (melt) temperature
Tm melting temperature
To reference temperature
Ts sample temperature
Tw temperature of quenched wall
T2 short term quench temperature
u velocity in x-direction
v volume (of spherulite)
w dimensionless time
x position of crystallization front or zone
x* thickness of highly oriented boundary layer
xm position of spherulite center
x0 position of spherulite nucleation
x dimensionless space
xy y} z coordinates

a nucleation rate; relaxation time; heat transfer coefficient

a 2 , oc3 surface/bulk relaxation rate
272 5 Crystallization

temperature sensitivity coefficient of G; constant in Eq. (5-104)

7 effective heat transfer coefficient
7 shear rate
optical retardation
r critical shear rate
7c
characteristic shear rate
wall shear rate
So Dirac function concentrated at t=0
e error
critical strain rate
viscosity
zero shear viscosity
e dimensionless shearing time
0 angle at maximum intensity
i characteristic length (see Eq. (5-18)); wavelength (of light):
thermal conductivity
A, A2, A3 intensity measure
A (A) expectation value of points in A
Aot dimensionless Ltot
nucleation frequency
degree of crystallinity
2> S(2)> S3' S(3) functions relating to degree of crystallinity due to surface nucleation/bulk
nucleation
probability
density; dimensionless square of shear rate
functions defined by Eq. (5-49)
activation time; time constant in Eq. (5-89b)
relaxation time
O heating power
(undisturbed) total volume of all spherulites grown per unit of volume
auxiliary functions
u Vi> 3 auxiliary functions
probability of an event B

CCT continuous cooling transformation

DSC differential scanning calorimetry
HDPE high density polyethylene
i-PP isotactic polypropylene
IR infrared
PE polyethylene
PETP polyethylene terephthalate
PP polypropylene
PS polystyrene
TTT time-temperature transformation

5.1 Fundamentals
5.i.l Disposition
In Fig. 5-1 a schematic drawing is given
of the consequences of a quench at the plane
x = 0 of the half infinite space filled with a
melt of initially uniform temperature above
the melting point. According to the classi-
cal theory of Neumann in the 1860s (see
Carslaw and Jaeger, 1959) and Stefan
(1891), the so-called square root law is
obtained, which means that the thickness of
the solidified layer will increase with the
square root of time (r) if the wall at x = 0 is
quenched to a temperature below the melt-
ing point at time zero. In this theory the
assumption is made that crystallization
occurs as soon as the thermodynamic equi-
librium melting or crystallization tempera-
ture is reached during cooling. It goes with-
out saying that such a description of the
progress of crystallization can only be valid
for a very slow process that proceeds in
quasi equilibrium. However, at short times
a fast process (with nominally infinite initial
slope) is predicted. This means that this the-
ory is inconsistent.
But what happens in reality? Crystalliza-
tion always starts from certain spots (called
nuclei) within the material or on its surface.
Figure 5-1. Schematic presentation of the progress
of crystallization starting at a quenched wall. For
explanation see text.
5.1 Fundamentals 273
If the average distance between nucleation
sites on the wall surface is small enough (see
below), a crystallization front starts at the
wall, as in the classical case. The initial
speed of progress of this front, however,
is finite and equal to the growth speed
of spherulites at the temperature of the
quenched wall (Eder and Janeschitz-Kriegl,
1984). The principal difference to the clas-
sical treatment, however, is that with a
supercooled crystallization front a certain
zone of the fluid in front of the already crys-
tallized layer is also supercooled. (In the
classical approach the fluid is above or at
the melting point throughout and does not
contain nuclei per definition). However, this
means that in a real situation nucleation in
the said zone of the fluid can no longer
be excluded. In practice it happens that,
because of diffuse nucleation in the bulk of
the fluid, a more or less diffuse crystalliza-
tion zone (Berger and Schneider, 1986),
comes into existence, which moves with a
higher speed into the melt than the said front
which, as a consequence, is superseded ear-
lier or later by this zone. Why the crystal-
lization zone moves faster can easily be
understood. The front movement can be
compared with a single runner on a sports
field. The movement of the zone, however,
reminds us of a relay race where with every
handing over of the baton two arm lengths
are gained. These two arm lengths are com-
parable with the radii of two impinging
spherulites, of which one is nucleated in
front of the other. If the overall speed of
crystallization is raised, e.g., by the creation
of more nucleation sites in the melt, the zone
becomes narrower and supersedes the front
at an earlier time. In the limiting case of an
infinite crystallization speed, the classical
front movement is obtained. Interestingly
enough, the location of the zone is indepen-
dent of the number of nuclei at the wall. If
this number is zero, the only difference is
274 5 Crystallization
that no crystallization front can be observed
in the beginning. This front movement has
been called transcrystallization (Wunder-
lich, 1973). Its footprints can be found in the
cross sections of quenched samples of crys-
tallizable polymers, and also in metal casts
(columnar phases). This sort of superstruc-
ture can even be found in volcanic rocks like
the well-known basalt pillars.
It goes without saying that the sketched
morphology is the result of a complicated
interaction of heat transfer and crystalliza-
tion kinetics. If, tentatively, a time tl/2 of half
conversion (into crystallized material) is
defined, a classification can be formulated.
In fact, with a slab of finite thickness D the
said time of half conversion must be com-
pared with the time tD of thermal equilibra-
tion, which reads (Astarita and Kenny, 1987)
(5-1)
Aa
where a is the heat diffusivity of the melt
and St is the Stefan number defined as
h (5-2)
St =
where T{ and Tw are the initial melt temper-
ature and the temperature of the quenched
wall, c is the heat capacity of the melt, and
h is the latent heat of crystallization per unit
mass. The denominator gives the amount of
heat that must be removed per unit mass if
no crystallization occurs. This amount is
removed during the time D2/(4a). The rela-
tive increase corresponding to crystalliza-
tion is expressed by the second term (in
brackets) of Eq. (5-1).
The ratio
(5-3)
h/2
is characteristic for the type of process
occurring. For a small value of R the sam-
ple is cooled down first and crystallization
occurs almost isothermally afterwards (thin
slab, slow crystallization: nucleation rate-
controlled process). For a large value of/?
almost the classical situation of a (narrow)
crystallization zone moving from the sur-
face into the slab is obtained (thick slab, fast
crystallization: heat diffusion-controlled
process). Berger and Schneider (1986) con-
sidered the cases of St = 0, whereas Astari-
ta and Kenny (1987) treated the cases for
St > 1, which are more relevant for metals.
Mathematical treatments of this situa-
tions were first given by Berger and Schnei-
der (1986) and Astarita and Kenny (1987)
for tl/2 being assumed as a unique function
of the temperature, with a maximum some-
where halfway between the melting point
and the glass transition temperature. Malkin
et al. (1984) treated crystallization like a
chemical reaction [see also Tadmor and
Gogos (1979)], assuming that the speed of
crystallization is a unique function of the
degree of conversion achieved (self-accel-
erating process). These treatments are bet-
ter than the classical treatment, where the
latent heat has simply been incorporated
into the temperature dependence of the heat
capacity as a peak at the melting point. Nev-
ertheless, these improved treatments do not
permit the prediction of structure (grain,
texture) of the final product and, moreover,
do not express one very important fact, i.e.,
that the speed of crystallization is by no
means a unique function of the temperature
or of the degree of conversion. This can eas-
ily be explained with the aid of a simple
example. For this purpose the process of
crystallization is compared for two samples
of the same material, one without (or with a
low portion) of nucleation agent (inocu-
lant), the other with a high content of the lat-
ter additive. At a certain stage of crystalliza-
tion (a certain volume fraction of crystal-
lized material), the first sample contains a
relatively small number of relatively large

spherulites, whereas the second sample con-
tains many smaller spherulites. At the same
total volume of these spherulites the growth
surface in the second sample is obviously
bigger, which means that in this sample the
rate of crystallization is higher than in the
first sample. And, in the general case, the
number of growing spherulites is also a
function of the thermal history. (Further
background on the crystallization of semi-
crystalline polymers may be found in
Chap. 4 of Vol. 12 of this Series.)
In this way we believe that we have char-
acterized the starting point for our investi-
gations sufficiently well.
5.1.2 The General Theory
With respect to the latest development of
the theory of crystallization processes, a
recent compilation, as given by one of the
present authors (Eder, 1997), will be fol-
lowed. As a starting point, the definition of
Poissonian point processes is used. If N(A)
is the number of points of a point configu-
ration (set) A in state space X, *(B) is the
probability of an event B and A (A) is the
expectation value of points in A, one has for
mutually disjoint sets Au ..., Am of the state
space and nonnegative integers ki9 ...,km
i) = ki for i = l , . . . ,
A(At)k' A(Ai) (5-4)
i=\
The quantity A is called the intensity mea-
sure of the Poisson process. The reader may
recognize that Eq. (5-4) is a generalization
of the ordinary Poisson distribution on the
line
n (5-5)
with the average number n in a certain inter-
val being replaced by the measure A(At) of
5.1 Fundamentals 275
the sets At. In that which follows, only a sin-
gle set A is considered and the question is
raised about the probability that the number
N(A) in this set is equal to zero. In fact, the
question will arise as to whether a certain
point in the melt is not yet swallowed by
crystallized matter.
As a first special case one may assume for
the expectation value in the four-dimension-
al coordinate system of space and time
A[(x, x + Ax) x (y, y + Ay) x (z, z + Az)
(5-6)
x (t,t + At)] = f(x) a(t) Ax At
where/(x) Ax is an abbreviation for/(x, y,
z) Ax Ay Az and a is the nucleation rate. For
homogeneous nucleation within a confined
volume M, the following specification will
be used
1 for x e M
/(*) = 0 (5-7)
otherwise
With respect to the growth of nucleated
crystallites, a deterministic point of view is
accepted in connection with the assumption
that for quiescent isotropic melts spherulites
are formed. The volume of a spherulite
nucleated at time s and considered at time t
will be according to these assumptions
v(t,s) = 4/r JG(U)AU (5-8)
where G(t) is the growth rate at time t. If the
further assumption is made that G is a
unique function of the (changing) tempera-
ture r, the time dependence of G is unique-
ly connected to the time dependence of T.
As is well-known, the growth speed as a
function of the temperature is a bell-shaped
curve showing a maximum somewhere
between the equilibrium melting point and
the glass transition temperature, reaching
zero at both ends (van Krevelen, 1978). If
the density changes by crystallization are
276 5 Crystallization
space
tine
Figure 5-2. Schematic space-time diagram for the
growth (G) of a single spherulite nucleated at time t0,
the growth speed being time-dependent (Eder, 1997).
(Courtesy of Marcel Dekker, New York.)
space
tine
Figure 5-3. Schematic presentation of a set Axj. If a
single nucleation event occurs within Axt, point x will
be covered at time t by a spherulite (Eder, 1997).
(Courtesy of Marcel Dekker, New York.)
ignored, the problem reduces to a purely
geometric problem provided the tempera-
ture gradients are small enough. In Fig. 5-2
the growth of a spherulite is symbolized on
the x-axis. If its growth starts at t-10 and the
temperature is varied during its growth, the
hatched area of Fig. 5-2 is obtained, where
the slopes of the two curves are equal at all
times except for the sign. If more spheru-
lites are nucleated at different times, a fam-
ily of curves are obtained, as shown in
Fig. 5-3, again where the curves have the
same slope at all times except for the sign
(as in Fig. 5-2). Now a kind of inverse
growth area Axt is drawn from the arbitrary
point xj backwards. Also for the confining
curves of this area, the respective slopes are
G{t). It becomes clear that the probability
n{xj) that at time t the point x is not swal-
lowed by any spherulite nucleated at an ear-
lier time is equal to the probability that with-
in the set Axt of Fig. 5-3 no nucleation has
occurred (k=0). In this way, the following
equation can be obtained from Eq. (5-4)
n{x,t) = (5-9)
This means that the degree of space cover-
ing is
(5-10)
The subscript "g" refers to the geometric
approach performed.
The set Ax t consists of all points (x\ t') of
our four-dimensional space for which the
distance between x and x is
x-x <r(t,t') with
(5-11)
Using Eq. (5-6) with/(x)= 1 (i.e., homo-
geneous nucleation in the unconfined three-
dimensional space), Kolmogoroff 's famous
equation (Kolmogoroff, 1937), is obtained,
i.e.,
(5-12)
jduG(u)
where a(t) is the nucleation rate at time t.
An additional equation for the number of
existing spherulites per unit volume is

obvious
Nc(t)= (5-13)
Both Eqs. (5-12) and (5-13) are not depen-
dent on the particular position. As can be
deduced from this derivation, these equa-
tions are the result of a correct stochastic
treatment of the problem. No "improve-
ments" are possible or desirable (Tobin,
1976), as long as the basic model remains
unchanged.
5.1.3 Some Special Cases
For the isothermal case, Avrami (1939)
assumed that a=0 and G = 0 for t < 0 and
a(t) = ~e~t/T and G{t) = Gc = const
(5-14)
for t > 0, with Nv being the number of poten-
tial nucleation sites per unit volume and x
being a mean activation time. Inserting
these assumptions into Eq. (5-12) gives
g (0 = 1 - exp [-8;r Nv G3 r 3 e4 (-t I x)]
(5-15a)
and
Nc(t) = (5-15b)
tlx
Nv \&u exp \-u - 8/r 7VV G3 T3
where e4(z)= X ~^ is an exponential rest
/=4
series. These equations contain the well-
known two limiting cases of a-const
(x> Oand a=NvS0(t), where 50 is the Dirac
function concentrated at t = 0 (x> 0). The
second assumption yields the familiar equa-
tions for a constant number of nuclei, i.e.
(5-16a)
and
(5-16b)
5.1 Fundamentals 277
where the exponent of Ms three ("Avrami
index" 3). For the first assumption an Avra-
mi index of 4 is obtained.
More importance has been ascribed to the
so-called isokinetic case. This case has been
constructed in order to enable the descrip-
tion of nonisothermal cases (Nakamura
et al., 1972). For this purpose the following
assumption was made for the nucleation rate
atf > 0
t
Au
-f- (5-17)
T()
with 7VV = const and with
G(t) x(t) = const = X (5-18)
defining a characteristic length A.
The latter equation expresses the isoki-
netic concept: The primary nucleation, as
governed by l/r(0, shows the same time
dependence (= temperature dependence) as
the secondary nucleation leading to G(t).
Here, again, the assumption is tacitly made
that, primarily, x and G are unique func-
tions of the temperature, which is related to
the time by the special heat transfer prob-
lem.
Equation (5-15 a) was obtained by partial
integration of the exponent of Eq. (5-12), in
which tlx is used as a new variable. The
same can be done when a dimensionless
time w defined by
( . _ r Au
v / J (5-19)
is used as the new variable. (In this equation
it can be assumed that the integration starts
at ?=0, because at temperatures above the
melting point the activation time is infi-nite.)
In this way, the following equations are
obtained for the isokinetic case
(5-20a)
278 5 Crystallization
and
(5-20b)
w(t)
Wv dw exp \-w - 8/r Ny A3
For us the most important result is the
final number of spherulites per unit volume
at t > oo, which forms a characteristic of the
obtained structure. Since w(i) usually goes
to infinity with time
Nc(oo)= (5-21)
Nv J Aw exp \-w - 8/r NY /L3
o
Because of this integral being a constant
independent of the thermal history of the
cooling process, the conclusion is reached
that the isokinetic approach is unable to pre-
dict a structure formation. The structure is
predetermined by the choice ofNv. The well-
known experience that, with many polymers,
the obtained spherulite number increases
strongly with increased speed of cooling, is
completely ignored by this approach. Even
the case where w(t) does not go to infinity,
which is the case when the glass transition
temperature is reached before crystallization
has finished, can only predict a smaller value
for the final number of spherulites than
Eq. (5-21). It remains questionable whether
the interaction of the evolved latent heat of
crystallization with the cooling process can
be described well enough with this method.
The present authors have warned their col-
leagues at several conferences, but so far
only a few have listened. For a correct treat-
ment of nonisothermal processes, a more
powerful method must be found. This meth-
od is described in the next section.
5.1.4 The Rate Equations
Because the equation of heat conduction
(or more generally the equation of energy in
a flowing system) is of the differential type,
it is not easy to combine this equation with
an integral of the type in Eq. (5-12). So it
has been considered useful to transform the
integral into a more suitable configuration.
This has been done by Schneider et al.
(1988) by differentiating the integral % in
the exponent of Eq. (5-12) step by step with
respect to time. With every step, a useful
auxiliary function cp{ is created. A system of
differential equations (the "rate equations")
is obtained in this way. It reads, in a slight-
ly modified version
(5-22)
for i= 1,2, 3 and p.(-oo) = 0.
The said auxiliary functions are
J dt'a(t') ]duG(u) (5-23)
where % is the (undisturbed) total vol-
ume of all spherulites grown per unit of vol-
ume
= An \ &t'a(t') jduG(u) (5-24)
being the total growth surface of the men-
tioned spherulites per unit of volume
&t'a(t') jduG(u) (5-25)
being 8/r times the sum of the radii of the
said spherulites per unit of volume and,
finally,
= Sn \&t'a{t') (5-26)
being 8/r times the number of these spheru-
lites per unit of volume, if impingement and
swallowing are disregarded. If the nuclea-
tion rate a(t) is required, Eq. (5-26) can be

differentiated another time. We obtain
(5-27)
Equation (5-22) is of particular interest for
/= 1. It reads, after rearrangement,
<Po(t) = G(t) <px(t) (5-28)
If impingement is taken into account, we
have
C^a\l) l~J\l) ip\ \J) e \Z)-Z*y)
This equation is obtained by differentiation
of Eq. (5-12). According to this equation,
the speed of crystallization is proportional
to the inner free surface <jf>i(l- g), which
is the only correct description of this pro-
cess.
If secondary crystallization can be disre-
garded in the course of a relatively fast cool-
ing process, the real degree of crystallinity
becomes
= />lg (5-30)
where p < 1 is the fraction of crystallinity in
the final product shortly after its manufac-
ture. If the equation of heat conduction is
written for a one-dimensional cooling pro-
cess, i.e.,
ul O 1 . ft /c ^5 1 \
= 0 _ ^ + _ (5-31)
it is immediately obvious the way in which
the equations are coupled by virtue of the
gradually evolved heat of crystallization h%.
In Eq. (5-31) a is the heat diffusivity of the
melt, c is its heat capacity, and h is the latent
heat per unit mass.
For the development of the morphology,
Eq. (5-13) can be used in its differential
form, which reads
lycyl) CX\T) e yD-JZ)
This equation can be integrated simulta-
neously with Eqs. (5-22), (5-27), and
(5-31).
5.1 Fundamentals 279
5.1.5 Nucleation Models
In the previous sections, the problem has
been solved in principle. But this does not
mean that practical use can directly be made
of these equations. Ways must be found to
determine the functions G{t) and a{t).
Major problems can be expected with
respect to the general form of the time and
temperature dependence of the nucleation
rate. From the examples given in the last two
sections, it is to be expected that a(t) will
not only depend indirectly on the time
through the time dependence of the temper-
ature, as is the case with the growth rate,
for which one has G(t) = G(T(t)) with G
describing the growth rate as a function of
the (instantaneous) temperature. For a(t), a
direct time dependence must also exist, as
Avrami's examples show.
Probably, the most general representation
of a (t) is in terms of an activation time spec-
trum (Eder et al., 1990), in analogy with the
well-known relaxation time spectrum of
viscoelasticity theory. In fact, at least three
mechanisms can be expected, i.e., thermal,
athermal, and heterogeneous nucleation
(e.g., Zachmann, 1964); in the latter case
various types of active centers can be
expected on a solid particle (edges, holes,
crystal surfaces). Hence
with (5-33)
ds
exp -J
The difficulty with such an equation,
however, is that it contains too many param-
eters that can never be determined experi-
mentally. In principle, there are two pos-
sibilities for simplification.
Avrami chose the case for a single mech-
anism with a constant N (number of nuclea-
tion sites) and a temperature-dependent acti-
280 5 Crystallization
vation time. In contrast to the isokinetic case,
a proof of deficiency cannot be given with
respect to the predictability of the structures.
On the other hand, as has been shown by
Mandelkern (1964), many crystallizable
polymers reveal an Avrami index of 3 at
slight degrees of supercooling, where the
processes are slow enough for the applica-
tion of traditional dilatometry. But an Avra-
mi index of 3 means that the activation time
must be so short that the limiting case
Bm(I- !->*(> (5-34)
is approached or, in other words, that the
activation time obeys the relation
\-l/3
(5-35)
where the right side gives the time needed
for the radius of a growing spherulite to
become of the order of the average distance
between nucleation sites. However, under
these conditions all potential nucleation
sites are activated even with slight super-
cooling. No additional sites are available for
crystallization at a lower temperature. But
this is in contrast to experience.
The only practicable alternative is to
assume a variety of activation temperatures
Tt for every type of nucleation, and to
simplify Eq. (5-33) by replacing the various
terms a((t) by Dirac functions concentrated
around the times when the sample temper-
ature T reaches the respective activation
temperatures during cooling. In other
words, the activation times T,, which are all
infinite at the melting point, jump from infi-
nite to zero one by one, when their activa-
tion temperatures T( are reached. It may be
noted that for athermal nucleation this
model can be particularly realistic because
of the fact that growth starts in this type of
nucleation around frozen-in fluctuations as
soon as their fixed size becomes critical dur-
ing cooling.
This latter model directly yields the num-
ber of nuclei per unit of volume as a unique
function of the temperature
N(T)= I Nj (5-36)
j with
Without further argumentation, such an
approximation has been proposed by Van
Krevelen (1978). Formally, in this case the
rate of nucleation becomes
(5-37)
at at
However, when the rate equations are
used, it is possible to start simply with
Eq. (5-26) instead of Eq. (5-27).
5.1.6 Influence of Temperature
Gradients x
Kolmogoroff s equation [Eq. (5-12)] and
its differential forms [Eqs. (5-22) and (5-
27)] describe spatially homogeneous crys-
tallization processes in unconfined samples.
However, due to the low heat conductivity
of polymer melts, rather remarkable temper-
ature gradients can result. For the first
attempt, these equations can be used with
the local kinetic quantities G(t,x) and a(t,x)
in Eq. (5-12). In this treatment only the local
temperature histories of small volume ele-
ments are taken into account, which are con-
sidered as a type of "physical volume ele-
ments" with their well-known restrictions:
small size compared with that of the appa-
ratus, but still containing many items.
In the preceding sections the assumption
was tacitly made that the crystallizing
entities are always spherical. This is, how-
ever, no longer true if the temperature gra-
dients become so large that the (tempera-
ture-dependent) growth speed G varies con-
siderably within one spherulite. Interesting
May be skipped at first reading.

derivations are given for such cases by
Schulze and Naujeck (1991), one of which
deals theoretically and experimentally with
the case where a single two-dimensional
spherulite grows in a stationary, linear field
of growth speed G(x) = G0(l +px) where Go
is the constant radial growth speed at x = 0.
Growth under these conditions results in
crystallites whose shape is again spherical.
However, the geometrical center of the
spherulite moves in the direction of the gra-
dient of the growth speed, and the radius of
the spherulite as a function of time is no
longer linear. The surface of a crystallite
nucleating at t = 0 and x = 0 is given by
(5-38)
with
xm(t) = g(pR(t))R(t)
(5-39)
r(t)=f(pR(t))R(t)
using
cosh(a)-l
u
f{^_ sinh(w)
and
R(t) = Got
Ifp R(t)<\, which is the case if the growth
speed variations in the spherulite are small,
concentric circles will grow with a constant
radial growth speed Go.
For a more realistic case we now study the
situation where the temperature field, and
thus the growth speed field, also varies with
time. As a first-order approximation one has
G(t, x) = G(T(t, x)) - G(T(t, *]
with (5-40)
If the coefficient p is not dependent on the
time t, for the shape of the crystallites the
5.1 Fundamentals 281
same formulae are obtained as given by Eqs.
(5-38) and (5-39), with R(t) = Got replaced
by
= \G(T(u,0))du (5-41)
To calculate the degree of crystallinity as
a function of the time and position we can
use Eq. (5-10). We only have to recalculate
the set Axt, which consists of all (nuclea-
tion) points Qc\f) leading to crystallites cov-
ering the point of observation x at time t.
After some elementary calculations, it can
be seen that this is the case if
[x'-xm{t\ t, x)f + ( / - yf < r{t\ t, xf
(5-42)
with
xm(t\ t, x)=x+(l+px) R(t\ t)g(p R(t\ 0)
r(f, t, x) = (\+px)R(t\ t)f(pR(t', 0)
and (5-43)
R(t', t) = R(t)-R(t')
As a next step, a(t\ x) has to be integrat-
ed in the integration domain given by
Eq. (5-42). In the case where the nucleation
rate is not dependent on xr(this assumption
seems to be reasonable because the third
power in G is of much more influence than
the first power in a), instead of Eq. (5-12)
the following result would be obtained for
the degree of crystallinity:
(5-44)
1 - exp -jdt'a(t')v(t',t,x)
with
According to Eq. (5-43), r{t\ t, x) is the
product of the factor (1 + p x) R (t\ t), which
is the radius of a spherulite growing under
282 5 Crystallization
local conditions with growth rate G(t,x) due
to Eq. (5-40), and a correction factor for the
gradient, i.e.,/(p/?(*', t)). Since/is an even
function with a lower limit of 1 and/(0) = 1,
we always have faster crystallization as com-
pared with crystallization under localized
conditions. If this factor/(/?/?(/^ t)) is close
to 1, the classical equation [Eq. (5-12)] is
obtained using the local kinetic parameters.
Deviations occur if the correction factor
f(pR(t', t)) becomes noticeably larger than
1 when the crystallization process has not yet
finished (i.e., when <^g < 1). In the case of
nucleation at time 0, i.e., a(t)=Nv80(t), a
simple criterion can be derived for the max-
imum tolerable temperature gradient. From
and the half time of crystallization for p = 0
given by
x _ J 3 In 2
the relative error at time tl/2 and x = 0 reads
* ( r 0 )
If this error is bounded by e, using series
developments for small and p and replac-
ing the function/(M) by 1 + w2/6 gives
2e
Vln2
With Eq. (5-40)
dT
3lnG
dT (5-45)
with
= 3.09
V31n2 Vln2
Allowing for a relative error of =0.05,
for the case of isotactic polypropylene
(i-PP) with typical values of l3lnG/3ri
= 0.2K"1 and N v =10 12 and 1015 nT3,
respectively, upper limits are obtained for
the temperature gradient of about 3xlO 4
and 3xl0 5 K/m, respectively, which are
frequently exceeded in practice.
5.1.7 Crystallization in Confined
Samples 2
Temperature gradients, as dealt with in
the preceding section, play a minor role if
the sample size or the cooling rate during
the crystallization process is small. Howev-
er, in both of these cases the influence of the
confining walls is important or even
becomes predominant. Kolmogoroff's
equation [Eq. (5-12)], however, describes
spatially homogeneous crystallization pro-
cesses in unconfined samples. Since in prac-
tice we always have confining walls or sur-
faces, which can even be active in the nucle-
ation process, there is a need to generalize
these equations for confined samples (Eder,
1997).
We deal here with the case of an infinite-
ly extended slab M of constant thickness D
(i.e., M=[-D/2, +D/2]xRxR) with bulk
nucleation and surface nucleation. Billon
et al. (1989) treated the case of isothermal
conditions and nucleation rates, as given in
Eq. (5-14). This approach was also later
generalized by the same authors for the non-
isothermal isokinetic case (Billon et al.,
1994), where temperature gradients within
the sample were ignored during the cooling
process (see Sec. 5.2.1). However, the con-
cept introduced in Sec. 5.1.2 also allows the
treatment of a more general nonisothermal
situation if the temperature gradients are not
May be skipped partly at first reading.

too large (see preceding section). We just
have to evaluate Eq. (5-10) using an appro-
priate intensity measure A, which due to the
two nucleation mechanisms is the sum of
two intensity measures
A = A2 + A3 (5-46)
with A3 being concentrated on M and A2
being concentrated on the surfaces of M,
i.e., on dM= {-D/2, +D/2}xRxR. Further-
more, we assume that within the sample as
well as on the surfaces we have no depen-
dences on the position. Thus we get
A3 [(x, x + dx) x (y, y + dy) x (z, z + dz)
x (f, t + dt)] = a3 (t) dt dx dy dz
if U K D/2 (5.4?)
A2 [{x} X (y, y + dy) x (z, z + dz)
x(t,t + dt)] = a2 (t) dt dy dz
if JC = D/2
and zero elsewhere. Here a2 is the surface
nucleation rate and oc3 the bulk nucleation
rate of the nucleation process. In this way
we obtain from Eqs. (5-10) and (5-11)
with
t
(po(t,x)= jdsa3(s) v(t,s,x)
and (5-48)
t
t,x)= jds a2(s) a(t,s,x)
The function v(t,s,x) is the volume of the
body, which a sphere with its center at x and
a radius r(t,s) [see Eq. (5-11)] cuts out of
the sample M. This may be either a full
sphere or a sphere truncated on one or both
sides by intersection with the wall. The
function a (t,s,x) is the area that a sphere with
its center at x and a radius of r{t,s) cuts out
of the sample surfaces dM. This is either
zero or consists of the area of one or two
disks.
5.1 Fundamentals 283
+D/2-
-D/2-
Figure 5-4. Classification of the variables t and x. For
explanation see text.
Table 5-1. Classification of variables {t,x).
Class Condition
1 \x\<D/2-R(t)
2+ \D/2-R(t)\<x<D/2
2- -D/2 <x<- ID/2 -R(t)\
3 \x\<R(t)-D/2
Next we introduce in Table 5-1 a classifi-
cation for the variables t and x (see also
Fig. 5-4), using R(t) = r(t, -). It is easy to
see that for (t,x) in class 1 and every s < t
the function v(t,s,x) is the volume of a full
sphere and a(t,s,x) = 0. For (t,x) in class 2+
or 3 (class 2 - or 3, respectively), we are able
to define auxiliary functions z+(t,x) [or
T_a*)] by
\
and (5-49)
t
J duG(u) = D
These functions give the time at which a
spherulite has to be nucleated at the right or
left surface, respectively, in order to reach
the position x within the slab exactly at time
t. If s represents an earlier time than z+(t,x)
[and/or r_(t,x)], then v{t,s,x) is a sphere trun-
cated at its right (and/or left) side, whereas
a(t,s,x) consists of disks from the right
(and/or left) sample surface. So, for exam-
284 5 Crystallization

pie, if (t,x) is in class 2+, for v(t,s,x) we may A set of rate equations equivalent to
have two cases depending on the particular those of Eq. (5-48) can now be derived, as
value of s, i.e., a full sphere or a sphere trun- Schneider et al. (1988) did with the clas-
cated at its right side. sical Kolmogoroff equation (see Sec.
Since our problem is symmetric with 5.1.4). First we define auxiliary functions
respect to x we may now assume x > 0, for / > 1
which simplifies further calculations.
Asymmetric cases with two different sur-
face nucleation rates on either side of the
slab may also be treated without difficulty. and
In our case we have T_(t,x) < T+(t,x). Using
h+(t,s,x) = r(t,s) - [(D/2) - JC] and h_(t,s,x) = Yi(t,x) =
r(t,s) - [(D/2) + x] (see Fig. 5-5) gives
with (5-52)
v(t,s,x) =
T+ < S < t G(t) dt
and
T_<S<T+
a{i)(t,s,x) = 1 3
G(t)dt'
fori>l.

(5-50) It is easy to see that vw = 0 for i > 4 and

a^ = 0 for / > 3. By successive differentia-
a(t9s,x) = tion we get the following set of rate equa-
0 T+ < S < t tions:
7ch+(2r-h+) z_<s<T+ (5-51)
~< Kh+(2r-h+)
+ 7th_(2r-h_)

dt

a3[T+(t,x)]
G(t)
G[r+(t,x)]
-D/2 +D/2
Figure 5-5. Schematic presentation of the intersec-
tion of a sphere with its center at x and a radius r(t, s)
with a slab of thickness D. (5-53)

and
a2[T-(t,x)]
+\2nG(t)
These equations are only valid for the
most complicated case, i.e., where (t,x) is in
class 3. For (t,x) in class 2+ or 1, the second
term in braces has to be replaced by zero,
for (t,x) in class 1 even the first term in bra-
ces disappears. These seven rate equations
have to be completed by two additional dif-
ferential equations for the quantities z+(t,x)
and T_(J,JC), which are obtained by differen-
tiation of Eqs. (5-49). They read
G(t)
G(T+(t,x)
and (5-54)
G(t)
dt
These equations are only applicable if (t,x)
is in class 2+ or 3 (first equation) and in class
3 (second equation). For the other cases, we
must replace the values of T+(t,x) and T_(t,x)
by -oo. The initial values for the functions
%, <p1? <p3, y/0, \j/x, y/2 are all zero.
In the case of unconfined samples (D >
oo), the variables (t,x) always belong to
class 1, and the rate equations under Eq.
(5-53) are exactly reduced to the rate equa-
tions by Schneider, i.e., Eqs. (5-22) and
(5-26).
5.1 Fundamentals 285
Let us now have a closer look at the crys-
tallization process if only bulk nucleation
[with 02(0 = 0, generating %3(t,x)], or only
surface nucleation [with a3 (t) = 0, generat-
ing 2(t,x)], is occurring. Under these cir-
cumstances
or (5-55)
With Eq. (5-48), for the combined process
we get
(t, x) = %2 (t, x) + 3 (t, x) - 2 (r, x)%3 (r, x)
(5-56)
The time derivative of this equation reads
+E (tx)\l- (t x)] (5 57)
"
The first term on the right side of this equa-
tion describes the increase of crystallinity
by the surface-nucleated spherulites multi-
plied by the probability that at time t point
x is not covered by bulk-nucleated spheru-
lites. Thus for the degree of crystallinity
%(2)(t,x) due to surface-nucleated crystal-
lites in the presence of bulk nucleation we
have
(5-58)
and in an analogous way for the degree of
crystallinity %(3)(t,x) due to bulk-nucleated
crystallites in the presence of surface nucle-
ation we obtain
Instead of Eq. (5-56) we now get the fol-
lowing simple addition for the crystalliza-
tion process in terms of (2) a n ^ o>
(t Y\ % (t r\ . % (t r\ (* ftm
286 5 Crystallization

The quantities <^(2) and <^(3) may be calcu- is initiated per unit of surface area on both
lated easily in a general situation using aux- sides of the slab. In Eder (1997) it has been
iliary functions, as introduced in Eqs. (5-48) shown that the solution of this problem can
and (5-52), i.e., be written as

xexp[-(po(t,x)-y/o(t,x)] with
and (5-61) (5-66)

and

Most interesting for practical purposes is the

case t > oo, i.e., the final profiles ^(2)(,x) with two auxiliary functions
and ^(3)(OO,JC), because these profiles can be
determined from experiment through opti-
cal investigation of the cross sections of the if r' < (1 - JC')
6
samples (seeFigs. 5-13 and5-14). Forthese
profiles we have, from Eq. (5-60) 6 24
(2) (oo, JC) + (3) (oo, JC)= 1 (5-62)
f'3_JL
For the number of existing bulk-nucleat- 6 24
ed spherulites per unit of volume N3iC(t,x)
and surface-nucleated spherulites per unit i f / ' > ( ! + *')
surface area N2c(t) we have, similar to
Eq. (5-32) and (5-67)
(5-63) g(t',x') =
xexp[-(po(t,x)-y/o(t,x)] 0 if f <{\-x)
2,c if) = a2 (t) (5-64)
xexp[-(po(t,D/2) y/o(t,D/2)] if (!-*')<*'

This section is finished with a simple

example concerning the isothermal case,
and is comparable to Avrami's case, as given
in Eq. (5-16), i.e.,
The solution written in dimensionless coor-
dinates (t\ x) is dependent on only two
parameter combinations, i.e., on
and (5-65)
^ _ 1
G = const
At time = 0, a number of A^v spherulites is and (5-68)
nucleated per unit of volume in the bulk of
the material and a number of NA spherulites

d A =10
d v =10
0.175
0.15
0.125 N 0.15
d v =0.1 t'=0.1
\\
0.075
0.05
0 i i i i i i i i i
0 1 0
Figure 5-6. Crystallinity profiles under isothermal conditions for various combinations of the parameters dw
and dA according to Eq. (5-66).
which are the characteristic distances
between neighboring bulk nuclei and sur-
face nuclei, respectively, on the length scale
of the sample thickness D.
In Fig. 5-6, crystallinity profiles are given
for the combinations of parameters, dA,
dw = 0.l, 1, and 10. If both dA and dv are
large compared to 1, growth from very few
nuclei is observed. This comes down to a 2D
growth of NVD + 2NA disks (of thickness D)
per unit of area. The crystallinity profiles
are uniform across the slab thickness (upper
left diagram in Fig. 5-6). In the case dA>\
and dv < 1 (lower left diagram), where
many bulk nuclei and only few surface
nuclei are present, crystallinity profiles are
obtained that are always flat in the center
and, for short times, drop to half the center
5.1 Fundamentals 287
d A =0.1
0.175
0.125 N
t'=0.1
\
0.075
0.05 \
i i i i i
1 0
value near the surface (x ~ 1). This behav-
ior is due to the fact that, initially, for a point
near the surface the probability of being
covered by some spherulite is exactly half
the probability observed for a point near the
center, because only half of the surrounding
volume of a surface point is filled with crys-
tallizable material. In the upper right dia-
gram (dA<l and dw>l), where there is
dense nucleation at the surfaces only, after
a short time, a frontlike growth occurs from
the surfaces towards the center, resulting in
a process which proceeds linearly with time.
If both dA and dv are small, a superposition
of frontlike (one-dimensional) growth from
the surfaces and uniform (three-dimension-
al) growth in the bulk of the sample is
obtained.
288 5 Crystallization

Table 5-2. Dimensionless time of half crystallization

and effective Avrami indices for various combinations
of dA and dy.

dA == 10 dA=l </A = 0.1

dv=\0 (6. 58/2.06) (1.11/3 .22) (0.513/1 .47)

dv=\ (1. 19/2.69) (0.904/2 .95) (0.483/1 .54)
dw = 0.l (0.1 11/2.97) (0.111/2 .97) (0.108/2 .95)
0.2 -

0.0
In Table 5-2 a compilation is given of the 0.0
dimensionless time t[/2 when the mean x'=2x/D
degree of crystallinity is 1/2, i.e., when
Figure 5-7. Final profile of the degree of crystallin-
ity due to bulk-nucleated spherulites in the presence
(5-69) of surface nucleation.

together with an effective Avrami index [see passes the position x. Thus
also Eq. (5-16 a)] defined as
(5-71)
(5-70)
d[ln(O] t'=t'\,2
= l-exp -
The effective Avrami index varies within the DJ
chosen set of values for dy and dA between
In particular the position JC1/2, at which we
1.47 and 3.22 (!). This is an effect of the spa-
have ^(3)(o, *1/2) = 1/2, can be used in this
tial arrangement of the nuclei only, while the
case to determine the number of nuclei in
spherulites themselves grow three-dimen-
the bulk
sionally, leading to an Avrami index of 3.00
in an unconfined volume.
Nv = 61n2 1
(5-72)
The crystallinity profiles (2)(f,Jc) and n (D-2xl/2y
%^(t,x) cannot be calculated analytically.
Similar considerations will be necessary
Some of the numerically calculated final
for the cases where the growth of two crys-
profiles (3)(, x) are shown in Fig. 5-7 for
tal modifications compete in the bulk, or
the parameter combinations used in Fig.
where two types of (compatible) polymers
5-6. In some limiting cases, however, we
start crystallizing in the bulk.
also have analytical solutions. If both dY and
dA are large, the final profile (3)(, x) is
constant with a value of 1/[1 + 2NA/(DNW)]. 5.2 Experiments in Quiescent
If dA is small, a superposition of a sharp
frontlike growth is obtained starting at the
Melts
surfaces with some process nucleated in the
5.2.1 Differential Scanning Calorimetry
interior. In this case the final profile
(as Applied to Isotactic Polypropylene)
(3)(oo, x) is given by the degree of crystal-
linity reached by the bulk-nucleated process This most popular type of thermal mea-
at the time when the crystallization front surement also attracted our attention in con-

nection with our search for physical data.
We found that, in principle, we were able to
determine the number of nuclei and the
growth speed as functions of the tempera-
ture. This statement, however, deserves
some elucidation.
To begin with, we have to investigate the
internal heat transfer problems arising at
higher cooling rates, which are needed for
the investigation of the crystallization kinet-
ics at lower crystallization temperatures. In
fact, it is well-known that the exothermal
peak of the differential scanning calorime-
try (DSC) curve shifts to lower temperatures
with increasing cooling rates.
The following balance equation was for-
mulated (Janeschitz-Kriegl, 1992, 1994;
Janeschitz-Kriegl et al., 1993 a, b; Eder and
Janeschitz-Kriegl, 1993; Wu et al., 1993)
-(ra p cp + ras
At At (5-73)
where mp and ms are the masses of the DSC
pan and of the sample, cp and cs are the cor-
responding heat capacities, h is the specific
heat of crystallization, Ts is the temperature
in the mid-plane of the sample, % is the
degree of crystallinity, 7 is an effective heat
transfer coefficient and
Tf(t) = Tfr + tft (5-74)
is the furnace temperature as a linear func-
tion of time, with ff < 0 the constant cool-
ing rate and Tfr the starting temperature of
the furnace.
The determination of the heat transfer
coefficient / i s based on the fact that the
DSC signal returns to the base line accord-
ing to an exponential function of time as
soon as the phase transition is complete. In
fact, for A%/At=O the solution of Eq. (5-73)
reads
(5-75)
5.2 Experiments in Quiescent Melts 289
with
a = m c r+ m c (5-76)
p p s s
where T{ can be any initial temperature, and
the base line is
r b (0 = r f (0- (5-77)
with Tf(t) according to Eq. (5-74). The DSC
signal itself is given by
0(t) = y[Ts(t) - Tb(t)] (5-78)
where & is the heating power.
If \ff\ln<P is now plotted against Tf
which, according to Eq. (5-74), takes over
the role of a time parameter, we have
f (5-79)
For a series of cooling runs (with varying
values of Tf), it is important that the sam-
ples fit exactly into the pan. Otherwise the
heat transfer coefficient /would vary too
much. The same sample cannot be used for
all runs with our strategy, because each sam-
ple is needed after the relevant cooling run
for a microscopic investigation, as we shall
see below.
In Fig. 5-8 a relevant plot is shown for an
industrial polypropylene. The cooling rates
are indicated near the curves. The expected
linearity and parallelism is clearly shown.
The slight curvatures at the lower ends of
the curves must be ascribed to small errors
in the base-line position. From the common
slope a, a value of y= 10 mW KT1 can be
deduced with the aid of Eq. (5-76) by insert-
ing the values of mp, ras, cp, and cs. If the
apparatus is calibrated with indium, a high-
er value of the heat transfer coefficient (=16
mW K"1) is obtained in accord with the fact
that metals have a higher heat conductivity.
For completeness it must be mentioned that
in these experiments three little knobs were
punched into the bottoms of the pans with
290 5 Crystallization
30 40 50 60 70 80
furnace temperature Tf [C]
the aid of a special tool. In this way the
reproducibility can be increased but, at the
same time, the heat transfer coefficient is
lowered a little bit. In a special publication
(Wu et al., 1993) it was shown that such a
measure improves the validity of the
approximation represented by the balance
equation [Eq. (5-73)].
If, in this balance equation, the time is
replaced with the aid of Eq. (5-74) by Tf and
an integration is carried out with respect to
this latter variable, we get
OC
(5-80)
Because of the starting temperature (Tfr)
of the furnace being outside the peak area
on the high temperature side, only the lower
limit Tf of the integral is of importance. If
Tf is chosen at the lower end of the temper-
ature scale of the furnace, i.e., also outside
the peak area, the well-established integral
is obtained over the whole peak which, as is
well-known, must be equal to p ms h I ff\
(because % = p%g with g = 1 at the lower end
of the scale). In fact, &(Tf) becomes zero as
soon as the base line is reached. However,
if Tf is chosen inside the temperature range
Figure 5-8. Plot of DSC curves
for an industrial polypropylene
(Daplen KS 10) according to
Eq. (5-79). The cooling rates
applied are indicated near the
curves (Janeschitz-Kriegl, 1994).
(Courtesy of Hiithig & Wepf Ver-
lag, Basle.)
90
of the peak, the first term on the right side
is of importance. So far, however, everyone
has overlooked the presence of a term that
is influenced by the heat transfer coefficient
through a. Equation (5-80) enables us to cal-
culate the progress of the crystallization as
a function of the time variable Tf. This is
shown on the left curve of Fig. 5-9 for the
industrial polypropylene of Fig. 5-8 and a
cooling rate of 100 K/min.3 Such a high
cooling rate is not easily achievable, as can
be seen from the next figure (Fig. 5-10). In
this figure the furnace temperatures are indi-
cated at which the control system of the
machine stopped to function at the various
cooling rates. Liquid nitrogen is strictly nec-
essary as a coolant for these measurements.
As can be seen, a cooling rate of 200 K/min,
which is only 3.33 K/s(!), cannot be realized
at all. (Later we shall return to the discus-
sion of this restriction in connection with the
determination of data that are relevant to
real processing conditions.)
3
The authors are very much indebted to Philips
Research, Eindhoven, The Netherlands, for enabling
two of our co-workers (P. Jerschow and C. Paulik) to
carry out these measurements on a properly equipped
machine.
 5.2 Experiments in Quiescent Melts 291

1,0

0,8
tf = -100 K/min
a = 0,16/s
0,6 y = 10,0 mW/K
ms = 15,9mg
m = 25,4 mg
p
0,4

0,2
-UTf)
0,0

20 40 60 80 100 120

T,[C],Tf[C]
Figure 5-9. The left curve gives the course of the crystallization of the polypropylene of Fig. 5-8 at a cooling
rate of 100 K/min, according to Eq. (5-80). The furnace temperature Tf takes over the role of time according to
Eq. (5-74) (Janeschitz-Kriegl, 1994). The right curve gives the course of the crystallization as a function of the
real temperature Ts in the sample.

250

200

150

100 -200 K/min "

100 K/min
- 80 K/min
50 - 60 K/min
- 4 0 K/min
20 K/min
- 10 K/min

50 100 150 200 250

Tf[C]
Figure 5-10. Directly measured heating power (uncorrected DSC curves) for seven runs at the indicated (nom-
inal) cooling rates for the polypropylene of Fig. 5-8. For the three highest cooling rates, the incipient failure of
the control system is indicated by full circles on the curves. The parts (of the curves) to the left of these points
are unreliable. The double arrow gives the restricted range in which the crystallization temperatures are actual-
ly located for cooling rates between 10 and 100 K/min (Janeschitz-Kriegl, 1994). (Courtesy of Huthig & Wepf
Verlag, Basle.)
292 5 Crystallization
Another important point is that, at higher
cooling rates than, e.g., 5 K/min, correction
of the peak temperature becomes strictly
necessary. In other words, the temperature
in the sample, where the crystallization
occurs, can become quite different from the
furnace temperature at the maximum of the
DSC peak. In fact, according to a combina-
tion of Eqs. (5-77) and (5-78), the internal
temperature in the sample is given by
(5-81)
a y
If this transformation of Tf(t) into Ts(t) is
applied to the abscissa of Fig. 5-9, the right
curve of this figure is obtained, which shows
that crystallization occurs virtually at a con-
stant internal temperature of 99 C in the
present case. If the left curve is differentiat-
ed with respect to time (r f c t), multiplied
by ms /z, and plotted against Tf(t), the right
curve of Fig. 5-11 is obtained, showing the
heat evolved by crystallization against the
furnace temperature. It cannot be consid-
ered, however, as an ideal DSC curve,
because the relevant cooling rate is not con-
tf = -100 K/min
150
a = 0,16/s
mW
Y = 10,0 mW/K
= 15,9mg
100 m
p
= 25,4 mg
-m
50
20 40 60 80
stant owing to the heat transfer problem
involved. In Fig. 5-11 the usual exothermal
DSC peak is plotted as the left line (cooling
rate 100 K/min).
As a next step we have to report on the
evaluation of the cross sections that were cut
from the samples removed from the DSC
pans after the runs. Photographs were taken
of these cross sections under a polarizing
microscope. On these photographs the num-
bers N of spherulites per unit surface were
counted. To a good approximation, the cor-
responding numbers per unit of volume TV
are simply (N)3/2. This method is indepen-
dent of the knowledge of G. This is a great
advantage, as will be seen below. The
obtained values of N are, of course, the min-
imum possible N-values. However, they
give just the information needed for our
approximate model, in which N is given as
a unique function of the temperature, as in
Eq. (5-36). (Remember the Dirac functions
are immediately activated when their acti-
vation temperatures are reached. For a sin-
gle activation mechanism, the Dirac func-
tion concentrated at zero time means a con-
Figure 5-11. The left curve
gives the exothermal peak
of the DSC curve for the
polypropylene of Fig. 5-8
at a cooling rate of
100 K/min. The right curve
is the heat evolved in the
time span represented by
the span of Tf. Both lines
are drawn against the fur-
nace temperature Tf.
100 120

i*io n -
1x10
105 110 115
Crystallization Temperature [C]
stant number of nuclei from the beginning,
so that all the nuclei can grow out into sphe-
rulites.)
In Fig. 5-12 the result of this determi-
nation is plotted as the number of nuclei
per unit volume against the real crystalliza-
tion temperature, as given by Eq. (5-81).
It can be seen that, for the investigated
industrial polypropylene Daplen, KS 10
(Mz= 1400000, Mw = 330000, Mn = 52000,
solubility in cold xylene: 2-3%), the num-
ber of nuclei increases by about two decades
when the crystallization temperature is low-
ered from 125 to 105 C. For completeness,
in Figs. 5-13 and 5-14 photographs are
shown of cross sections of samples from the
same polymer, after cooling runs of 5 and
50 K mnT1. The differences in the structures
are clearly seen. In particular, at the lower
cooling rate part of the crystallization is
caused by nucleation at the wall of the pan.
This transcrystallization becomes more and
more important with lower and lower cool-
ing rates, and can even cause a small shoul-
der on the high temperature side of the DSC
5.2 Experiments in Quiescent Melts 293
Figure 5-12. Number of spherulites per
unit volume against true crystallization
temperature for the polypropylene of
Fig. 5-8. (Unpublished work by C. Paulik.)
120 125
peak (Billon et al., 1994; Eder and Jane-
schitz-Kriegl, 1993). The theoretical treat-
ment of such a situation has been sketched
in Sec. 5.1.7 [see also Eder (1997)]. From a
practical point, however, low cooling rates
are not so important. It will also be particu-
larly difficult to find the numbers of nuclei
per unit surface at the wall and per unit vol-
ume in the melt simultaneously.
Finally, we arrive at the interpretation of
the left curve in Fig. 5-9. Because of the fact
that the crystallization occurs practically at
a specific constant temperature, Avrami's
equation [Eq. (5-16 a)] for an index of 3 can
tentatively be applied, i.e.,
(5-82)
with t0 being the time when the actual crys-
tallization temperature is reached.
The shape of the left curve in Fig. 5-9 sug-
gests that the best way of evaluating the
parameter G (AT being known from the just-
mentioned procedure) is to take the time
derivative of <L at <^ =0.5. This differentia-
294 5 Crystallization

Figure 5-13. Cross section

through a sample of the
polypropylene of Fig. 5-8,
as obtained from the DSC
pan after a cooling run of
5 K/min.

Figure 5-14. As in Fig.

5-13, after a cooling run of
50 K/min.

tion yields for t=tU2 (with g = 1/2)

2/3
^yVG3(?1/2-?o)3=ln2
(5-83)
= 1.894Nin G
Introducing 7f instead of t finally gives
This result is explained by the fact that the
exponential function remains intact during
G(T) = 0.528 (5-84)
the differentiation and that Eq. (5-17) yields W(T)

1x10 I I
lxl(T
I lxl 7
s lites of the polypropylene of Fig. 5-8 as a
O lxlO'8
lxlCP
100 110 120 130 140
Temperature (C)
In this equation d^g/dTf and ff are both
negative, so their product is positive. With
the aid of this equation, the G values are
obtained; these are plotted in Fig. 5-15
against the crystallization temperature with
the aid of filled symbols. Unfortunately, the
DSC values cannot be extended to higher
temperatures because of the growing and
disturbing influence of transcrystallization.
The curves obtained at higher temperatures
with the aid of optical measurements will be
discussed in Sec. 5.2.2.3. In previous mea-
surements we have used transcrystallization
with a steep temperature gradient (in order
to suppress the diffuse nucleation in the
bulk) in order to obtain G values at lower
temperatures. Discrepancies must be
cleared up before the sketched DSC meth-
od can be used for high density polyeth-
ylene, for which so far only a few values
of G(T) have been obtained in the tempera-
ture range relevant for practical process-
ing. With high density polyethylene, elec-
tron microscopy is needed to count the
spherulites in the cross sections of DSC
samples.
5.2 Experiments in Quiescent Melts 295
Figure 5-15. Growth speeds of spheru-
function of the crystallization tempera-
ture, according to Eq. (5-84) (unpublished
work by C. Paulik, E. Ratajski, and G.
Eder). Solid line from optical measure-
ments.
5.2.2 Other Measurements Concerning
the Growth Speed
of Isotactic Polypropylene (i-PP)
In principle, the reliability of the growth
data, as obtained from DSC measurements,
can only be enhanced by comparison with
the results of alternative methods. A num-
ber of these methods will be discussed in the
following sections.
5.2.2.1 Dilatometry
This method has been used successfully
for the investigation of the overall rates of
crystallization by Boon et al. (1968 a, b). In
particular, it was applied to isotactic poly-
styrene (PS), which is a very slowly crystal-
lizing polymer. In this context the density
measurements of van Antwerpen and van
Krevelen (1972) on samples of polyethylene
terephthalate (PETP) should also be men-
tioned. This polymer also crystallizes rath-
er slowly and has the advantage that the den-
sities of samples quenched from several
crystallization temperatures after several
296 5 Crystallization
crystallization times to room temperature
can be measured in a density column. How-
ever, for quickly crystallizing commodity
polymers, like polyethylene (PE) or isotac-
tic polypropylene (PP), this type of mea-
surement cannot be applied.
5.2.2.2 Optical Measurements
First we must mention hot stage micros-
copy, which has been used quite successful-
ly both for the determination of the numbers
of nuclei and for the growth speeds at not
too high degrees of supercooling. In this
context the works of von Falkai (1960) and
Padden and Keith (1959) on polypropylenes
should also be mentioned. Lovinger et al.
(1977) took pictures in a temperature gradi-
ent for the first time using this method.
Magill et al. (1973) have carried out a tre-
mendous amount of measurements on spe-
cially prepared polymers of sufficiently low
rates of crystallization. It would be possible
to write a special review on all these mea-
surements, including very recent develop-
ments. In the present context, however,
results from von Falkai (1960), Padden and
Keith (1959), and Lovinger et al. (1977)
will be used to complement the results
that have been obtained for isotactic poly-
propylenes by the faster methods described
below.
Light scattering should also be mentioned
here. An interesting method of measuring
depolarized light scattering, as caused by
the formation of spherulites [four-leaved
clover patterns, as detected and interpreted
by Stein's school (Stein and Rhodes, 1960;
Stein and Misra, 1973; Stein et al., 1977;
Higgins and Stein, 1978)], has also been
used by van Antwerpen and van Krevelen
(1972) for PETP and by Keijzers (Keijzers,
1967; Keijzers et al., 1968) for isotactic PS.
However, as Keijzers pointed out, the sphe-
rulites of isotactic PP are not sufficiently
regularly built for the application of this
method. Also, some still unpublished meas-
urements in our own laboratory indicated
that quickly crystallized samples of PP and
PE did not show noticeable depolarization
effects. As will be shown below, however,
another quite simple interpretation of
increasing light scattering, as occurs during
rapid crystallization, has been successfully
used in our laboratory (see Sec. 5.2.2.4).
5.2.2.3 Transcrystallization4
On this occasion the reader is reminded
of Fig. 5-1. From this figure we learn that,
depending on the ratio of the average dis-
tances of nuclei on the wall and in the bulk,
the crystallization front, starting at the mold
wall, is superseded earlier or later by a dif-
fuse crystallization zone. However, in order
to suppress the occurrence of the diffuse
crystallization zone, we created a steep tem-
perature gradient in the sample. This can be
achieved in a rather thin tablet of the sam-
ple. This tablet is quenched to the desired
crystallization temperature on one side only,
whereas the other side is kept at the origi-
nal high temperature. An additional advan-
tage is that in a rather thin tablet the transi-
tion to a linear temperature profile occurs in
a rather short period of time, before the layer
growth from the quenched surface becomes
considerable.
In Figs. 5-16 and 5-17 two situations are
depicted. In both cases the mentioned wall
was quenched from 200 C to a temperature
in the range where the growth speeds are
close to their maximum, i.e., 100 C in both
cases. As is well-known, this maximum
occurs somewhere half-way between the
melting point and the glass transition tem-
perature (Magill et al., 1973). In the first
picture, a layer is shown which is obtained
Wunderlich(1973).
 5.2 Experiments in Quiescent Melts 297

Figure 5-16. Transcrystal-

lized layer of the a-modifi-
cation after quenching the
lower side to a temperature
of 110C for a contact time
of 48 s. Notice the bright
/3-cones! Incidentally, the
apex of the cone in the mid-
dle is practically in the sur-
face of the cross section,
hence "Lovinger's angle"
can easily be determined.
Thickness of a-layer:
0.15 mm.

Figure 5-17. Transcrystal-

lized layer of the /3-modifi-
cation with "a-spherulites"
included. For this purpose
the surface (lower side) has
been treated with Cinqua-
sia-gold. Temperature of
the quench 110 C, contact
time 80 s. Thickness of
/3-layer: 0.105 mm.

after a "contact time" (i.e., the time between
first and final quench) of 48 s. Because no
special precautions were taken, the layer is
mainly built up of the a-crystal modifica-
tion5. However, /3-nucleation could not be
5
The term a-modification stands here for the
spherulites of low positive birefringence, reportedly
of the monoclinic type (Norton and Keller, 1985). A
similar remark holds for the spherulites of high (neg-
ative) birefringence of the j3-type of hexagonal sym-
metry.
excluded completely. As a consequence,
several bright cones are visible between
crossed polars. [Because of epitaxial
growth, the birefringence of the ce-modifi-
cation is much lower (Padden and Keith,
1959).] According to Lovinger et al. (1977),
the ratio of the growth speeds can be calcu-
lated from the opening angle of the cones:
The speed of the /3-modification is shown to
be a factor of 1.27 higher in the demonstrat-
ed cases. As the ^-modification dominates
298 5 Crystallization
at the front of the layer, the conclusion must
be drawn that, in contrast to the results
obtained at higher temperatures of the
quenched wall, there is no reliable way to
determine the growth speed of the a-mod-
ification from transcrystallization in a tem-
perature range between 115 and 90 C. This
was shown by Ratajski (1993).
On the other hand, preparation of the sam-
ple surface with a nucleation agent for [3-
nucleation [Cinquasia-gold (Leugering,
1967)] leads to a transcrystallization layer
of the latter modification, as shown in
Fig. 5-17 [see Ratajski (1993)]. Some of the
a-spherulites show the shape of a pear with
its stem in the growth direction, as first
observed by Lovinger. But these inclusions
do not seriously disturb the advance of the
layer front. In principle, the growth speed at
the temperature of the quenched wall is
obtained by plotting the layer thicknesses,
as determined under the microscope on
cross sections of the completely solidified
samples, against the contact times. The
initial slopes of the obtained curves give the
required growth speeds at the wall (Jane-
schitz-Kriegl et al., 1987 a). However, as is
well-known, it is difficult to draw such an
initial slope on the basis of scattered experi-
mental points.
In order to cope with this problem, a
curve-fitting method has been developed
(Eder, 1993) [see also Ratajski (1993); Ra-
tajski and Janeschitz-Kriegl (1996)], which
is based on the following assumptions:
a) In the vicinity of the wall temperature Tw
the growth speed as a function of the tem-
perature can be approximated by
G(T) = G w e x p [ - p ( r ~ r w )] (5-85)
where Gw is the growth rate at the wall
temperature and /3 is the temperature
sensitivity coefficient of the growth rate.
b) The evolution of the latent heat of crys-
tallization has no important influence on the
temperature in the sample (Eder et al.,
1990), if the temperature gradient is steep
enough.
c) The heat diffusivity a is considered to be
independent of the degree of crystallinity.
d) The Fourier number
(5-86)
D2
(with D the sample thickness and t the time)
is large enough for a practically linear tem-
perature profile to exist when the first mea-
surement is taken. In fact, this holds for Fo >
0.5. With D= 1 mm and a= 10"7 m2 s"1, this
means
t>5 s (5-87)
With these assumptions and with x as the
distance of the crystallization front from the
wall, we get
x(t) = Gw (5-88)
where G is put equal to i, T{ is the initial
temperature, and Tw is the wall temperature
after the quench. This is a differential equa-
tion for x(t), which can easily be integrated.
The logarithmic version of the solution of
this differential equation reads
with
D
r= (5-89b)
For several assumed values of r, the sec-
ond term of Eq. (5-89 a) is calculated as a
function of time. Such a plot is given in
Fig. 5-18, where a logarithmic time scale is
also used for t for convenience. On log [x(t)]
vs. log(0 scales the experimental points are
shifted in a vertical direction until the best
fit with the shape of one of the theoretical
curves is obtained (see the crosses in the fig-
 5.2 Experiments in Quiescent Melts 299

ure). In this way a value of r is obtained. ments on the hot stage of a microscope. In
According to Eq. (5-89 a), the vertical shift the range of overlap the agreement is quite
of log x(t), which leads to the described good. On the other hand, it becomes quite
curve fitting, gives a (quite reliable) value of obvious that the use of transcrystallization
Gw. A rather inaccurate value of /? can also extends the range of measurements over as
be calculated from the obtained value of T. much as 30 degrees to lower temperatures.
In Fig. 5-19 the results obtained with the For a calculation of the growth speeds of the
aid of this method are presented (full cir- a-modification from these data, with the
cles) together with Lovinger's values (open aid of the mentioned cone angles (see Fig.
rhombs) and some of our own measure- 5-16), Sec. 5.2.2.6 on data compilation
should be consulted. In fact, the data for
the a-modification are of greater impor-
P-PP = -100 ,
tance, because PP crystallizes mainly in the
T=120C a-modification if no special nucleation
log(G[m/s])=-5.848
agents for the /^-modification are applied.

5.2.2.4 Crystallization Zone 6

Again, the reader is reminded of Fig. 5-1.
This time the diffuse crystallization zone is
considered. In Fig. 5-20 this zone is meas-
ured for an industrial PP (Daplen PT 55) for
log(t) several temperatures of the quenched wall,
Figure 5-18. Curve fitting for the determination of as indicated near the agglomerations of
the growth speed G, as explained in the text. Temper-
ature of the quench 120 C. Logarithm of the time of
thermal adjustment 0.7. Ederetal. (1990).

90 100 110 12C) 130 140

i | r
! !

-5- -5

* : :
p-Polypropylene j "
'
i
:
' radial growth rate 1 Figure 5-19. Growth speed
. ' '.
of /3-spherulites as a func-

tion of temperature, as
ST -6- - -6
: : : o : :
obtained from transcrystal-
o
o lization experiments
: ; : co : :
: : o ; ; (closed circles) (Ratajski
o : <
- -7 and Janeschitz-Kriegl,
2 -7- o 1996), optical microscopy
Ratajski/optical
(closed squares) (Ratajski
Ratajski/front growth data : <>o ;
o Lovinger
: o :

and Janeschitz-Kriegl,
-8- 1996), and from zone crys-
tallization by Lovinger
et al. (1977) (open rhombs).
90 100 110 120 130 140
Temperature (C)
300 5 Crystallization

1
i 1 1
X
XX
X X X X
XX
XX
100C
X X X
X X X X
X X X XX
X XX X X X
X X X X
XXX
XX
XXX X
X

XX
XXX >(
X X
XXX x
D
oD 1 10C
X XX
x D D DCD
X XX an a D DO
XX CD D D
- X D a CD
an o o o o o
a
o o o
D
XX
XXX c r D o o o
V D
m
D
CD O OO
o o
X
X
x
D
D
D o
o
OO O O o 120C
a o
X
D o o o
Q oo
CD OO
~ X D 0
m o

X DD oSo + + +
+ + +
x nn
DD
oS
X D og^ + + + +
+
130C
OO

x a? O
X
OO + +-r + +
a 1 1 + + -H 1 I

) 500 1000 1500 20(

t [sec]
Figure 5-20. Progress of diffuse crystallization zones (compare with Fig. 5-1) for i-PP Daplen PT 55 with time.
The temperatures of the quenched wall are indicated near the "curves", which are according to Ratajski (1993).

points indicating the respective zones zone advanced, larger and larger portions of
(Ratajski, 1993). The initial melt tempera- the microscale became undiscernible. (The
ture Tx was 200 C after slow cooling from advancement of this zone cannot be
240 C. For these measurements a cylinder observed with the aid of a cathetometer from
of the polymer of 20-mm diameter and about outside because of the bending that light
10 mm in height was used. This sample was rays experience in a strong temperature gra-
melted in a glass tube in which hollow metal dient.)
pistons were inserted from both ends, touch- Previously, we tried to calculate the
ing the polymer cylinder with their end sur- shapes of the zones by drawing lines at
faces. The polymer sample contained a degrees of crystallinity of 0.2, 0.5, and 0.8.
microscale printed on a little strip of paper. These lines were obtained with the aid of
This scale was situated along the central line Schneider's rate equations (Eq. (5-22) using
and touched the piston to be quenched. For preliminary data for G(T) and N(T) (Eder
the quench of this piston, which was effec- et al., 1990; Ratajski, 1993). In this way we
tuated with the aid of a heat-transfer fluid could show that these shapes were in qual-
pumped through its interior, a time of about itative agreement with theoretical expecta-
3 s was required. The microscale was tions. Recently, however, we have discov-
observed with the aid of a telescope which ered that the locations on the time axis where
was inclined at an angle of 30 with respect the respective zones become apparent are
to the end surfaces of the sample. (Because accessible to a quantitative interpretation.
of the larger refractive index of the sample, For this purpose it has to be realized that,
an angle of about 20 resulted inside the at the chosen wall temperature, crystalliza-
probe.) When the diffuse crystallization tion starts in the bulk of the fluid by the for-

mation of little Ray lei gh scatterers. (The
transcrystallizing boundary layer, which
cannot be disregarded at the higher wall
temperatures, does not disturb the observa-
tion of the initiation of the diffuse zone.) For
Rayleigh scatterers, however, the intensity
of light scattering grows with the square of
their volume. Because of this volume being
proportional to (Gt)3, we obtain
= CN(Gtf (5-90)
where N is the number of scatterers per unit
volume and C is a mostly optical constant.
Actually, when the scattering losses are so
large that the microscale becomes undis-
cernible in our experiment, S should have a
certain fixed value. However, when this
happens, it is no longer in the regime of Ray-
leigh scattering. But one fact is clear: The
more complex scattering phenomena can
never occur earlier than the preceding Ray-
leigh scattering.
From Eq. (5-90) we obtain
1/6
G JS-)
1 choosing very small samples (little droplets,
= (5-91)
c) NU6 tc
where tc indicates the "starting point" (i.e.,
the center) of the zone along the time axis.
In order to determine the effective value
of the constant SVC, use is made of the fact
that in the range of higher temperatures, e.g.,
near 130 C for PP, N(T) and G(T) are well-
known from other types of experiments (see
Figs. 5-12 and 5-15, where the full line is
from microscopic determinations). In order
to obtain values for G(T) also at lower tem-
peratures, we now have to assume that the
origins of light scattering always pass
through the same stadia, which may not be
completely true, but should suffice for our
present purpose. In the case of PP the tem-
perature-dependent value of N can be taken
from curves like the one given in Fig. 5-12.
However, because of the occurrence of the
sixth root of N in Eq. (5-91), the influence
5.2 Experiments in Quiescent Melts 301
of N is of minor importance. It can almost
be absorbed in the constant SIC. This meth-
od of determining G(T) has been rather suc-
cessful, as will be shown in Sec. 5.2.2.6,
where a compilation of results will be
shown.
For the moment only one comment may
be made. The possibility of an interpretation
of the locations of the starting points in
Fig. 5-20 in terms of the growth speeds of
spherulites throws a critical light on the
myth of a temperature-dependent incuba-
tion time, which is suggested if only a super-
ficial glance is taken at this figure.
5.2.2.5 Quenching of Extremely Thin
Samples
As is well-known from experimental work
on PE [by Barham et al. (1982) as well as by
Chew et al. (1989)1 and also from theoreti-
cal considerations (Billon et al., 1989 - see
also Sec. 5.1.6), the number of interfering
nuclei per unit of volume can be reduced by
thin threads, or thin slices). The only condi-
tion is that the confining continuous phase
does not initiate nuclei at the phase boundary.
For our PP samples we have chosen thin slic-
es prepared with the aid of a microtome.
Thicknesses down to 10 \xm were chosen.
These slices were sandwiched between cover
glasses and heated between metal plates. A
first quench was carried out by dropping
these sandwiches into a thermostat bath at
the desired crystallization temperature. (This
thermostat was filled with diethylene glycol
at the appropriate temperature.) After sever-
al exactly measured residence times in this
bath, the samples were finally quenched in
tap water and, subsequently, viewed and pho-
tographed under a polarizing microscope
(Ratajski and Janeschitz-Kriegl, 1996).
The purpose of this procedure was to
enable the material to create larger spheru-
302 5 Crystallization
lites, which (of course) were virtually two-
dimensional. At the relatively low temper-
atures of interest, impingement terminates
their growth untimely if the material is
investigated in the bulk. In Fig. 5-21 a pho-
tograph is shown of a sample that was crys-
tallized at 110C for 32 s. On this figure,
areas can be observed where impingement
has occurred. These areas are of no interest
for the determination of the growth speed G.
There is also a shrink hole which, apparent-
ly, is caused by the shrinkage undergone by
the sample during crystallization. But there
are also a few flawless a-spherulites sur-
rounded by a fine-grained structure which
was certainly formed during the final
quench. At some places, these a-spherulites
are surrounded by a structureless continu-
um. As is well-known, such areas can also
be formed in PP during a rapid quench (Pic-
carolo et al., 1992).
Measurement of the diameters was
always carried out on the biggest spheru-
lites. If the crystallization times are account-
ed for, this procedure must lead to a fair esti-
mate of the growth speeds at crystallization
temperatures between 120 and 80 C. This
becomes obvious from a plot of the radii of
Figure 5-21. Photograph
of spherulites from a micro-
tome slice of 5-jim thick-
ness. Temperature of the
quench 110 C, time of the
quench 32 s. Diameter of
the biggest spherulite
0.14 mm (Ratajski and
Janeschitz-Kriegl, 1996).
the biggest spherulites against the crystal-
lization times for several crystallization
temperatures. Nice straight lines are
obtained in this way, as shown in Fig. 5-22.
5.2.2.6 Compilation of Growth Data for
the a-Modification of i-PP
Finally, in Fig. 5-23 a compilation is
given of growth data for a-PP, as obtained
by the methods discussed. As all these meth-
ods are subject to limitations, such a com-
parison of data is of great importance. The
reader may notice that, previously, reliable
data were only obtained at temperatures of
more than 110C. For our part, data from
PP Daplen KS 10 were mostly used. How-
ever, as the good agreement of the literature
data, as obtained on very different PP
grades, with our data suggests, the growth
speed of spherulites of industrial polypro-
pylenes must really be independent of the
molar mass, as Magill (1967) pointed out
previously with the aid of an interesting
model polymer. On inspecting Fig. 5-23, the
following features may be noticed: The col-
lected data roughly indicate the height of the
growth speed maximum. This is important
 5.2 Experiments in Quiescent Melts 303

0,20 -,

0,18 -
Temperature:
0,16- * 81C
85C
0,14 - 90C
0,12 - 95C
* 97C
0,10 - A 100C
cr: * 105C
0,08- v 110C
0,06- * 115C
o 117C
0,04- * 120C

0,02-

000
0 20 40 60 80 100
t (sec)
Figure 5-22. Radii of the biggest spherulites against growth time for a series of quenching temperatures for
i-PP Daplen KS 10 (Ratajski and Janeschitz-Kriegl, 1996).

0.5 0.6 0.7 0.8 0.9

1
i i
' i. .' ! i. ; J :
: : A
T
: '
:
: : A
A %^o; A : a-Polypropylene
-6- - -6
~. '. ', ', radial growth rate

: \
;
O
-7-
K ! i - -7
"
; 2 : : :
-8- -. A -: -;..._
: : o : ;
A

: : o * :
-9- - -9

' m

-10 -10
80 90 100 110 120 130 140 150 160
Temperature (C)
Figure 5-23. Compilation of growth speeds for the (^-modification of i-PP vs. temperature from various sourc-
es. Literature data are indicated by open symbols [Lovinger et al., 1977 (rhombs); Padden and Keith, 1959 (cir-
cles); von Falkai, 1960 (triangles); Olley and Bassett, 1989 (stars)]. Values calculated from /3-transcrystallization
with the aid of Lovinger's cone angles (closed squares) (Ratajski, 1993), from microtome slices (closed circles)
(Ratajski and Janeschitz-Kriegl, 1996), from DSC according to Eder's method [closed triangles pointing upward
(Paulik, 1993), closed diamonds (Ratajski and Janeschitz-Kriegl, 1996)], and from the so-called incubation times
of Fig. 5-20 (closed triangles pointing downward) (Ratajski and Janeschitz-Kriegl, 1996) are also given.
304 5 Crystallization

because of the symmetry of the growth
curve postulated previously by Magill et al.
(1973). So, it is at least possible to guess the
course of the curve at lower temperatures.
For practical calculation purposes, Fig. 5-
23 will provide a sufficient amount of infor-
mation because the exact course of the line
at temperatures below 80 C seems to be of
minor importance for cooling processes.
An inspection in more detail reveals the
following facts:
a) The data derived from transcrystalliza-
tion experiments on the /3-modification [by
taking into account the cone angles (see Fig.
5-16)] provide points above those from all
the other measurements.
b) The data derived from DSC measure-
ments according to the method described in
Sec. 5.2.1 give rise to the lowest points.
c) Probably, the most reliable data are from
the quench of extremely thin samples. In any
case, these points reach down to the lowest
temperature (81 C).
d) The points from the starting points of the
diffuse crystallization zone (closed trian-
gles pointing downwards) are in between
the other points. The point of adjustment lies
at 130 C.
With respect to item b) there are some com-
ments: The DSC points may really be too
low. Notwithstanding the fact that the role
of the internal heat transfer coefficient has
been thoroughly investigated, there still
remains the problem of the time delay
caused by the internal control system.
because of its low speed of crystallization.
But the low speed of crystallization makes
it very useful for fundamental investiga-
tions. The classical investigation was car-
ried out by Boon et al. (1968 a, b). The
growth speed of spherulites was investigat-
ed on the hot stage of a microscope. These
measurements cover practically the whole
range of interesting temperatures, as can be
seen from Fig. 5-24. At this point it should
be emphasized that Magill (Magill et al.,
1973; Magill, 1967) got similar results for
a tremendous number of mostly specially
synthesized polymers. We have chosen the
work of Boon and co-workers because of its
completeness with respect to the methods
chosen. The melting point of this polymer
was found by an extrapolation method to be
240 C.
An interesting experience with this poly-
mer was that the thermal history had a sub-
stantial influence on the number of nuclei
Nv per unit volume. This fact is reflected by
Fig. 5-25, in which the dilatometric curves
are shown for a crystallization temperature
of 140 C, dependent on a previous short
term (-10 min) of supercooling to several
lower temperatures T2 indicated on the fig-
ure. The results are given in Table 5-3 with
y- l/r=the nucleation frequency. In the
third column the effective Avrami expo-
nents (n) are quoted. Clearly, the limiting
Table 5-3. Data of the curves of Fig. 5-25 for differ-
ent values of T2.
T2 (C) tm (min) n v(min ]) Ns, (crrT3)

20-75 29 3.6 0.08 3.4 XlO11

5.2.3 Crystallization Kinetics Data for 80 32.5 3.2 0.30 7.6 xlO 1 0
Some Other Polymers 82 62 3.3 0.19 l.OxlO 1 0
86 70.5 3.1 0.47 1.1 xlO 1 0
5.2.3.1 Isotactic Polystyrene 90 82.5 3.0 6.2 x 109
As is well-known, this polymer is of no 100 153 3.1 0.17 1.1 xlO 9
110 535 2.7 2.8 xlO7
industrial interest. In fact, it cannot be used 140 730 2.4 1.0 xlO 7
as an amorphous or crystalline polymer
 5.2 Experiments in Quiescent Melts 305

Figure 5-24. Growth speed of the

spherulites of isotactic polystyrene
against the crystallization tempera-
ture, according to Boon et al. (1968 a).
(Courtesy of John Wiley, New York.)

0.99 -

0.98 -

0.97 -

20 -co 80 100 200 00 800 1000 2000

t[min]

Figure 5-25. Dilatometer curves (Vt vs. log t) for isotactic polystyrene. Crystallization temperature 140C; the
previous short term quench temperatures (T2) are indicated on the graph (Boon et al., 1968 b). (Courtesy of John
Wiley, New York.)

cases for spherulitic growth, i.e., n = 3 (neg- On the same sample of isotactic polysty-
ligible activation time r) and n = 4 (sporad- rene, Keijzers (1967) carried out small-
ic nucleation) are not fulfilled. Values small- angle light-scattering measurements. He
er than 3 cannot easily be explained for bulk used a slightly modified version of the well-
crystallization, but are frequently reported known equation
(see Sec. 5.1.7). In the fifth column, the
respective numbers of nuclei are quoted 4.U
(5-92)
47rsin(0/2)
 5 Crystallization
200 400 600 aoo
as derived by Stein and Rhodes (1960)
for small-angle light scattering between
crossed polars, where R is the radius of the
spherulite, X is the wavelength of the light,
and <9is the angle at the maximum intensity
of the obtained four-leaved clover pattern
(see Fig. 5-27 in the next section). In this
way he determined the growth of the (aver-
age) spherulite radius. One of Keijzers'
results is shown in Fig. 5-26. In this figure
the growth of R is given at 140 C for the
case where the sample was directly
quenched to this temperature (adjustment
time about 5 min) from 265 C. A growth
speed G of 0.044 |Lim/min was obtained from
the initial slope of this curve, whereas Boon
found a value of 0.036 |Lim/min (see his
Fig. 1). As can be seen from Fig. 5-26, the
value of R levels off after about 700 min at
25 |iim. The reason for this is that growth is
stopped by impingement of the spherulites.
The final size of these spherulites was
observed under the microscope to be near-
ly equal. The effect of interference between
these spherulites on the scattering was dis-
regarded. Assuming for simplicity a degree
of packing of unity (hexagonal close-pack-
ing being 0.74), it is possible to estimate
the number of nuclei Ns with the aid of the
Figure 5-26. Spherulite radius
against crystallization time at a crys-
tallization temperature of 140 C for
isotactic polystyrene, according to
Keijzers et al. (1968). (Courtesy of
The American Chemical Society.)
1000
equation
(5-93)
In this way Keijzers obtained Ns=l.l x
1013 nT3, while Boon obtained iV s =1.0x
1013 nT 3 under the same thermal conditions.
These agreements are quite good in view of
the difficulties encountered. Over a range of
temperatures between 240 C (melting
point) and 150C, the number of nuclei
increased by about two decades. When the
samples were quenched first from 256 C to
below the glass transition temperature
(-100 C), these numbers were enhanced by
five decades.
5.2.3.2 Poly(ethylene terephthalate)
The growth rates of the spherulites of a
great number of poly(ethylene terephtha-
lates) of different molar masses were inves-
tigated by van Antwerpen and van Kreve-
len (1972) by the light-scattering method.
To demonstrate the four-leaved clovers seen
between crossed polars, Fig. 5-27 is intro-
duced. For large scale investigation, how-
ever, a proper photometer was developed, in
Fig. 5-28 the results are given for a series of

Scattering
angle (rad): 0 7T/6 0 7T/6
tcr>st(s): 16 25
Figure 5-27. Four-leaved clover pattern [see Stein and Rhodes (I960)] for an industrial poly(ethylene tereph-
thalate) at the indicated crystallization times after a quench to 175 C, according to van Antwerpen and van Kre-
velen (1972). (Courtesy of John Wiley, New York.)
120
470
T(K)
Figure 5-28. The spherulite growth rate versus the
crystallization temperature for poly(ethylene tereph-
thalate) samples of various number average molar
masses (van Antwerpen and van Krevelen, 1972), 1)
19000, 2) 22 300, 3) 24 800, 4) 27400, 5) 30100, 6)
35400, 7) 39 100. (Courtesy of John Wiley, NY.)
polymers for practically the whole range of
interesting temperatures. From the figure it
can be seen that the growth rates are strong-
ly dependent on the molar mass, the poly-
mer of the lowest molar mass showing the
5.2 Experiments in Quiescent Melts 307
0 7l/6
58
highest growth rate. The full lines are the
result of curve fitting on the basis of an ana-
lytical equation, as proposed by Hoffman
(1964) for the case where the formation of
secondary nuclei on the crystal surface is the
rate-determining step in crystal growth.
Apparently, this assumption is realistic for
slowly crystallizing polymers like isotactic
polystyrene or poly(ethylene terephthalate).
Hoffman's equation is a product of three fac-
tors, a temperature-independent factor Go,
an exponential function for the transport
processes, and an exponential function
(Boltzmann term) containing the free ener-
gy of the newly formed (crystalline) phase.
From the mentioned curve fitting, Go must
be inversely proportional to the number
490 average molar mass according to the equa-
tion
G0(nm/s) =-35 x 106 (5-94)
n (g
For infinite molar mass, a negative value of
Go would result. This is, of course, impos-
sible. This result means that Go must level
off with increasing molar mass at some pos-
itive value of Go outside the range of molar
masses used in this investigation. This
would be in agreement with the observa-
tions of Magill (1967), according to which
308 5 Crystallization
120 140 160
upperlimit of the
3-
2-
390 430
Crystallization temperature (K)
the growth speeds of polymers formed by
reasonably long chain molecules should be
independent of the molar mass.
In Fig. 5-29 the final spherulite radii [see
Fig. 5-26, from the work of Keijzers et al.
(1968)] are given as a function of the crys-
tallization temperature, when plain and dry
PETP samples were quenched from 285 C.
Here the influence of the molar mass is also
quite obvious. Using Eq. (5-93), the corre-
sponding numbers of nuclei can be derived.
Interestingly enough, for PETP this number
seems to be practically independent of the
crystallization temperature, at least for high
molar mass samples. As we know, this is in
contrast to the findings with other polymers.
This Ns is of the order of 1016 nT 3 . In the
work of van Antwerpen and van Krevelen
(1972), the positive influence of several pul-
verized solid additives on this number is
also investigated. Small amounts of liquid
additives enhance the growth speed. The
reader is exhorted to look up the original
literature if he wants to know more details.
In the thesis of van Antwerpen (1971),
180 200
39,100
Figure 5-29. Final spherulite radii
of plain poly(ethylene terephtha-
late) samples of the indicated
molar masses against the crystal-
lization temperature (van Ant-
werpen and van Krevelen, 1972).
(Courtesy of John Wiley, NY.)
450 470
the results of the measurements are tabulat-
ed.
The conclusion is that for sufficiently
slowly crystallizing polymers a host of data
is available. The reason for this fact is that,
with quenching, we are clearly in the regime
of the nucleation rate-controlled processes
(see Sec. 5.1.1). Unfortunately, the situation
is less clear for some very important indus-
trial polymers.
5.2.3.3 Linear Polyethylene
If, for isotactic polypropylene, crystal-
lization kinetics data are unavailable for the
temperature range below a temperature half-
way between the melting point and the glass
transition temperature, then the situation is
even more serious for linear polyethylene,
which is probably the most important poly-
mer for the production of commodities. For
linear polyethylene with a melting point of
146 C, no detailed data are available below
121 C, whereas the glass transition is at
-80 C. Certainly, the reason for the diffi-

culties encountered with this polymer is the
high speed of crystallization at temperatures
below 120 C.
In spite of the tremendous amount of
papers devoted to the crystallization kinet-
ics of polyethylene, we have to be selective,
focusing on the present purpose. From a
paper by Ergoz et al. (1972) we learn that,
except for extremely low molar masses, the
Avrami index has been found to be very
close to 3 in a temperature interval between
126C and 132 C, which is accessible by
dilatometric measurements. At the same
time, it is found by these authors that with
increasing molar mass, the final degree of
crystallinity decreases from about 80% at
relative molar masses between 50000 and
660000 to only about 30% at a relative
molar mass of 8000000. However, this
means that the concept of the impingement
of growing spherulites becomes shaky even
in the narrow temperature range investigat-
ed. In fact, the first (downward) deviation
5.2 Experiments in Quiescent Melts 309
from the curve predicted by Avrami [Eq. (5-
16 a)] for the degree of crystallinity as a
function of time occurs at lower and lower
degrees of crystallinity (and shorter times)
with increasing molar mass. So, it is prob-
ably no longer possible to speak of an Avra-
mi plot in the proper sense for the highest
molar masses, for which an apparent index
of 2 has been found. For us, the index 3
would show that our kinetic model with a
number of nuclei depending only on the
temperature, but not explicitly on the time,
should be applicable to polyethylene. So far,
however, it is not altogether clear whether
with polyethylene the number of nuclei per
unit volume is dependent on the tempera-
ture. Chivers and co-workers (Chivers et al.,
1982) claimed that no evidence could be
found down to 75 C (see below). Probably,
the most interesting figure from the paper
by Ergoz et al. (1972) is reproduced here as
Fig. 5-30. It seems that the minimum time
for the development of 1% crystallinity is
Figure 5-30. Minimum time for
the development of 1 % crystallin-
ity (To.oi) at the indicated crystal-
lization temperature against the
molar mass of linear polyethylenes
according to Ergoz et al. (1972).
(Courtesy of The American Chem-
ical Society.)
310 5 Crystallization
affected by two counteracting processes: In
the low molar mass range the growth speed
may decrease with increasing molar mass as
with polyethylene terephthalate. In the high
molar mass range primary nucleation may
become increasingly active. The range of
crystallization temperatures is larger than
indicated above. However, no numerical
data were obtained for the whole range.
Explicit values for the growth speed as a
function of the temperature were first given
by Chivers et al. (1982) and Barham et al.
(1982). These values were, however,
derived in a quite indirect way. In the first
paper the growth speed was found as a "fit-
ting parameter" for the actual melting point
of lamellae. Interestingly enough, the right
order of the growth speed was found near
T c =120C [compare with the value given
in Chew et al. (1989) (see below)].
In the second paper a procedure was
developed to select those particles that, after
remelting on a glass slide coated with lano-
lin, crystallized at the lowest temperature. It
was assumed that these particles contained
a minimum of heterogeneous nucleation
centers, in the ideal case a single one. The
time that such a particle of known diameter
needed for its transformation from an amor-
phous ball to a birefringent particle was esti-
mated. The minimum growth speed at 80 C
was believed to be 2 m s"1. We recall this
experience in order to emphasize the diffi-
culties encountered with this polymer.
The most recent approach is the one pub-
lished by Chew et al. (1989). This paper
contains a complete set of isothermal crys-
tallization results for the temperature range
between 121 and 129 C. Some nonisother-
mal experiments were also carried out in
order to evaluate the influence of the ther-
mal history on the results. However, in the
present context we restrict ourselves to the
isothermal measurements by the authors, as
the nonisothermal experiments did not show
a significant influence of the thermal histo-
ry on the results. Observations were made
using a Mettler FP-82 hot stage, mounted on
a microscope. Heating and cooling were
controlled by a Mettler FP-80 unit. (The
maximum heating and cooling rates were
20 K mm"1.) Photographic recording was
applied using the phase-contrast mode rath-
er than the polarizing mode. The method
was essentially two-dimensional since the
smallest observable spherulites of radius
5 |im were already larger than the sample
thickness. Successive photographic nega-
tives were projected onto a screen in order
to determine the spherulite radii (or the half-
lengths of axialites). From the known time
intervals the growth speeds were obtained.
The fraction of material transformed into the
crystalline state was obtained with the aid
of a point-counting technique. For this pur-
pose a square grid of points was superim-
posed onto the photographs. The ratio of the
number of points lying within the spheru-
lites and the total number of points was
taken as the above-mentioned fraction. The
number of nuclei was also determined
directly as a function of time. For this pur-
pose the number of just-visible spherulites
was determined as a function of the time of
observation. The real time of the birth of a
nucleus was obtained by extrapolating back
with the aid of the known growth rates, the
order of the primary nucleus being assumed
to be of the order of 10 nm. The nucleation
rate in the untransformed material was
found by dividing the observed rate by the
area of still untransformed material. In
Fig. 5-31 the spherulite radii (in |im) are
plotted against the time of crystallization for
several crystallization temperatures. In
Fig. 5-32 the fractions of transformed mate-
rial are plotted against time for various tem-
peratures. Finally, in Table 5-4 the half-con-
version times (tl/2), the growth rates (G),
and the numbers of nuclei (n) are gathered

0.5x103 1.0x103
Time of crystallization (s)
for all applied crystallization temperatures
(Tc). There was no pronounced dependence
of the number of nuclei on the time of obser-
vation. This is the most complete set of data
known so far. It seems quite possible to
extend these data to lower crystallization
5.2 Experiments in Quiescent Melts 311
Figure 5-31. Spherulite
radii of linear polyethylene
with time of crystallization
for the indicated crystal-
lization temperatures,
according to Chew et al.
(1989). (Courtesy of But-
terworths.)
1.5x103
Figure 5-32. Fraction of
transformation ("degree of
crystallinity") against time
for various indicated crys-
tallization temperatures for
a linear polyethylene,
according to Chew et al.
(1989). (Three sets of mea-
surements indicated by
three different symbols.)
(Courtesy of Butterworths.)
temperatures using better quenching modal-
ities and electronic devices fro monitoring.
At 121 C the growth speed is similar to
the one obtained by Chivers et al. (1982)
andBarhamet al. (1982). At higher temper-
atures, however, the growth rates of Table
312 5 Crystallization

5-4 fall below the ones determined in the From electron microscopic pictures and
1982 papers of the latter group. So, extrap- from extremely thin slices investigated
olation of the tabulated growth rates to under the light microscope, as obtained
lower temperatures, e.g., 80 C, does not from DSC samples after varying cooling
seem justified. rates, we learnt that the number of (tiny)
We should probably mention a recent, spherulites (diameter=10 |im) is quite inde-
quite remarkable experience, which was pendent of the crystallization temperature
obtained on the basis of Eq. (5-91) for line- for a medium density polyethylene and has
ar high density polyethylene (HDPE). As a a value of about 5 x 1014 m~3. For truly lin-
prerequisite for the use of this equation, the ear polyethylene the situation seems quite
number of nuclei per unit of volume are similar. In fact, in Chew et al. (1989) prac-
needed as a function of the temperature. tically the same value of N is quoted for
HDPE. Since N = const can be absorbed in
the constant of Eq. (5-91), the growth speed
Table 5-4. Results of isothermal experiments on high
density polyethylene (HDPE)a
can be derived from tc anyway, if the con-
stant S/C is calibrated at 121 C from the
rc(c ) *1/2(S) G (nm/s) n (mm 2) data of Chew etal. (1989). In this way
Fig. 5-33 is obtained, which contains the
121 30.5 3.5 523 135 577 data from Table 5-4 (full squares) and, in
122 65 5 245 58 545
123 115 10 142 17 524
addition, data derived in our laboratory with
124 250 20 77 7.5 465 the aid of Eq. (5-91), where the tc values are
125 650 70 41.5 4.5 282 taken from Fig. 5-34, which gives similar
126 1800 200 13.7 2.1 481 plots for an HDPE as shown in Fig. 5-20 for
127 4700 400 5.74 0.6 387 an i-PP. Remarkably, the data of Chew and
128 25 000 2500 1.55 0.12 373
129 195 000 25 000 0.287 0.00 303
co-workers can be extended over at least
another ten degrees to a temperature range
Chew etal. (1989). between 105 and 110C (Fig. 5-33). One

70 80 90 100 110 120 130 14

1
i i i i i '

0-
- 0
Polyethylene
Figure 5-33. Growth speed
-2-
radial growth rate -_ -2 of spherulites of various
polyethylenes versus the
CO crystallization temperature,
- -4

as obtained with the aid of
3 o a variety of methods:
O "6-
Chew etal. (1989) (opti-
O : - -6
cal microscopy, HDPE),
Barhametal. (1982)
-8- _ (use of tiny particles),
' : : O Ratajski and Janeschitz-
: ; : Kriegl, 1996) (from incipi-
. *
-10- I i i -10 ent light scattering, HDPE).
70 80 90 100 110 120 130 140
T(C)

Tw=100C
3- Tw=105C
Tw=110C
Tw=115C
Tw=120C
2-
Tw=125C
E
E
1-
t1/2
single point (filled diamond), as obtained by
Barham et al. (1982), should be added for
completeness. This point, however, cannot
be very trustworthy. In fact, at a growth
speed of more than 1 m s"1, the time elaps-
ing between the quench and the opaque
appearance of the particle must have been
extremely small, less than milliseconds.
And how much time did the quench need?
Was this process really nucleation rate-con-
trolled? (See Sec. 5.1.1). This question also
holds for the low temperature points from
our laboratory in Fig. 5-33.
5.2.3.4 Some Complementary
Measurements on i-PP
So far the measurements on i-PP, as
reported in this review, have the character
of exemplary measurements for the illustra-
tion of proposed experimental techniques.
In order to obtain a more complete picture
of the behavior of i-PP, some other interest-
ing measurements should also be men-
tioned, notably the work that was carried out
at the University of Palermo. It dawned
5.2 Experiments in Quiescent Melts 313
Figure 5-34. Location of
the crystallization zone
(rather narrow for HDPE)
versus the square root of
time. The temperatures of
the quenched wall are indi-
cated (Ratajski, 1993).
upon these investigators some time ago that
cooling rates, as are obtainable with the
DSC machine, are unrealistically low when
compared with those characteristic of real
processing conditions (Piccarolo et al.,
1992;Piccarolo, 1992).
For this purpose an i-PP sample of
Mw = 476000 and Mn = 79 300, as provided
by Himont, was investigated by these
authors. Thin samples of 5 0 - 100-|Lim thick-
ness were sandwiched between 20-|im alu-
minum foil and enclosed in a suitable cop-
per block which was quenched in a variety
of liquid coolants. The temperature of the
copper was monitored. In this way a great
number of cooling histories could be real-
ized. The cooling speed obtained when the
samples passed a temperature of 70 C was
chosen as a characteristic parameter. After
the quench the samples were kept at -20 C
for further investigation. They were charac-
terized by their densities, as obtained in a
density column, by their morphologies, as
determined from optical microscopy
between crossed polars, and by their crys-
talline structures, as obtained with the aid of
wide-angle X-ray scattering.
314 5 Crystallization
0.92
0.91
s o
o <> <> <>
0.9
Q
0.89
O.fi
0.1
dT/dt @ 70 C (C/sec)
Figure 5-35. Densities of i-PP samples vs. the cooling rate at 70 C, as obtained from a density column. Filled
symbols refer to results from DSC measurements (Piccarolo et al., 1994). (Personal gift from Prof. Piccarolo,
Palermo.)
In Fig. 5-35 the densities are plotted
against the cooling rate at 70 C. A contin-
uous decrease of the density is observed
with increasing cooling rate. This is an
important observation in view of our
assumptions made so far, i.e., that the effect
of density changes can be disregarded to a
first approximation. At extremely high cool-
ing rates, where X-ray investigations show
the almost exclusive formation of a meso-
morphic crystal modification, a lower lim-
iting plateau is obtained for the density.
After relatively low cooling rates, the mor-
phologies reveal impinging (monoclinic) a-
spherulites. After higher cooling rates, this
type of spherulite eventually becomes insu-
lated, being surrounded by a weakly bire-
fringent medium formed by the mesomor-
phic phase. This is demonstrated in Fig. 5-
36 for six selected, widely differing cooling
rates.
This method has also been applied to a
polyamide 6 (Brucato et al., 1991, 1993), to
a polyethylene terephthalate (Brucato et al.,
1994), and to an investigation into the influ-
0 o <^
oo
>! <
<
o oi ic
10 100 1000
ence of the molar mass and nucleation activ-
ities of several samples of i-PP 7 (Piccarolo
etal., 1994).
5.3 Flow-Induced Crystallization
5.3.1 Introduction
In the following only crystallization as
induced by shear flow, and in particular,
what we have called, short term shear flow
will be treated. The basic experience under-
lying this method is that during short term
shearing no major effects are observed,
whereas after the cessation of flow, struc-
ture development proceeds conspicuously
at a quite slow pace so that it can easily be
monitored. Conclusions can be drawn (from
these measurements) with respect to the pro-
cesses that have occurred during the shear
treatment. In fact, if shearing is continued
7
The present authors are very much indebted to Pro-
fessor S. Piccarolo for his kind assistance with the fig-

70K/s 1 K/s
- 100
at shear rates that are realistic for practi-
cal processing until solidification starts
(Lagasse and Maxwell, 1976), changes will
finally happen in fractions of a second and
a lot of latent heat will be freed almost at
once (Larsen et al., 1991). Another point
which deserves our attention is a rule of
thumb of rheologists, according to which
after a total shear of about five shear units
a steady flow situation is always created for
polymer melts. This serves as tremendous
bonus for our method, because total shear,
as applied in our experiments, easily
exceeds the mentioned five shear units:
Take short term shearing at a shear rate of
100 s~l for 1 s. This means that one hundred
shear units are produced. An important con-
sequence for our experiments is that steady
flow rheology can be applied, e.g., the well-
known Carreau equation (e.g., Bird et al.,
1987 a) or, in less sensitive situations, the
power-law rheology (Bird et al., 1987 b).
These equations can be applied without
wavering because the melt rheology is not
changed much during the flow period. In
5.3 Flow-Induced Crystallization 315
Figure 5-36. Optical
micrographs as obtained
between crossed polars
from cross sections of i-PP
samples that underwent the
indicated cooling rates at
70 C. (Personal gift from
Prof. Piccarolo, Palermo.)
0.2 K/s
fact, a noticeable degree of crystallization is
only observed after cessation of this short
term shearing.
5.3.2 Apparatus
The experimental setup is shown in
Fig. 5-37(Liedaueret al., 1993). The essen-
tial part of the apparatus is formed by an
oblong duct of rectangular cross section of
aspect ratio 1 x 1 0 (mm2). Behind the
entrance to this duct, a pressure gauge is
mounted flush in one of the large side walls
of the duct. Close to the exit, two glass win-
dows are mounted in opposite positions in
the large side walls of the duct for optical
monitoring purposes. The temperature is
controlled by electric heating bands
clamped to the outer cylindrical surface of
the part containing the duct, and also, alter-
natively, by a heat transfer fluid circulated
through the hollow body of the part. The
whole arrangement is mounted on the head
of an ordinary single screw extruder. The
chamber situated between the extruder head
316 5 Crystallization
piston
accumulator
valve
pressure
gauge
extruder
bypass
and the duct possesses two lateral outlets.
An accumulator is mounted on one of them
and a valve is attached on the other, form-
ing a bypass. The piston, which fits sliding-
ly in the tube of the accumulator, can be
loaded by various weights for the purpose
of creating the desirable constant pressures.
With another valve the entrance to the duct
can be closed. In order to check the obtained
pressures, there is also a pressure gauge in
the wall of the chamber.
Before the experiment is started proper-
ly, the part containing the duct is heated by
the electrical heating bands to a temperature
well above the melting point of the polymer.
The extruder barrel is kept at the same tem-
perature. For polypropylene, a temperature
of 200 C was chosen. A normal extrusion
through the duct is carried out for a while,
before flow through the die is stopped by
closing the valve in the entrance and stop-
ping the extruder. Of great importance is the
introduction of a sufficient time of rest so
that the melt in the duct can completely relax
and forget the previous treatment. If a suf-
ficient time for relaxation has elapsed, heat
transfer fluid of a temperature according to
the level of desired supercooling is pumped
through the body of the duct (i.e.,
duct
Figure 5-37. Schematic
representation of the appa-
windows ratus for measuring short
term shearing (Liedauer
etal., 1993). (Courtesy of
Hanser-Verlag, Munich.)
143-157 C for our experiments with iso-
tactic polypropylene). After thermal equili-
bration has taken place in the surrounding
of the duct, extrusion is resumed for a sharp-
ly determined period of time. In this time
hot melt from the extruder is pushed into the
duct. This measure is necessary to avoid
crystallization at the entrance under the
influence of the stretching flow characteris-
tic for the entrance zone [see van der Vegt
and Smit (1967)]. But this use of the hot melt
does not matter so long as it does not pene-
trate down to the windows, where the iso-
thermal process is monitored with the aid of
the growing optical retardation and/or tur-
bidity.
In order to obtain short term extrusion at
a constant pressure, the following measures
are taken: With the entrance to the die
closed, the extruder is started up again.
Because there is no other escape, the melt
ejected from the extruder screw pushes the
loaded plunger into the accumulator. The
valve at the duct entrance is subsequently
opened. After the intended shearing time,
the valve in the bypass is opened. This was
found to be the most convenient way of
creating a "box-like" pressure-time profile
at the duct entrance. The success of this pro-

cedure was checked by the pressure gauge
in the duct wall.
For the purpose of a practically continu-
ous monitoring of the optical retardation, a
system was developed in which a rotating
analyzer was used. Whilst the polarizer was
kept at 45 to the flow direction, the analyz-
er periodically changed its position from
parallel to perpendicular to the polarizer. In
this way, the intensities I and / could be
determined practically continuously (at a
frequency of -30 s"1). The optical retarda-
tion follows from the well-known equation
sin (5-95)
where Fis the retardation and A is the wave-
length. For further information the turbid-
ity, which increases with the progress of the
crystallization, can be obtained. A more
quantitative interpretation of this turbidity
was recently obtained after completion of
this manuscript.
5.3.3 Results
In Fig. 5-38 the optical retardations are
shown for PP Daplen KS 10 as functions of
the monitoring time after a wall shear rate
yw = 108 s~* at a temperature of 150 C for
the shearing times ts (in seconds), as indi-
cated near the curves. Notice how short
1500
6.05
t (s)
5.3 Flow-Induced Crystallization 317
these shearing times are when compared
with the monitoring times during which the
optical retardations grow from practically
zero. Also of importance is the observation
that, initially, these curves show a rather
long linear part. So, it makes sense to deter-
mine the monitoring times tm a t which the
retardation reaches half the wavelength.
These monitoring times are something like
the reciprocal initial slopes of these curves.
In Fig. 5-39 these monitoring times t^2 a r e
plotted against the shearing times ts on dou-
ble logarithmic scales for a shearing tem-
perature of 143 C. The wall shear rates (yw)
applied are indicated near the straight lines,
which are drawn with a slope of -2 at ver-
tical distances equal to 4 log (7;/7/-i)> where
Yi is the wall shear rate for one series of
measurements. Very similar sets of lines are
obtained for the shearing temperatures of
150 and 157 C. Only these lines are shift-
ed in a vertical direction by roughly one and
a half and three decades, respectively, to
higher monitoring times. Interestingly
enough, these shifts nearly correspond to the
temperature dependence of the growth
speed of spherulites in a quiescent melt, so
that the product of (t^2 G) depends only
slightly on the temperature. (This may point
to a kinematic mechanism of nuclei forma-
tion.) Because of the slopes and the mutual
Figure 5-38. Optical retardation
against monitoring time for PP
Daplen KS 10 with yw= 108 s"1
and T= 150 C, shearing times
being indicated in seconds near the
curves (Liedauer et al., 1993).
(Courtesy of Hanser-Verlag,
Munich.)
800
318 5 Crystallization

T=143C positions of the lines in Fig. 5-39, the con-

log (tX/2>
1
log ( t . )
Figure 5-39. Double logarithmic plot of the observa-
tion time at which a retardation of half the wavelength
is reached against the shearing time at 143 C for the
polymer of Fig. 5-38 (Liedaueret al., 1993). (Courte-
sy of Hanser-Verlag, Munich.)
clusion may be drawn that for shear-induced
crystallization, precursors are formed dur-
ing the flow, which reach the same effec-
tiveness at y 4 1 \ - const. This curious result,
which has never been found previously, puz-
zled us for years!
From the samples that were extracted
from the duct after complete solidification,
a host of further information was obtained.
Cross sections were prepared from these
samples. One type of cross section was
obtained by cutting in a direction parallel to
the small side walls of the duct at a plane
somewhere in the middle (at sufficient dis-
tances from the small side walls, where the
two-dimensional flow profile is undis-
turbed). A photograph of such a cross sec-
tion, as taken under a polarizing micro-
scope, is shown in Fig. 5-40. This picture
was obtained after a shear treatment of
ts = 15.6 s, at a wall temperature of 150C,
and a wall shear rate yw = 67.8s~1. Two
types of layer are found under the surface of
this sample. One highly oriented layer is
found close to the surface. A second fine-
grained layer forms an intermediate area
between the highly oriented layer and the

Figure 5-40. Cross section

through a sample of PP
DaplenKS 10 after short
term extrusion for 15.6 s at
a temperature of 150C,
with a shear rate of
yw = 67.8 s"1 at the duct
wall (Liedauer et al., 1995).
(Courtesy of Hanser-Ver-
lag, Munich.)

(spherulitic) core. The applied shear treat-
ment can be classified as being of medium
strength. After strong shearing, as occurs in
the mold of an injection-molding machine,
only an oriented layer is found. The much
more complicated texturing, as found in the
latter molds, can be ascribed to the fact that
a melt front first moves into the empty mold,
causing some stretching flow behind the
melt front [Tadmor's fountain flow (Tad-
mor, 1974)]. There is also the effect of the
packing stage. In our experiments, pure
shear flow is obtained. With only weak
shearing, a fine-grained layer is found.
In Fig. 5-41 the critical shear rates yc at
the boundary between the fine-grained layer
and the core are plotted against the shearing
time ts on double logarithmic scales for a
temperature of 143 C. These shear rates
were calculated with the aid of Carreau's
modified equation
] (5-96)
where 7] is the viscosity and y is the shear
rate, with its parameters A, a, n, r/0 fitted to
the flow curve of the polymer melt extrap-
olated to 143 C with the aid of the
time-temperature superposition principle
(Ferry, 1980). In this way the shear rate pre-
1 -
5.3 Flow-Induced Crystallization 319
vailing during the flow at the distance of the
said boundary from the duct wall can be cal-
culated quite accurately. In fact, it can be
assumed that the rheology of the melt does
not change very much during short term
shearing. Obviously, the straight line, as
drawn through the points at a slope of-1/2,
represents the dependence of log (yc) on log
(ts) quite well. Similar results were also
obtained for 150 and 157 C. If the boun-
dary is characterized by a constant critical
number of nuclei (per unit volume), it
becomes quite obvious that our characteris-
tic parameter here is y\ ts = const. (Admit-
tedly, a higher power, e.g., y\ t\ would also
be possible, because its consequences
would be the same in such a plot.)
In Fig. 5-42, the critical shear rates yc at
the boundary between the highly oriented
layer and the fine-grained layer are plotted
against the shearing time ts on double loga-
rithmic scales. In this case a slope of -1/4
is found to a good approximation. This
would point to a characteristic parameter
y4 ts= const. A more detailed discussion
will follow.
A second type of cross section is obtained
by cutting the sample perpendicular to the
previous flow direction. It is remarkable that
the birefringence in such a cross section is
Figure 5-41. Critical shear rate yc
at the boundary between the fine-
grained layer and the core for PP
Daplen KS 10 at 143 C and the
following wall shear rates:
67 s"1, 85 s"1, 106 s"1,
and O 131 s"1 (Liedauer et al.,
1995). (Courtesy of Hanser-
Verlag, Munich.)
log U s ] 2
320 5 Crystallization
2-
log t. [s]
zero. If electron microscopy is applied, star-
like structures are discovered, as will be
shown below.
5.3.4 Theoretical Considerations
The striation of the highly oriented layer,
which becomes apparent at high resolution,
and the starlike objects seen in a cross sec-
tion perpendicular to the previous flow
direction lead us to the conclusion that
during shear flow thread-like precursors
result as a primary structure for the highly
oriented layers, probably by liquid-liquid
phase separation (Vrahopoulou-Gilbert and
McHugh, 1984; Keller and Kolnaar, 1993).
The latter conclusion is also backed up by
the experience that shearing at temperatures
well above the melting point also leads to
the same type of highly oriented layers after
swift quenching (Eder et al., 1990; Jane-
schitz-Kriegl et al., 1987 a, b).
The following mechanism has been con-
cocted by our group (Liedauer et al., 1993):
As a first step, spotlike primary nuclei are
formed sporadically with a frequency pro-
portional to y 2 . The square of the shear rate
is assumed because it is the most simple
even function of y. (This process is not
allowed to depend on the direction of shear-
Figure 5-42. Critical shear rates
yc at the boundary of the highly
oriented layer at 143 C for the
polymer and for the wall shear
rates indicated in Fig. 5-41 (Lie-
dauer et al., 1995). (Courtesy of
Hanser-Verlag, Munich.)
ing.) The formation of these nuclei is
assumed to be governed by the following
differential equation
(5-97)
Jn
where N is the number of nuclei per unit vol-
ume, yn is a characteristic shear rate, gn is a
factor of the dimensions m~3 s"1, and Tn is a
relaxation time. Such a relaxation time
seems necessary because, according to our
previous experience at higher temperatures,
the ability of a melt to crystallize in the men-
tioned way relaxes if the time span between
the cessation of flow and the quench is
increased (Janeschitz-Kriegl and Eder,
1990; Eder et al., 1989).
In a subsequent step it is assumed that
some of the spotlike nuclei grow out into
threadlike precursors during further shear-
ing. For the length of these precursors the
following differential equation is proposed
(5-98)
7/
where again y7is a characteristic shear rate,
g7is a factor of the dimensions m s"1, and xi
is a relaxation time.

Finally, we are interested in the total
length Ltot of precursors per unit volume.
For this length, with Ls(t) being the solution
of Eq. (5-98) for the initial condition
Ls(s) = 0
2\dsN(s)Ls(ts) (5-99)
o ter result means that Tn must be large com-
In order to be able to carry out this inte-
gration, it is necessary to assume Tn =o for
those nuclei growing out into threads. In
orther words, it is assumed that these par-
ticular nuclei cannot cease to exist. With this
qualification we obtain
7 transition from Eq. (5-101) to Eq. (5-102)
7n7/
(5-100)
If the exponential term is expanded to the
second order
74 : be characteristic for the boundary of the
(5-101)
Indeed, the first term of the expansion
cancels against the first term in the square
brackets of Eq. (5-100). Equation (5-101)
does not contain r^and gives a very satisfy-
ing result, i.e., that Ltot = const means
y4 tl = const. Apparently, Fig. 5-39 is
explained quite simply by this equation, in
that T must have been rather large compared
with ts in all cases leading to Fig. 5-39 and
to similar figures at the other temperatures.
Another interesting situation is if T is
small compared with ts. In such a case a
steady growth of Ltot is obtained
T/ ts (5-102)
7n 7/
From this equation Ltot = const for
y\ = const. This latter combination
reminds us of the relation between yc and ts
at the boundary of the highly oriented layer
5.3 Flow-Induced Crystallization 321
(see Fig. 5-42). Apparently, at this boundary
there is a fixed critical value of Ltot. A sim-
ilar conclusion can be drawn from Fig. 5-41
with respect to a fixed critical value of N at
the boundary between the fine-grained layer
and the core, except that such a fixed value
is linked to a fixed product y\ ts. This lat-
pared with all shearing times ts applied at
the reported temperatures. In fact, for ts < Tn
the solution of Eq. (5-97) reads N=(y/yn)2
Looking once more at Eq. (5-100), it can
be seen that the dependence on the shear rate
is concentrated in the front factor, so that the
only depends on the chosen shearing time.
This fact caused us to look later for a more
realistic version of the theory.
At this point the reader might puzzle
about an acceptable physical explanation,
why a constant value of Ltot(oc y4 ts) should
highly oriented layer. For this point it has to
be realized that there is a relation between
Ltot and the average distance D between
threadlike precursors. The total length Ltot
of threads per unit volume can be compared
with the total length of wooden logs of thick-
ness D and of 1 m length each, in a stack of
1 m3. This leads to the relation
, _ 1 (5-103)
So it can be imagined that the distance
between threads becomes so large at a cer-
tain (low) value of Ltot that the human eye
perceives a disintegration of the layer.
In fact, one big problem still remains to be
solved. Figure 5-39 seems to show that a
light beam transmitted perpendicularly
through the oriented layer always indicates
the validity of Eq. (5-101), whereas at the
boundary Eq. (5-102) holds. This may mean
that at the same shearing time ts the value of
322 5 Crystallization
T must be much higher than ts in the interi-
or of the layer and much lower at its boun-
dary. This leads us compulsorily to the
assumption that Ti will be a function of the
process conditions, which are most severe at
the duct wall but ease off towards the boun-
dary. The simplest solution is to assume a
linear function of the length of the individ-
ual thread (Liedauer et al., 1995), i.e.,
= a+ /3L (5-104)
For long lengths this assumption leads to
a negative constant second term of Eq. (5-
98), i.e., -l/p. For short lengths, however,
the term a cannot be omitted to avoid a finite
speed of decay for a thread of zero length,
which is, obviously, physical nonsense.
So, a quite acceptable physical picture is
developed, even if a much stronger depen-
dence on L may finally turn out to be more
realistic: A sufficiently long thread can only
decay at a constant speed, probably as a
function of temperature, from its ends. Only
very short and still unstable threads can be
ruptured by thermal motion at any point
along their contour, which is related to a
constant relaxation time a. (Later we will
see that an estimate of a leads to a value of
about 0.25 s, which is smaller than any
shearing time applied in the presented mea-
surements!)
It turns out that Eq. (5-99) can be inte-
grated in its closed form if r^is taken from
Eq. (5-104) (Liedauer et al., 1995). In the
present context, however, only the numeri-
cal results are presented in Fig. 5-43. Unfor-
tunately, the dimensionless variables and
the dimensionless curve parameter are rath-
er cumbersome and must be explained a lit-
tle more explicitly. On the ordinate axis the
logarithm of the dimensionless variable
P=(?/Y/)2 g//?is plotted. On the abscissa is
the logarithm of 6 = tja. This means that the
dimensionless square of the shear rate is
plotted against the dimensionless shearing
-2 -1 3 Iog0
Figure 5-43. Results of the theory, as expressed by
Eqs. (5-97, (5-98), and (5-104) with rn = oo. For an
explanation of the dimensionless variables and the
curve parameter see the text (Liedauer et al., 1995).
(Courtesy of Hanser-Verlag, Munich.)
time. (Observe the different influences of p
and a in these variables!) The mentioned
curve parameter is
P2 rl gi
Ant = " (5-105)
2a y]2
At first sight it seems very difficult to
decide what the physical meaning of this
parameter is. One thing is clear: If ^decreas-
es (i.e., if the influence of the thread length
on x decreases), we move down along the
p-axis. A factor of 10"1 in p means a factor
10~2 in Atot. At 6-values smaller than unity
this means that a change of a factor 10~2 in
Atot just causes a change of 10"1 for p. All
the curves are parallel and reflect pO =
const, which means y11^-const. In fact,
small values of 6 mean that a is much larg-
er than ts. An analytical solution for this lim-
iting case reads (Liedauer et al., 1995)
pe = ^l2At0{ (5-106)
On the other hand, if the 0- values are larg-
er than unity, ts will be larger than a. In such
cases it depends on p, and implicitly on j8,

whether another limiting case with
p 2 6 = const, is actually obtained (which
means y4 ts = const, lower right side of the
graph). For this lower right corner of
Fig. 5.43 the analytical limiting relation
reads
z over practically the whole interior of the
P e=Au (5-107)
For p<\ the transition between the parts
of the curves referring to these limiting
cases occurs at
0=2 or t=2a (5-108)
(i.e., at the intersection of the limiting
straight lines). This corresponds to the
behavior of Eq. (5-100), with y showing up
only in the front factor. In fact, starting at
low values of the curve parameter Atot and
moving up to a value of Atot = 1, this tran-
sition is always found at the just-mentioned
fixed 0-value. At higher values of Atot, how-
ever, the bend in the curves shifts to higher
values of 6. At the same time a more com-
plicated shape of the curves is obtained at
0-values above the value where the bend is
noticed.
Now the reader is reminded of Fig. 5-42,
where the limiting case of y\ ts = const, is
localized at the boundary between the high-
ly oriented layer and the fine-grained layer,
at least for ^-values larger than 0.5 s. At the
same time the conclusion was drawn that in
the interior of the highly oriented layer
Eq. (5-101) must be valid, because this was
proven by the transmitted light (see Fig. 5-
39). According to Fig. 5-43, this means that
the critical value for Atot must be near unity,
because at lower values of Atot the bend in
the curves is invariably at 0 = 2. This also
means that by moving in a vertical upward
direction (i.e., at a constant value of 0) from
the lower right parts of the curves, at values
of Atot > 1 the domain where the said bend
shifts to higher values of 0 is reached. This
is important because /s is the same over the
5.3 Flow-Induced Crystallization 323
whole cross section of the sample. Howev-
er, on entering the said domain of Fig. 5-43
within the unfortunately rather narrow
range of /-values characteristic of the
oriented layer, y\ ts = const is characteristic
for the boundary, while y\ t\ = const reigns
layer. (This explains our desire for a strong-
er dependence of r^on L.)
So, we can consider the fact that
Aot,cnt. = 1 to be an interesting and persuad-
ing criterion. Unfortunately, so far we are
not able to give a verbal argumentation as
to why this simple principle should hold.
When comparing the theoretical curves of
Fig. 5-43 with the experimental curves
given in Figs. 5-41 and 5-42, it is possible
to arrive at the conclusion that the bend
shown in Fig. 5-43 for A tot = 1 at 0 = 2 must
be expected at about ts = 0.5 s in Fig. 5.42.
This speculation is based on the observation
that the extrapolation of the straight line
with slope -1/4 in the latter figure to values
of ts < 1 s (log (/s) < 0) leads to a crossing
point with the straight line in Fig. 5-41.
Because the assumption has been made that
the threadlike precursors grow out of some
of the spotlike nuclei, the existence of
threadlike precursors cannot be expected to
the left of the straight line of slope -1/2.
Admittedly, for direct proof the experimen-
tal window is too small. However, accept-
ing the indicated consideration, the value of
ainEq. (5-104) must be 0.25 s = fs>c/2, with
tsc being the Rvalue observed at the bend.
If our speculation should be invalid, an even
smaller value of a would be the conse-
quence.
5.3.5 Towards a Quantitative
Evaluation
As is quite obvious from the experimen-
tal results, the initially linear growth of the
optical retardation occurring after the ces-
324 5 Crystallization
sation of flow (see Fig. 5-38) must be due
to the lateral overgrowth on the threadlike
precursors formed during the short shearing
period. As this overgrowth occurs in a stag-
nant fluid, we can assume that the speed of
growth is equal to the speed of growth as
observed on spherulites in a quiescent melt.
This saves us from determining a further
parameter as a function of temperature. A
second conclusion can be drawn from the
observed linearity of the curves shown in
Fig. 5-38. If lateral overgrowth on the
threads occurs in cylindrical symmetry,
quadratic initial growth of the optical retar-
dation should be expected. Previously, the
linear initial section led us to assume the
presence of membrane like precursors. Only
the electron microscopic pictures of cross
sections perpendicular to the flow direction
brought us round to believe in threadlike
precursors. This contradiction can be over-
come by the assumption that the lateral
growth gradually loses its regularity with
increasing distance from the thread. Elec-
tron microscopic pictures also supported
this supposition. Actually, it seems that the
lamellae growing out of the central area
maintain a practically constant thickness,
like the spokes of a wheel 8 . For such a case,
the share of highly oriented lamellae in the
crystalline overgrowth is very nearly b/r,
with r being the distance from the center and
b being a constant. In this way the accretion
of oriented material during an increase of r
by dr is not 2/r rLtot dr but only 2/r bLtot dr
or In bLioi Gdt, if dr = Gdt.
Because of the fact that in this experiment
in a rectangular duct the shear rate y is not
a constant over the trajects of the transmit-
ted light beam, but varies mainly in the
8 of D is uniquely related to L t o t . If L t o t w is
Professor B. Lotz of Strasbourg informed one of the
present authors (G.E.) that, in fact, lamellae of i-PP
do not branch at these relatively high crystallization
temperatures (Lotz and Wittmann, 1986).
direction of the duct height H, it is neces-
sary to carry out a corresponding integration
of the space coordinate. Integration of the
time coordinate becomes very simple for the
linear range of F vs. t: Because of the fact
that no impingement of laterally growing
bodies takes place over this range, J dt = t.
(In fact, the observed saturation tendencies
of the curves in Fig. 5-38 must be ascribed
to impingement. Later on we shall make use
of this fact.) So, we have for the said linear
range
/2
= 27i(tG)Ancb J (5-109)
where Anc is the birefringence in the order-
ly crystallized lamellae, t is the monitoring
time, L t o t (x,ts) is the total length of threads
per unit volume at distance x from the mid-
plane [according to Eq. (5-101)], and ts is
the shearing time, which is the same for all
distances from the mid-plane.
For the integration of Eq. (5-109), the
power-law rheology can be used
Aln
(5-110)
H )
where n is the power-law index, which is
usually 0.33 for industrial polypropylenes
(Petrochemie Danubia, 1993). There are
still two unknown parameters in Eq.
(5-109), i.e., Anc and b. Fortunately, these
parameters appear as a product
Anc b = An^ (5-111)
In this equation (4b/D) is digested as the
fraction of orderly oriented material in a cyl-
inder of diameter Z), and An is the resulting
birefringence of the macroscopic body. As
already expressed by Eq. (5-103), the value
the total length of threads per unit volume
at x = H/2 (i.e., at the duct wall), after inte-
gration of Eq. (5-109) with the help of
 5.3 Flow-Induced Crystallization 325

Eq.(5-110)

Anw H (5-112)
(4 + n)
where D w is the (average) distance between
threads at the wall. Apart from D w , all the
parameters of Eq. (5-112) are accessible by
direct measurement. In fact, the monitoring
time t can be specified as t^ a t which F
reaches half the wavelength A/2. Replacing
r by A/2 and solving Eq. (5-112) with
respect to D w gives

(5-113)
A (4 + n)
This is a remarkable equation, permitting
the calculation of the microscopic quantity
D w from independently measurable macro-
scopic quantities. In principle, An must be
measured by a light beam directed in a per-
pendicular direction to the large sample sur-
face. However, because of the experience
that the birefringence of the sample is zero
in a cross section perpendicular to the flow
direction, Anw can easily be measured at the
rim of a cross section that is cut parallel to
the small side walls from the middle of the
sample. Direct proof of Eq. (5-113) was
obtained with the aid of electron microsco-
py. As a first satisfying experience it is
noticed that the average distance between
the centers of the starlike structures in cross
sections perpendicular to the flow decreas-
es inversely proportional with the square of
y. In view of Eq. (5-103), this is very satis-
factory.
In Figs. 5-44 and 5-45 electron micro-
graphs are shown from a cross section
perpendicular to the flow for a sample that
has undergone a shear treatment of ts = 7.0 s
at a wall shear rate of y w =72 s"1 and a
temperature r=150C. The first micro-
graph covers a distance from the rim to
11 |Lim, the second covers a distance from
55 |xm to 66 |im from the rim (in the verti-
Figure 5-44. Electron micrograph of a cross section
perpendicular to the flow direction of a sample of PP
Daplen KS 10 after a shear treatment of yw = 72 s"1
and ts = l s at 150C. In the vertical upward direction
this picture stretches from the rim to about 11-jim
inward (Liedauer et al., 1993). (Courtesy of Hanser-
Verlag, Munich.)
cal directions on the micrographs). The
already described starlike structures (which
are thrown into relief after a staining with
RuO4, where the dark areas show the areas
of lower crystallinity) are clearly seen. It
can easily be imagined that, as long as
these distances Ax of only 11 (im are small
compared with the distance from the mid-
plane x, the pictures within such fixed dis-
tances Ax must be similar after appropriate
changes of scale. A distance of 55 \im from
therimmeansanx-valueof 350 |im-55 |um
= 295 |Ltm. Hence, Ax is certainly small com-
pared with x. As a next step it is necessary
to calculate the proper enlargement of the
picture taken at the rim in order to make that
picture match the one at 55 jam. Because of
Eq. (5-103), this enlargement will not be
326 5 Crystallization
Figure 5-45. Electron micrograph of a cross section
perpendicular to the flow direction, as in the previous
picture, but stretching from 55 |um to 66 |im from the
surface (Liedauer et al., 1993). (Courtesy of Hanser-
Verlag, Munich.)
(2x/H)4/n but only (2xlH)2ln = (2x/H)6.
From a practical point of view, however,
it is more convenient to apply an appro-
priate change of scale to both pictures in
order to meet somewhere halfway. So
we decided to enlarge the picture from
the rim by a factor of 1.5 and to reduce
the picture from 55 |Lim by a factor of 0.54,
since 1.5/0.54 =2.8 = (350/295)6.
This comparison is shown in Fig. 5-46.
The similarity is (except for the natural dif-
ference in sharpness) quite convincing. This
means that the electron micrographs direct-
ly confirm the fourth power dependence of
Ltot on 7, as has been demonstrated in a quite
different way by Fig. 5-39.
This seems an appropriate moment for a
quantitative comparison between the result
of Eq. (5-113) and the electron micro-
graphs. For the mentioned shear treatment:
7 w =72s~ 1 ,r s = 7.0s,and7=150 o C,avalue
Figure 5-46. Comparison of parts of Figs. 5-44 and
5-45 after an appropriate enlargement or reduction,
respectively (Liedauer et al., 1993). (Courtesy of
Hanser-Verlag, Munich.)
of txi2 = 316 s was found. The growth rate G
at this temperature is G= 1.32 x 10~9 m s"1
(see Sec. 5.2.2), the duct height#=0.7 mm,
and the wavelength A=550 nm. The bire-
fringence at the edge of the cross section of
the solidified sample was Arcw =0.016. With
the aid of Eq. (5-113)
Dw = 5.92 x 10-7 m = 0.6 jam (5-113 a)
was calculated. A look at Fig. 5-44 confirms
that this is the right order of magnitude, the
height of this figure corresponding to
Let us now return to the evaluation of Sec.
5.3.4. The line for A tot = 1 in Fig. 5-43 shows
two sections. According to Eq. (5-101), the
steeper part corresponds to a total length of
threads per unit volume of
r - S g y4 2s
(5-114)
22 '
2 7
Mot ~ 7n 7/
7

For the less steep part Eqs. (5-102) and
(5-104), with pL <c a, give
T -
.? 2 (5-115)
Mot
7n7/
Because A,tot,cnt = const = 1, the left sides
of these equations should be equal. By divid-
ing Eq. (5-114) by Eq. (5-115), the result of
Eq. (5-108), i.e., tsc = 2a, is obtained, as
should be the case. However, this is the easi-
est step in a further evaluation. It should be
noticed that (5 has no influence on these
results. A reason for this will be shown below.
If, with the aid of Eqs. (5-113) and
(5-103), Ltot w is calculated instead of Dw for
the just-evaluated shear treatment [see
Eq. (5-113 a)], we obtain
Aot,w = 1-648 x 1012 nT2 (5-116)
4 4 2 belt is supported by a heatable pad. A tun-
Also, with y t\ being 7 2 x 7 = 1.317
x 109 s~2, for the factor of Eq. (5-114) we
have
= 1.26xl0 3 s 3 nT 2 (5-117)
With rs c at the bends of the experimental
curves of yc vs. ts being 0.5 s, a value of
0.25 s is obtained for a. Taking the value of
~108 s~3 for y4 ts from a figure correspond-
ing to Fig. 5-42, but for T= 150 C, it is pos-
sible to calculate the limiting total length of
150C with the aid of Eqs. (5-117) and
(5-115). In this way we obtain
Aciim = 6-3 x 1010 m-2 (5-118)
It appears that for this experiment the value
at the wall is 26.2 times this limiting value.
5.3.6 Further Evidence for the
Correlation Between the Model and
Reality
The title of an early paper from our group
was "Shear Induced Crystallization, a
5.3 Flow-Induced Crystallization 327
Relaxation Phenomenon in Polymer Melts"
(Eder et al., 1989). In the corresponding
experiments the melt of an industrial poly-
propylene was sheared at temperatures well
above the melting point, where no shear-
induced crystallization occurred during or
after shearing in an isothermal experiment.
However, crystallization in the form of a
highly oriented boundary layer occurred if
the melt was quenched after the cessation of
flow. Two methods were developed for this
investigation.
According to one of these methods, the
melt was extruded from a slit die (rectangu-
lar duct of large aspect ratio) of variable
length onto a conveyor belt made of an
extremely thin stainless steel strip welded
together at its ends. The apparatus is shown
in Fig. 5-47. Along its horizontal part the
nel is mounted in segments on this heatable
pad, so that its length can be adjusted to the
length of the transport path, which is varied
by shifting the whole support of the convey-
or belt in a horizontal direction, so that the
low side of the duct exit touches the belt at
varying distances from the chill roll (Rj)
where the extrudate is quenched after an
adjustable temper time in the tunnel. In fact,
extruder, duct, heating pad, and tunnel seg-
ments are all kept at the extrusion tempera-
Figure 5-47. Apparatus for the measurement of the
relaxation of precursors: E extruder, D slit die
(exchangeable), T tunnel (in segments), U heatable
pad, F conveyor belt, R^ chill roll, R2, R3 pulleys, B
bath (Eder et al., 1989). (Courtesy of Steinkopff Ver-
lag, Darmstadt, and Springer-Verlag, New York.)
328 5 Crystallization
ture, for which 200 C was chosen. After the
quench, cross sections were taken in a plane
parallel to the extrusion direction and per-
pendicular to the axes of the pulleys. For
zero tunnel length (i.e., zero temper time),
it was found that the thickness of the high-
ly oriented layer increased not only with the
extrusion speed but also with the duct
length. (In fact, at a constant extrusion speed
the duct length is linked to the shearing
time.)
In contrast, no influence was found of the
duct length on the rheology. For this inves-
tigation the flow birefringence was mea-
sured at the duct exit with the aid of a light
beam directed perpendicular to the large
side walls of the duct. For this purpose a
suitable adaptor containing the necessary
glass windows was mounted at the duct exit.
The conclusion was that the precursors,
which were formed during the shear flow
and which were responsible for the layer
thickness growing after the quench, were so
tiny (so thin) that they did not influence the
rheology. Truly an important conclusion for
the later work!
The most interesting results, however, are
put together in Fig. 5-48. In this figure layer
thicknesses are plotted against the temper
time in the tunnel. All curves below the
curve labeled 200 C have the same temper
temperature of 200 C. The largest available
duct length of 110 mm was chosen for these
experiments. The extrusion speeds (average
speeds over the slit cross section, chosen a
little lower than the belt speeds for reasons
of workability) form the curve parameters.
It can be seen that the layer thicknesses at
zero temper time (zero tunnel length)
decrease with decreasing extrusion speed.
The most striking feature of these experi-
ments is that the ability to form oriented
layers dies out with increasing temper time.
This experience led us to introduce the
model reflected by Eqs. (5-98) and (5-104).
Figure 5-48. Thickness of the highly oriented boun-
dary layer as a function of the residence time tT in the
tunnel. Length of slit die 111 mm, extrusion temper-
ature 200 C, chill roll temperature 10 C. Parameters
near the curves: extrusion speeds and tunnel temper-
atures (Janeschitz-Kriegl et al., 1987b; Eder et al.,
1989). (Polypropylene Daplen KS 10, courtesy of
Alfred Hiithig-Verlag, Basle, Steinkopff Verlag,
Darmstadt, and Springer-Verlag, New York.)
Except for the extrusion speed of 60 mm/s,
the curves show the occurrence of deforma-
tion at short temper times. We believe that
these deformations are the consequence of
the change of the flow profile at the exit of
the duct from nearly parabolic to flat. With
this transition fluid layers leaving the duct
near the duct wall are stretched, but form a
very thin layer on the conveyor belt, where-
as fluid layers at larger distances from the
duct wall are upset (uniaxially compressed)
during this transition and form a rather thick
core on the conveyor belt. In fact, at higher
extrusion speeds precursors are also formed
at larger distances from the duct wall. It
seems that these precursors at larger distanc-
es are destroyed by this compression. For
the apparently undisturbed curve at
60 mm/s a relaxation time of about 1.5 s is
estimated. (Another interesting feature of
Fig. 5-48 is that lowering the temper tem-
perature has a substantial effect. At 130C
no relaxation of the ability to form a highly
oriented layer is found within the available

temper times. From this experience it can
easily be explained why chill roll tempera-
tures which could only be varied between
10 and 90 C had no effect, which puzzled
us tremendously in the beginning.)
The success and failure of the just-
described arrangement instigated Wippel
(1989) [see also Eder et al. (1990)] to change
the experimental conditions. This author
quenched the duct itself, extracted the solid-
ified strip, and investigated the birefrin-
gence in a cross section taken parallel to the
small side walls of the duct from the middle
of the strip. At the same time they estimat-
ed the residence time distribution over the
cross section after steady state extrusion at
200 mm/s. As is well-known, these resi-
dence times change from infinite at the duct
wall to a lowest finite value in the center.
With increasing time lapses between the
cessation of flow and quenching they found
a decrease in the birefringence of the said
cross section. Plotting the logarithm of this
birefringence against the temper time, they
obtained a straight line, the slope of this line
characterizing a particular relaxation time.
For an extrusion speed of 200 mm/s and a
temperature of 200 C they found a relaxa-
tion time of 7.3 s. Our puzzle - which
remained unsolved until recently - was why
this relaxation time was so much larger than
the one found in the above-mentioned
experiment.
Wippel extended his measurements at an
invariant extrusion speed of 200 mm/s to a
variety of extrusion temperatures between
190 and 210 C. He found that the relaxa-
tion times varied from about 60 s down to
about 1 s over this range. In Fig. 5-49 a dou-
ble logarithmic plot is given of the zero
shear viscosity vs. the said relaxation time.
Along this curve the temperature changes
from 210 C to 190 C. If a relaxation pro-
cess of an orientation distribution function
of single molecules was traced by these
5.3 Flow-Induced Crystallization 329
log
4-
3-
log r
Figure 5-49. Double logarithmic plot of zero shear
viscosity vs. the relaxation time of precursors of PP
Daplen KS 10 after extrusion at a speed of 200 mm
s"1 and various extrusion temperatures varying
between 210 and 190 C (Eder et al., 1990). (Courte-
sy of Pergamon Press.)
relaxation times, the line in Fig. 5-49 should
occur at an angle of 45. The slope of this
line is obviously much lower. At the time
we concluded that this fact gives indirect
evidence of the decay of a supermolecular
structure. Recently we detected that all these
phenomena are in qualitative agreement
with our new model.
In order to show this, Eq. (5-112) must be
rewritten in a form still containing the prod-
uct of Anc b. Anw is determined in an addi-
tional measurement. We find
(5-119)
After completion of the crystallization
(the case of completed impingement),
tG = Dw/2. For this case Eq. (5-119) chang-
es into
F1 Tj
(5-120)
x/3 A (4 + n)
[Dw is replaced by LtotjW according to Eq.
(5-103).] In this equation C is a constant
independent of the shear rate at the wall (the
output rate).
330 5 Crystallization
From an experimental point of view, how-
ever, Eq. (5-120) is not useful. Because of
the relatively high turbidity of the complete-
ly solidified sample, it is not possible to
measure the optical retardation with a light
beam directed perpendicular to the large
surfaces of the sample. Thin slices must be
taken and the contributions added up.
Another possibility is to cut the sample near
the middle in a plane parallel to its small
side. The found birefringence distribution
can be added up for our purpose, because in
a plane perpendicular to the flow direction
the birefringence is zero. (Uniaxial symme-
try!) For his measurements, Wippel (1989)
used the birefringence near the rim of such
a cross section. This only changes the con-
stant in Eq. (5-120).
For the interior of the highly oriented
layer we have to assume that pL > a. As can
be seen from Eqs. (5-98) and (5-104) with
7 = 0, this means that above the melting
point the decay of the precursors should
occur during the temper time according to
the linear equation
(5-121)
where La is the average length of threads
obtained during previous flow. For t <La/3
the logarithmic version of Eq. (5-120)
reads, with
(5-121a)
(5-122)
In this way the relaxation time Tpr, as iden-
tified by Wippel's experiment [In
vs. t],
(5-123)
v=
Based on this equation, our prediction is that
Tpr must increase with the extrusion rate.
However, this is what we actually found and
what puzzled us for such a long time. In fact,
the ratio of the respective extrusion speeds,
i.e., 200/60, is about 3.3. Because La
depends quadratically on the shear rate, a
factor of 10 is expected, which is not too
high in view of the limited accuracy of the
underlying experiments.
However, our model can also give a qual-
itative explanation for the strong depen-
dence of rpr on the temperature. In fact, f3
will depend on the temperature in a strong
way (the destruction of a supermolecular
strand starting at its ends).
5.3.7 Towards the Recognition
of Molecular Parameters
Crystallization is obviously tremendous-
ly enhanced by flow. For solutions of low
molecular weight compounds, an interesting
explanation was given by Larson and Gar-
side (1986 a) only about ten years ago. Clus-
ter formation is observed in supersaturated
solutions of these compounds. Apparently,
the tendency to cluster formation is related
to the fact that the surface tension of a newly
formed phase is not constant, as supposed so
far, but decreases with the decreasing size of
the newly formed aggregates (Larson and
Garside, 1986 b). This fact causes an unex-
pected (flat) minimum in the curve describ-
ing the free energy of the newly formed
phase as a function of its size, e.g., its radi-
us. This minimum occurs very close to zero
radius. The energy barrier, well-known from
the work of Becker and Doring (1935),
occurs only at larger radii. Whereas in the
latter theory the assumption was made that
a sufficiently large number of solute mole-
cules gathers spontaneously to form a nucle-
us of over-critical size - which is incredibly
improbable (!) - according to Larson, stable
subcritical clusters can be formed because
of the said minimum. The experimental evi-

dence for the existence of these clusters was
given with the aid of several methods
[infrared (IR) Boltzmann distribution, or
density in a column of only 40 cm]. A low
number of these clusters (two or three)
would suffice to form an overcritical nucle-
us after their unification. However, the ther-
mal motion will have insufficient impetus
for producing an encounter between these
clusters. But, stirring will be immediately
successful, as experience shows.
The nagging question is what kind of
model consideration can replace the one that
is valid for solutions of low molecular
weight compounds by one suitable for poly-
mer melts. Some time ago Vrahopoulou-
Gilbert and McHugh (1984) showed that,
from a thermodynamic point of view, a stack
of oriented chain molecules will differ suf-
ficiently from a haymow of unoriented
molecules for the formation of a separate
phase. However, nothing could be said
about the kinetics of the required phase tran-
sition. In this respect the pioneering work of
Keller and Kolnaar (1993) on elongational
flow can provide the clue (see Chap. 4 of
this Vol.). In a nonuniform polymer, pos-
sessing a broad molar mass distribution with
a long tail at the high molar mass end, the
longest molecules are susceptible to a com-
plete stretch, while the shorter molecules
still behave as a kind of solvent in an almost
unoriented, random state. For this model the
said authors have given evidence with the
aid of several ingenious experiments. If the
process of stretching continues, as happens
near the stagnation point of a proper flow
field, more and more of the long molecules
join the new extended phase. The same hap-
pens at the tip of a needle immersed into a
stream in a downstream position. At this tip
a stagnation point is also formed. [This is
well-known from solution work (Rietveld
and McHugh, 1983)]. With a continuously
increasing (Hencky) extension rate, the
5.3 Flow-Induced Crystallization 331
initially low flow birefringence suddenly
rises to a plateau value at a critical strain rate
c. This strain rate was found to correlate
with the molar mass M by
cocM~L5 (5-124)
This was found for solutions of (noncrys-
tallizable) standard polystyrenes (Narh
et al., 1992). But such a process also seemed
possible in the melt of a nonuniform crys-
tallizable polymer if molecules were select-
ed by their length. The whole idea was based
on the resemblance of the crystalline shish-
kebab structures found for both the solutions
and the melts of crystallizable polymers,
polyethylene in particular.
In contrast to Keller's school the group of
the present authors concentrated on shear
flow. Although the described effects seem
to be much more pronounced in elongation-
al flow, shear flow is more related to what
happens in extrusion and injection molding.
But there is also another advantage: With
elongational flow a truely steady state situ-
ation is difficult to achieve from a Lagran-
gian point of view (for an imaginary observ-
er moving with a molecule). In fact, new
molecules are continuously transported
towards the stagnation point, which is sur-
rounded by only a rather small area where a
steady state exists for these molecules. This
becomes obvious from Mackley's experi-
ments (Mackley and Keller, 1973), where a
rather narrow birefringent string is found
between the opposite orifices through which
the melt leaves the pressurized vessel con-
taining the stagnation point at its center.
According to Ziille et al. (1987), a constant
Hencky strain measure is comparable with
a shear rate increasing exponentially with
time. This means that shear flow at a con-
stant shear rate will create a much more per-
spicuous situation. In fact, it was shown
some time ago by Wolkowicz (1978) that
after the sudden onset of such a shear flow,
332 5 Crystallization
a steady state situation can be reached
before shear-induced crystallization de-
velops noticeably. The question which
remained unsolved was whether a highly
oriented second phase, as known from elon-
gational flow, could also be created in shear.
So far, the suspicion has prevailed that this
kind of phase was only created in the con-
vergent entrance flow to a capillary or along
some obstacles in the fluid. In our work,
however, we could clearly demonstrate the
occurrence of such a phase in clean shear
flow at sufficiently high shear rates relevant
for normal processing conditions9. Appar-
ently, because of the high level of control of
the mechanics of shear, a quantitative eval-
uation of data became feasible.
So far, the measurements in shear have
been carried out on the industrial polypro-
pylene i-PP Daplen KS 10, as quoted in Sec.
5.2.1. In order to enable at least a nascent
discussion on the influences of molecular
parameters, another industrial polypropy-
lene was recently included in our experi-
mental program. In fact, this second i-PP
goes under the same code "i-PP Daplen
KS 10", but with a date of production of
about one decade later than the "old" mate-
Recently, Monasse (1995) reported a quite interest-
ing process occurring in the supercooled melt of a
polyethylene. For the purpose, this author produced
shear flow between parallel glass plates in order to
enable optical observation in a direction perpendicu-
lar to the shearing plane. At rather low rates of shear
(~2 s"1), birefringent strings were formed perpendic-
ular to the flow direction. At slightly higher rates of
shear, some of these strings were diverted into the flow
direction. This is possibly a primary process overcom-
ing the disturbing influence of the rotational compo-
nent of shear flow on the far going orientation of sin-
gle macromolecules in the flow direction. Inspired by
Monasse's observation, we recently found (Jerschow
and Janeschitz-Kriegl, 1996), that the same has hap-
pened in the above-mentioned fine-grained zones, the
white spots simply being the cross sections through
these structures extending perpendicularly to the sur-
faces of the cut.
Table 5-5. Molar mass averages for two industrial
Daplen grades of i-PP a.
Grade
OldKSlO 1360 322 47 6.8
NewKSlO 545 235 77 3.1
a
PetrochemieDanubia(1993).
rial of which, at the time, quite an amount
was laid in store. In Table 5-5 the usual
molecular mass averages are given for these
polymers. Meanwhile, it was realized that
the tail of the molar mass distribution at the
high molar mass side, as is characteristic for
the "old" material, is responsible for the for-
mation of the highly oriented layers in injec-
tion molding, which are undesirable from
the point of product quality.
As can be seen, the so-called centrifuge
average Mz is particularly high for the
outdated Daplen KS 10. As Mz is defined
as I f i f M f / d ^ M ? ) [with M w =I/i l -M?/
(Ln( Mi) and Mn = w,- M;/!>;], a high value
of Mz is indicative of the presence of a large
fraction of very long molecules. As we shall
see, the choice of the outdated grade of
Daplen KS 10 was very lucky. As it turned
out, we were able to obtain the described,
very pronounced results because of the very
broad molar mass distribution of this poly-
mer. These results could only be vaguely
reproduced with the new material (Jer-
schow, 1994).
However, the new grade unexpectedly
provided us with further ways of proving the
correctness of the given model theory. In
fact, as the achievable (average) length L of
the threadlike precursors may depend on the
said high molar mass tail of the distribution
function of the molar masses, the extension
of the theory, as given by Eq. (5-104) for the
relaxation time r/5 may become superfluous
for a narrower molar mass distribution. In
such a case, T, may be so small that the

10
Shearing time t [s]
approximation of Eq. (5-102) is even valid
for the measurements in transmitted light.
This has actually been found (Jerschow,
1994), and is shown in Fig. 5-50. On com-
parison with Fig. 5-39, it is noticed that the
vertical distance between the lines for equal
shear rates is still 4 log (%/%_]); the slope of
log t^ 2 vs - lg ^s is> however, equal to minus
one instead of minus two. Both findings are
in accord with Eq. (5-102). Would anybody
have been able to interpret such a result with-
out having the experience with the old grade?
Also, the determination of layer thicknesses
turns out to be much more difficult with the
new grade: Of course, there is no longer a
sharpening mechanism, with the second term
in Eq. (5-104) having no influence.
Another situation may prevail if a nucle-
ation agent (inoculant) is added to the poly-
mer. In such a case the number N of primary
nuclei per unit of volume will become vir-
tually constant. Integration of the appropri-
ately modified Eq. (5-99) would lead to
f ** (5-125)
5.3 Flow-Induced Crystallization 333
Figure 5-50. New Daplen KS 10:
Plot similar to that of Fig. 5-39; verti-
cal distance 41og()'z/7/_]), slope - 1 ,
r=150C(Jerschow, 1994).
This prediction has also been implied
recently (Janeschitz-Kriegl, 1995), as is
shown in Fig. 5-51. Here we see that the ver-
tical distance is only 2 log (fc/fc_i)> where-
as the slope of log t^2 vs. s is - 1 , as should
be the case.
In conclusion, more systematic investiga-
tions should be carried out with a basic poly-
mer of rather narrow molar mass distribu-
tion, to which various amounts of long
molecules are added in order to check their
influence on T/. An alternative way would
be to investigate a series of well-defined
reactor grades with widely varying average
molar mass distributions. Last but not least,
this type of research should also be trans-
ferred to other polymers, like polyethylene.
5.3.8 Chances for Numerical
Simulation
Assuming that around a threadlike pre-
cursor space is gradually occupied by later-
al growth, in which not only the oriented
334 5 Crystallization

D 51s"1
O 32 s-1
A 19 s-1

\0z

101

Figure 5-51. Nucleated i-PP: Plot

similar to that of Fig. 5-39, vertical
distance 21og(y, //,_]), slope - 1 ,
10u 7 = 1 5 0 C (Janeschitz-Kriegl, 1995).
10 1 10' 102
Shearing time t [s]

lamellae, as discussed in the previous sec- become of less importance. On the whole
tion, are involved, but also the less orderly the lateral extension of the highly oriented
crystallized volume elements, we obtain layer is determined by the existence of
for the "unrestrictedly" growing volume threadlike precursors in a sufficient den-
per unit volume due to oriented growth (p0 or sity.
(disregarding impingement) Equation (5-126) can be differentiated
twice with respect to time without any dif-
ficulty
jduG(u) (5-126)
1
G(t) dt,
where, again, the assumption is made that t t
(5-127)
the growth speed G(t) is unaffected by flow = 47i\dLioi(s)\duG(u)
despite our intention to also use this equa- 0 s
tion for the more general situation of later- This is the internal growth surface per unit
al growth during flow. In fact, this assump- volume, as in the case of spherulitic growth
tion seemed fair for lateral growth occurring
after the cessation of previous flow. But here 4^Ltoott(r) (5-128)
a more rigorous situation is envisaged. ^orw G(t) dt ^
However, trusting Wolkowicz (1978), who This is 4;r times the total length of precur-
reported that mainly the primary nucleation sors per unit volume.
is affected by flow, the assumption does not So far we have followed Schneider's
seem to be too bad. Also, if the average method in the use of G(t). Using Eq. (5-99)
distance between threadlike precursors for Ltot together with the differential equa-
becomes small, the exact values of G(t) tion [Eq. (5-98)], the next rate function <p3 or
 5.3 Flow-Induced Crystallization 335

can easily be defined

?>3,or(0 =

dt
= $n N(t) (5-129)

which is proportional to the number of

threads per unit of volume. This simple
equation holds only if T is not dependent
on the length of the individual threads
[i.e., )3=0 in Eq. (5-104)]. Using the diffe-
rential equation [Eq. (5-97)] for N, the
following equation is finally obtained for
</>3,or

dt ^-| (5-130)

The main problem is always the determi-

nation of the parameters, which are Tn, T/5
gjj2w and g//y| in the present case, as func-
tions of temperature. As a new aspect, the
local shear rates should be linked to a change
in the rheological behavior by proceeding
lateral growth on the precursors. As we have
seen in the previous sections, with isother-
mal short term shearing experiments only
the temperature dependence of the product
of the latter two parameters can be deter-
mined [see Eq. (5-117)].
In principle, there should be a method for
the separate determination of N. In fact, the
mean length of the threads < L > is given by
(5-131)
N Eq. (5-116) by this < L >, which is obtained
which should be accessible to independent
evaluation from electron micrographs. This
becomes evident from Fig. 5-52. This
micrograph covers a distance of 20.8 |am in
the vertical direction and is taken from a
cross section parallel to the previous flow
direction near the duct wall. (See the dam-
age at the lower side which indicates the
Figure 5-52. Electron micrograph of a cross section
from the middle of the sample in a plane perpendicu-
lar to the large duct surface for the PP sample and the
shear treatment described under Fig. 5-44. In the ver-
tical upward direction this picture stretches from the
rim to about 20.8-|Lim inward (Liedauer et al., 1993).
(Courtesy of Hanser-Verlag, Munich.)
presence of the rim.) The length of the
strands can be estimated to be of the order
of 10 |im. So far, however, no micrographs
have been taken with the intention of carry-
ing out this evaluation. Nevertheless, it is
possible to try to obtain an impression of the
value of Nby dividing the value of Ltotfrom
under identical conditions. In this way, for
r=150C, 7=72 s"1, andfs = 7 s
N = 1.7 x 10 17 nT 3 (5-132)
which seems of the right order of magnitude
in view of the fact that in quiescent melts
values up to 1015 m~3 have been found for
polypropylene.
336 5 Crystallization
However, this method will be quite inac-
curate (even in isothermal short term shear-
ing), so that from a temperature and shear
rate dependence of N it will be difficult to
conclude on a respective dependence of L.
Probably, another principle may be useful in
this connection, i.e., the time-temperature
superposition principle (Ferry, 1980). This
principle may be useful despite the fact that
Wippel's (1989) experiments show a quite
different temperature dependence of the
relaxation of precursors. This deviating
dependence may be due to the factor (5 in
Eq. (5-104). This factor should describe the
disintegration of a supermolecular structure
in a quiescent melt under the influence of
thermal motion, whereas the creation of
nuclei by flow and their growth may be
influenced by the behavior of single mole-
cules. The same may hold for a in Eq.
(5-104), which describes the disintegration
of very loose aggregates in their nascent
state. With this argumentation as a back-
ground, it may be assumed that
and (5-133)
N(t, Y,T) = N(tla, fa, To)
where To is a reference temperature and a
(T) is a shift factor obtained from rheologi-
cal measurements on the melt. Such an
assumption would be in line with the fact
discussed earlier in this paper, according
to which a plot of (Gt^2) against Y\ ts no
longer shows a significant temperature
dependence, as is shown in Fig. 5-53. As
pointed out previously, the main influence
of the temperature on the curves, as shown
in Fig. 5-39, was ascribed to the large tem-
perature dependence of G(T). At this
stage in our knowledge, no further attempts
at an evaluation should be tried, however.
Apparently, the problems are still formid-
able. In fact, convective terms also have to
be included if practical processes are mod-
eled.
Finally, some remarks with respect to the
goal of such calculations should be made.
The main purpose of such a calculation will
certainly be the calculation of the distance
from the wall where the highly oriented
layer breaks down. A critical value Ltot>lim
was given earlier [see Eq. (5-118)]. If such
a value is accepted, the procedure given by
Eqs. (5-126) to (5-130) must be carried out,
where in Eq. (5-130) Tn is always put equal
to infinity (omission of the second term on
the right), whereas Eq. (5-129) must be used
in two forms, i.e., with T = and T -a.
Finally, the solution is used for which Ltot lim
is reached at a later time or, at a given shear-
ing time, at a smaller distance from the wall
(higher shear rate).
In fact, for isothermal short term shear-
ing this procedure can be explained quite
easily. This is demonstrated by a sketch
given in Fig. 5-54. This figure reminds us
of Figs. 5-41 and 5-42. If the scale of ts is
extended to lower values, which may be
characteristic for injection molding, the
bend which is also shown in Fig. 5-43 is
obtained. In our sketch the two lines drawn
show the location where Ltot lim is reached,
if Eqs. (5-101) or (5-102) are used, respec-
tively. If the growth process is followed at
a sufficiently high value of ycl (above the
bend), a corresponding horizontal line is
moved along until the steeper line is crossed.
This is the end of our process, which means
that after crossing this cross-over Ltot
becomes larger than LtotVim. However, at a
yc 2, which is below the bend, the descrip-
tion varies. Assuming the validity of Eq. (5-
101), Ltot,iim will be reached at the cross-
over of our horizontal line with the steeper
line. However, when the corresponding time
is reached, the validity of Eq. (5-101) is no
longer given. With further growing time a
transition is passed through, as given by
 5.3 Flow-Induced Crystallization 337

log(G(T)t x/2 )
-o?

-6
4
A "
??A - f t -
-o O

A - TfT %. ^

Q- Figure 5-53. Double logarithmic plot of

-7 O the product Gt^2 against the product yj t
9
for PP Daplen KS 10. Temperatures of
V experimentation: 143 C (little squares:
67 s"1 bib right, 85 s"1 bib down, 110 s' 1
-a A bib left, 139 s"1 bib up); 150 C (rhombi:
83 s"1 bib right, 104 s"1 bib down, 133 s"1
bib left, 169 s"1 bib up); 157 C (large
squares: 151 s"1 bib right, 195 s"1 bib
down) (Liedauer et al., 1993). (Courtesy
-8 of Hanser-Verlag, Munich.)

log (Ywt a

3-

01
o Figure 5-54. Sketch for the
calculation of the boundary
of the highly oriented layer
according to the text. The
scales are similar to those
r in Figs. 5-41 and 5-42, but
extended to lower ts values,
which may be expected
under real injection mold-
ing conditions.
logtjsl

Eq. (5-100), and reaches the cross-over with for the total degree of crystallinity
the less steep line, corresponding to Eq. (5- g = 1 - exp[-(p 0 (t,x) - y/0 (t, x) - <p0,or (t, x)]
102).
One final remark, however, seems worth- (5-134)
while: According to the method of the Pois- No simple relation can be obtained for the
son processes [see Eqs. (5-10) and (5-48)], morphology, however, like Eq. (5-13). Nev-
338 5 Crystallization
ertheless, from the course of the calculation
it will become apparent which type of pro-
cess will be predominant locally and deter-
mine the morphology.
5.4 Closing Remarks
Obviously, one goal of this investigation
should be the simulation of a realistic pro-
cess, e.g., injection molding. From our
experience of cooperation with industrial
partners, however, we also know that just
the understanding of a process itself is of
nearly equal importance. In fact, if the final
structure of a product should be predicted
by numerical calculations, these calcula-
tions would be terribly involved. We think
that this has become clear from the content
of this chapter. For the manufacturer, the
way he has to alter the composition or the
chemical structure (e.g., the molar mass dis-
tribution) in order to achieve a desirable
physical structure (morphology) is of great
importance. And with very involved com-
puter programs, the calculation still takes
more time and is more costly than a simple
molding experiment. The design of such an
experiment is almost as important as the
design of an adequate computer program.
If the progress made so far for numerical
simulations is considered, it is immediately
clear that the respective authors had an
insufficient knowledge of the real process-
es. A popular assumption that is usually
made is the existence of an induction time.
However, we have clearly shown (at least
for i-PP) that such an incubation time does
not exist (see Fig. 5-22 and Sec. 5.2.2.4,
where the growth speed of spherulites could
be calculated from the time span character-
istic for the occurrence of noticeable light
scattering). Another important point is that
with the growth of a shear-induced layer, the
width of the duct (strip mold) is effectively
reduced. However, in our National Working
Party on Injection Moulded Parts S 33,
Fleischmann and Koppelmann (1987) car-
ried out injection-molding experiments with
short shots. This means that the stresses
were immediately released when the filling
procedure was stopped. Nevertheless, the
well-known highly oriented layers were
found in the cross sections. In our terminol-
ogy, these experiments were short term
shearing experiments. This means that at
least part of the layers was developed only
after the cessation of flow, i.e., where the
temperature did not decrease, e.g., below
140 C, during the filling procedure. In this
area, the rheology was not noticeably influ-
enced during flow by crystallization.
The energy equation for the filling of a
rectangular duct of large aspect ratio cor-
rectly reads
'U dx dt dx
(5-135)
ay
where u is the velocity in the x-direction
(flow direction), y is the coordinate in the
gap-wise direction, h is the heat of crystal-
lization per unit mass, p is the density, cp is
the specific heat, X is the heat conductivity,
y(y, t) is the shear rate as a function of the
distance from the mid-plane, and r\(T, y) is
the viscosity as a function of the tempera-
ture and shear rate. The two expressions in
parentheses are the total derivatives with
respect to time of the temperature DT/Dt and
of the degree of crystallinity D^/Dt.
The problem with this equation, howev-
er, is similar to that of Eq. (5-31), i.e., that
the rate of crystallization D^/Dt is not a
function of the local state variables as used
in Eq. (5-135), i.e., (t, x, y) and T(t, x, y).
In fact, % is a function of the previous shear
and temperature history, as we have clearly
shown in Sec. 5.3.

The most widely used crystallization
kinetic equation in computer simulations is
a generalization of Avrami's equation, as
given by Nakamura et al. (1972)
\K(T(t'))dt' (5-136)
where n is the Avrami index, t{ is an induc-
tion time, and K(T) is a kinetic function,
which can be determined from the half time
of crystallization under isothermal condi-
tions. Since this equation has the property
that the time derivative of can be written
in the form
| (0 = K(T{t)) /( (t)) (5-137)
with some function/, the rate of crystalliza-
tion is not dependent on the current crystal-
line structure and therefore also contains no
information on it [see Eq. (5-21) of the
present review]. An assumed continuous
change in the Avrami index n from 3 to 1
with increasing shear stress could be the
only indication of structural changes
(Hsiung and Cakmak, 1991).
The only exception where a reasonably
realistic structure can be predicted is for
high temperature polymers that show a glass
transition temperature above the mold and
room temperatures. Such a treatment has
been carried out in an early paper by Berger
high stress intermediate stress
fast cooling intermediate cooling
I Tw
time
skin shear zone
Figure 5-55. Cooling curve and CCT curve for slowly crystallizing material at three different positions in the
mold. (Courtesy of the Society of Plastics Engineers.)
5.4 Closing Remarks 339
and Schneider (1986) for the quiescent melt,
who assumed a unique temperature depen-
dence of the overall speed of crystallization,
which became zero at the glass transition
temperature (Tg) and at the melting point
(r m ). These authors predicted an amorphous
vitreous layer between the quenched wall
and the crystalline interior. However, except
for a continuous increase of the degree of
crystallinity from zero to a maximum final
value at a sufficient distance, no more
detailed structural features could be predict-
ed.
An analogous case was treated by Hsiung
and Cakmak (1991) for the injection mold-
ing of a high temperature polymer (poly-
phenylene sulfide). These authors could
predict for intermediate mold temperatures
(not too far below the glass transition tem-
perature) a three-layer structure: a vitreous
layer close to the mold wall, a crystalline
layer at some distance from the wall, and,
again, a vitreous region in the core. Qualita-
tively, this structure can be explained by Fig.
5-55. In this figure a situation is character-
ized with the aid of the nearly parabolic, so-
called CCT (continuous cooling transfor-
mation) or TTT (time-temperature transfor-
mation) curve. This curve stretches along
the ordinate axis over a temperature span
from Tg to Tm. The crystallization time is
plotted on the abscissa. With nonzero stress
low stress
low cooling
time
core
340 5 Crystallization
it is supposed to have an apex at a shorter
time and at a temperature closer to Tm when
compared with the curve assumed for a
quiescent melt. Nevertheless, for the high-
est shear stresses, which occur close to the
duct wall, the cooling rate, as represented
by the monotonically decreasing curve, is so
high that the apex of the CCT curve is not
touched. At a distance more remote from the
wall, the shear stress is lower, so that the
CCT curve shifts to a lower temperature and
to a higher time. However, due to the lower
cooling rate, the CCT curve is cut by the
cooling curve. This causes the occurrence
of crystallinity. In the core the CCT curve
retracts drastically, because of nearly zero
shear stress. Even if the cooling is even
slower there, the cooling curve is again to
the left of the CCT curve. This causes the
vitreous core region. It will not surprise the
reader that at a mold temperature above Tg
the whole sample crystallizes, whereas at
an extremely low mold temperature, the
whole sample vitrifies. However, this model
cannot predict details of the crystalline
structure. The "structure" of the sample is
solely determined by the gradual transition
from the amorphous to the crystalline state.
The CCT curve is a concept taken from met-
allurgy (Kalpakian, 1989). It represents the
occurrence of a certain crystallinity, e.g., =
1/2. Also, the shape of the curve will
depend, at least in the case of a shear treat-
ment, on the previous shear and temperature
histories, and cannot be a unique function
of the shear stress.
5.5 Acknowledgements
The financial support by the Austrian
"Fonds zur Forderung der Wissenschaftli-
chen Forschung" in Vienna, which was sup-
plied for a national working party S 33
"Injection Moulded Parts" over many years,
is acknowledged, as well as the more recent
aid received from the Christian-Doppler-
Society in the form of a senior research fel-
lowship "Flow and Solidification of Ther-
moplastics". The authors are also indebted
to Petrochemie Danubia for its direct inter-
est and cooperation in this subject. In this
connection, the "Forschungsforderungs-
fonds fur die gewerbliche Wirtschaft"
should also be mentioned. Several details
from classified work could later be used to
round off the general picture.
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6 Fundamentals of Reactive Extrusion: An Overview
Guo-Hua Hu and Morand Lambla+

Laboratoire d'Extrusion Reactive, Ecole d'Application des Hauts Polymeres,

Institut Charles Sadron (CRM - EAHP), Strasbourg, France

List of Symbols and Abbreviations 346

6.1 Introduction 348
6.2 Fundamentals of Reactive Extrusion 351
6.2.1 Scientific Classification 352
6.2.2 Basic Features 353
6.2.3 Fundamental Principles 353
6.2.3.1 Continuous Flow Reactors 353
6.2.3.2 Screw Extruders as Continuous Flow Reactors 357
6.3 Case Studies 362
6.3.1 Melt Chemical Reactions in a Batch Mixer 363
6.3.1.1 Functional Reactions 363
6.3.1.2 Free Radical Grafting of Monomers onto Polymers 375
6.3.2 Screw Extruders as Continuous Flow Reactors 381
6.3.2.1 Functional Reactions in a Microfluid 382
6.3.2.2 Free Radical Grafting of Monomers onto Polymers 383
6.3.3 Screw Extruders as Reactive Blenders (Compounders)
for the In Situ Compatibilization of Immiscible Polymer Blends
by One-Step Reactive Extrusion 388
6.3.3.1 Devolatilization: A Critical Sequential Operation 390
6.3.3.2 Effects of Processing Parameters 392
6.3.4 Residence Time Distributions in Screw Extruders: A Statistical Theory . . . . 394
6.4 Conclusions 396
6.5 References 400

Materials Science and Technology

Copyright WILEY-VCH Verlag GmbH & Co KGaA. All rights reserved.
346 6 Fundamentals of Reactive Extrusion: An Overview

List of Symbols and Abbreviations

A total final interfacial area

total initial area
a, b initial molar concentration
A,B apparent initial molar concentration
C concentration
D electron-donating monomer
D diffusivity; axial dispersion coefficient; diameter
f(0 residence time distribution density function
F{t) residence time distribution function
g(T) dimensionless residence time distribution density function
h diffusion length
K equilibrium constant
^app apparent rate constant
k\,k'2 forward and reverse reaction rate constants
ku kXc; k2, k2c forward and reverse intrinsic kinetic constants
L length
M n , M_n number-average molecular weight
MW,MW weight-average molecular weight
n number
N screw speed
nx,n2 molar number of functional group
P conversion
Pe Peclet number
Q feeding rate
r bla
R reaction rate
S(k'uk'2,) objective function
t residence time
t mean residence time
T temperature
*D diffusion time
*R reaction time
U axial velocity
U velocity; specific energy
u average velocity in axial direction
Vi volume of reactive polymer
Vi volume of inert polymer
X zIL
axial coordinate

a (A+B + 1/IQ
7 total strain
A \/a2-4AB
 List of Symbols and Abbreviations 347

partition coetticient; areal chain density

e tIE
T dimensionless time

Cat catalyst
CSTR continuously stirred tank reactor
CTC charge transfer complex
DBTDL dibutyltin dilaurate
DBTO dibutyltin oxide
DHBP 2,5-dimethyl-2,5-di(ter/-butylperoxy)hexane
DIPP l,3-bis(terr-butylperoxy-isopropyl)benzene
DTFR dispersion tubular flow reactor
EMA poly(ethylene-c6>-methyl acrylate)
EPR ethylene and propyl rubber; electron paramagnetic resonance
EVA poly(ethylene-co-vinyl acetate)
GMA glycidyl methacrylate
HPLC high performance liquid chromatography
IBVE isobutylvinylether
MA maleic anhydride
MAc methyl acrylate
MMA methyl methacrylate
NMR nuclear magnetic resonance
NVP N-vinylpyrrolidone
OL12 1-dodecene
PA polyamide
PBT poly(butylene terephthalate)
PGMA poly(ethylene-co-ethyl acrylate-glycidyl methacrylate)
phr part per hundred resin
PLR plug (piston) flow reactor
PP polypropylene
PPOH 3-phenyl 1-propanol
PS polystyrene
PSOH mono-hydroxylated polystyrene
PVC poly(vinyl chloride)
REX reactive extrusion
RTD residence time distribution
SEC size exclusion chromatography
ST styrene monomer
TMVS trimethoxyvinylsilane
VAc vinyl acetate
VCH vinylcyclohexane
348 6 Fundamentals of Reactive Extrusion: An Overview
6.1 Introduction
For years, both chemistry and engineer-
ing practice involving polymer systems
used inert liquid carriers to avoid complica-
tions caused by the high viscosity of undi-
luted bulk systems; these systems are other-
wise difficult to handle in classical reactors
of a stirred-pot version, such as beakers, ket-
tles, and tanks. When a polymeric system
was too viscous, it was simply diluted with
more liquid effluents.
During the last three decades and due to
ever-increasing concerns and tougher gov-
ernment regulations about the excessive
use of solvents, reactions have more and
more been run in solventless polymer
melts using polymer processing machines
as chemical reactors, e.g., batch mixers
and screw extruders. However, the absence
of solvent may raise other complications:
high temperature, heterogeneity of the
reacting media, low mass and heat transfer,
low polarity, etc., rendering proper control
of the selectivity and the rate of reaction dif-
ficult.
The same period of time has also seen
increasing demands for polymeric materials
of high performance. Due to high R&D and
reactor start-up costs, introducing new
monomers (formerly the most frequently
practised method by polymer chemists to
create new polymers), has gradually given
way to other methods in response to these
demands. Resin suppliers, speciality com-
pounders, and even end-product users are
now trying to diversify existing polymers by
chemically modifying or reactively blend-
ing them inside a screw extruder.
In fact, the use of extruders as chemical
reactors and reactive blenders (or corn-
pounders), nowadays commonly called
reactive extrusion (REX), has proven to be
a critical technology in the polymer indus-
try to achieve more decisive property
enhancements than would have been pos-
sible with classical reactors. This has been
confirmed by our recent literature survey
(Lambla, 1993): the majority of people who
are active in REX are industrial scientists
and engineers rather than academic
researchers; there were about 800 patents
compared to about 100 papers in the open
literature during the 1980s. Apart from the
aforementioned commercial interests, the
primary reason for the success of REX is
that as a reactor or a blender, a screw extrud-
er has the unique ability to convey and mix
highly viscous fluids and to facilitate the
staging of multiple process steps in a single
machine, including feeding, solids convey-
ing, melting, mixing, reacting, side-stream
incorporation (reactants, fillers, and/or
stripping gases), degassing, pumping, and
under some circumstances, shaping.
Based upon the above discussion, reac-
tive extrusion (REX) may be defined as a
manufacturing process that combines the
traditionally separated polymer chemistry
(polymerization or chemical modification)
and extrusion (blending, compounding,
structuring, devolatilization, and shaping)
into a single process carried out in a screw
extruder. This definition indicates that from
an engineering standpoint, REX bears vir-
tually all the basic features of classical
extrusion processes; from a chemistry view-
point, REX is the use of screw extruders as
chemical reactors. This duality provides
REX with two important fields of applica-
tion:
1) The use of screw extruders as chemical
reactors for the polymerization of
monomers and the chemical modifica-
tion of existing polymers.
2) The use of screw extruders as blenders
to reactively blend existing polymers
(sometimes in the presence of fillers or
other additives).

Listed below are four main advantages of
using screw extruders as chemical reactors
or reactive blenders:
1) Solventless polymerization/polymer
modifications. A typical solution-pro-
cess reactor usually comprises sol-
vents/diluents 5-20 times the weight of
the desired polymer product. This means
that some big commercial processes of
this type use up to more than ten tons of
solvents per day. Therefore the
extruder's unique ability to handle high-
ly viscous polymer fluids without the
need for solvents results in dramatic cost
reductions in raw materials, solvent
recovery, product separation, and drying
equipment. The absence of solvents also
makes REX a process that is more envi-
ronmentally friendly and less bulky
compared to a classical polymer reaction
process.
2) High overall reaction rate. This is main-
ly due to much greater concentrations of
reactive species in the melt than in solu-
tion. Also, the reaction temperatures are
usually 50-150C higher than in solu-
tion.
3) Continuous and flexible process for low
tonnage trials or production. Making
new materials of low tonnage (e.g.,
below 5000 tons per year) does not usu-
ally justify the expense of reactor start-
up and associated costs. Screw extrud-
ers are ideal for such processes. Under
certain circumstances, speciality com-
pounders can just use their extruders and
make products in a ready-to-use form in
order to meet specific needs without
having to rely on their resin suppliers.
4) Staging of multiple reactions. Owing to
the unique ability of an extruder to per-
form multiple and sequential operations,
including side-stream reactant incorpo-
ration and multi-venting systems, vari-
6.1 Introduction 349
ous reactions can be carried out along
the extruder length. Thus, polymers that
are sometimes "impossible" to make in
a classical reactor can be made in an
extruder.
Of course REX also has disadvantages:
1) Short residence times. If the residence
time required for accomplishing a reac-
tion is long (e.g., more than 30 min), an
extruder is unlikely to be an economical
reactor. This means that slow reactions
are not good candidates for REX.
2) Limited heat transfer capacity. The lim-
itations on heat transfer out of an extrud-
er are the primary concern when reac-
tions releasing a large amount of heat are
to be performed in an extruder. For
example, breaking one mole of the car-
bon-carbon double bond of vinyl
monomers by free radical initiation
yields a heat of some 50-90 kJ. The heat
released on converting 1 kg of styrene
may reach as high as 700 kJ. This
amount of heat may be too much for
common extruders to handle. Very often
a well controlled reacting system on a
laboratory scale extruder may run into
trouble when it is processed on a pilot or
an industrial scale machine simply due
to a reduced heat transfer capacity.
3) Side reactions. Because of disparity in
the temporal, compositional, and ther-
mal mixing histories the reacting species
may have experienced in a screw extrud-
er, side reactions may become important
and difficult to control.
Whatever the pros and cons of REX
described above, virtually all types of chem-
ical reactions developed in polymer chem-
istry can, in principle, be processed by REX.
From an engineering viewpoint, these reac-
tions can be classified into the following
three main categories:
350 6 Fundamentals of Reactive Extrusion: An Overview
1) Polymerization of monomers. The vis-
cosity of the system rises as polymeriza-
tion proceeds. In the case of some free
radical polymerization reactions, heat
run-away may be another important
challenge; for condensation reactions,
which release volatile products, effi-
cient removal of these volatile products
by devolatilization may be crucial for
obtaining high molecular weight poly-
mers.
2) Chemical modification of existing poly-
mers. In many cases, a small amount of
a low molecular weight reagent is used
to chemically modify the backbone or
pendant groups of polymers. Thus the
viscosity change is usually less dramat-
ic than in the case of polymerization.
Nonetheless, it may be difficult to inject
and/or to achieve adequate dispersion of
a low molecular weight reagent into a
molten polymeric fluid due to a large
disparity both in the viscosity and the
volume fraction between them.
3) Polymer-polymer reaction. Here again,
the viscosity rise is usually less pro-
nounced than what is often encountered
in free radical polymerization. However,
because of the fact that chemical reac-
tions between two immiscible polymers
take place primarily at their interfaces,
an efficient interfacial renewal becomes
the most critical parameter that controls
the overall reaction rate.
Shown in Table 6-1 are selected examples
of these three types of reactions of REX.
In fact, these last two types of reaction in-
volve the underlying chemistry for the in
situ compatibilization of existing immis-
cible polymer blends. This latter is probably
the most important application of REX. A
well-studied example is the reactive blend-
ing of an ethylene and propylene rubber
(EPR) with a poly amide (PA 6 or PA 66). As
PA 6 has amine groups at its chain ends
while EPR is chemically inert with respect
to it, the in situ compatibilization of this
blend requires that the latter be functional-
ized with a monomer bearing desired func-
tional groups by free radical grafting. The
free radical grafting of maleic anhydride
(MA) is the process most employed for this
purpose. The MA-grafted EPR then reacts
with the amino group of the PA 6 to form an
amphiphilic copolymer (EPR-g-PA 6)
through interfacial reaction during extru-
sion.
It is not the purpose of this chapter to give
an overview of the state-of-the-art of REX
in a systematic manner by retrieving all the
published results. This is because REX as a
new engineering discipline is still in its
infancy despite the knowledge that has been
gained in an ever-increasing number of aca-
demic and industrial laboratories. Also,
there is already an excellent monograph
which attempts to review the state-of-the-
art of REX [Xanthos (Ed.), 1992]. As such,
this chapter will attempt only to provide
some general guidelines on selected funda-
mental problems raised in REX, rather than
an exhaustive list of published examples
and/or industrial applications. Specifically,
the following aspects, which to a great
extent constitute the framework of REX,
will be addressed:
the behavior of chemical reactions
involving polymers in the melt in a batch
mixer;
the performance of screw extruders as
continuous flow reactors;
the performance of screw extruders as
reactive blenders or compounders;
the residence time distribution in screw
extruders.
This will be done exclusively using exam-
ples investigated in our laboratory. For the
sake of readability, a brief overview will be
 6.2 Fundamentals of Reactive Extrusion 351

Table 6-1. Selected examples of chemical reactions explored by REX.

Reaction Free radical reactivity Functional reactivity

Bulk poly- polymerization of styrene synthesis of polyurethane

merization of (Stober and Amos, 1950) (Fryeetal., 1966)
monomers heat HOOC(CH )COOH + HO(CH )OH
into polymers 2RO*

(OCNH- -NHCO(CH ) )

Chemical grafting of maleic anhydride onto poly(ethylene-c<9-vinyl acetate) to

modification polypropylene (Flat, 1991) poly(ethylene-co-vinyl alcohol)
of existing (Bouilloux et al., 1987)
polymers heat CH-CH
ROOR " 2RO* 2 I
I ROH
CII CH C=O
I 3
-CH-CH + RO* 'CH C + ROH CH
2 *

H CH=CH
3 I I
^c c> - CHCH*
I I
C Cv

"W + CH-C-OR
3
H

Polymer-polymer polymeric free radical coupling polymer-polymer coupling

reaction (Zouikri, 1982) (Scott and Macosko, 1988)
o

\ \
CH CH
I 2 | 2
CHCH
* \

given in the first part of this chapter on some
fundamental aspects of using screw extrud-
ers as continuous chemical reactors from the
chemical engineering viewpoint.
6.2 Fundamentals of Reactive
Extrusion
Disregarding the above mentioned vir-
tues and vices of REX and its industrial
applications, it is important to point out that
REX has become a distinct engineering spe-
ciality which combines the multiple disci-
plines of polymer chemistry, physical chem-
istry, polymer processing, chemical engi-
neering, mechanical engineering, fluid
mechanics, etc. Owing to this multi-disci-
plinary nature, REX has attracted increas-
ing attention from scientists and engineers
of different backgrounds, therefore provid-
ing a common interest in relation to which
they can communicate and interact. Inter-
estingly, people with different backgrounds
or interests see REX differently. For chem-
ists REX is the use of screw extruders as
352 6 Fundamentals of Reactive Extrusion: An Overview
special chemical reactors to carry out chem-
ical reactions involving polymers in the
absence of solvents. On the other hand,
chemical engineers consider screw extrud-
ers as special chemical reactors of a plug
flow form which operate on the principle
of drag flow (relative motion between
screws and barrel). Transport phenomena,
mixing and chemical reactions associated
with non-Newtonian polymeric and often
heterogeneous fluids in these strange reac-
tors give the traditional chemical and poly-
mer reaction engineering a new horizon of
research.
6.2.1 Scientific Classification
From a geometrical viewpoint, a REX
process is basically the same as an extrusion
line, except that in the former case addition-
al auxiliary equipment may be needed, such
as for the side-stream feeding of reactants
and the devolatilization of unwanted vola-
tile products. In other words, the extruder
constitutes the heart of a REX process
(Fig. 6-1). The assembly of a REX line may
be divided into three parts:
1) the interior of the extruder (barrel,
screws);
2) the exterior or auxiliary equipment
(side-stream feeding, devolatilization,
pelletizing system, etc.);
3) data acquisition and control systems
(temperature, feeding, screw speed,
pressure, etc.).
solid feeding
i liquid injection
Figure 6-1. A geometrical diagram of a REX line.
This way of dividing a REX process
reveals that mechanical engineering,
electrical engineering, and process control
are also important for REX.
While mechanical engineering, electrical
engineering, and process control are impor-
tant for REX, they are, to some extent, aux-
iliary disciplines of REX. The core of REX
as a new engineering discipline is more a
cross between chemical engineering and
science and polymer engineering and sci-
ence. This is illustrated in Fig. 6-2. This
hierarchy chart shows how REX features in
relation to various disciplines. When a
screw extruder is used as a chemical reac-
tor, REX is a branch of polymer reaction
engineering. This latter in turn is part of
chemical reaction engineering. Of course
chemical reaction engineering is included in
chemical engineering and science. When a
screw extruder is used as a reactive blend-
er, REX can be considered as a blending or
compounding process with chemical reac-
tions involved. Blending and compounding
are two important topics of polymer pro-
cessing. Needless to say, polymer process-
ing falls into the general area of polymer
engineering and science. This hierarchy
chart also indicates that chemical engineer-
ing and polymer engineering interact at each
hierarchical level of REX.
Although the above description may be
oversimplified or artificial, the real message
it intends to convey is that a good under-
standing of REX requires the understanding
of chemical engineering and science and
devolatilisation

HIERARCHY OF REX
the use of screw extruders as
chemical reactors
\ f
polymer
reaction engineering
1r
chemical reaction
engineering
\ f
chemical engineering
& science
polymer engineering and science, as well as
interactions between the two.
6.2.2 Basic Features
The basic features of screw extruders as
chemical reactors which distinguish them
from other types of reactors are as follows:
A screw extruder can be considered as a
continuous tubular reactor due to its
lengthwise geometry (length-to-diameter
ratio 15 <LID< 50).
A screw extruder is capable of carrying
out chemical reactions in molten poly-
mers owing to its unique transport mech-
anism.
As a screw extruder is used primarily for
transporting highly viscous fluids, the
flow pattern is laminar.
Owing to the fact that the flow in a screw
extruder is laminar, the extruder has the
ability to perform various operations in a
6.2 Fundamentals of Reactive Extrusion 353
the use of screw extruders as
reactive blenders
\ r
blending and
compounding
f
polymer
processing
r Figure 6-2. Hierarchy
chart of REX in the context
polymer engineering of chemical engineering
& science and science and polymer
engineering and science.
sequential manner: feeding, solids con-
veying, melting, mixing, reacting, vent-
ing, pumping, and shaping.
Today's screw extruders for REX are
so well designed that the geometrical
boundaries that demarcate these individ-
ual sequential operations are more or less
well defined, which facilitates the control
of a REX process.
These features make screw extruders
ideal chemical reactors for performing reac-
tions involving highly viscous, molten poly-
mers in the absence of solvents.
6.2.3 Fundamental Principles
6.2.3.1 Continuous Flow Reactors
Regardless of the above features for the
use of screw extruders as chemical reactors,
they are nonetheless continuous flow reac-
tors. In a continuous flow reactor a reaction
occurs on a continuous basis with reactants
354 6 Fundamentals of Reactive Extrusion: An Overview
entering continuously at one end of the reac-
tor and products leaving at the other. Such
a system is usually designed for steady-state
operation, implying that the conditions at
any point in the reactor are time-invariant.
This contrasts highly with a batch reactor
where the fluid elements all experience the
same time in the reactor, and the composi-
tion is time-dependent.
The ultimate goal in understanding the
performance of a reactor, be it continuous
or batch, is to be able to predict the extent
of reaction. The extent of reaction in both
types of reactor is determined by the follow-
ing three aspects: time, concentration, and
temperature. As suggested previously (Hu,
1994), these three independent aspects may
be unified by one single word: mixing, if this
is defined as a process that is intended to
alter the state of a mixture in terms of time,
composition, or temperature. A process
whose aim is to reduce the compositional
Batch reactor Continuous flow reactor
Extent of reaction
temporal aspect compositional
of mixing aspect of mixing
residence time compositional
distribution distribution
macromixing micromixing
difference is called spatial mixing. Obvious-
ly, spatial mixing aims to promote physical
motion of the components involved in the
mixture. Physical motion is induced by
three basic methods: mechanical agitation,
eddy diffusion, and molecular diffusion.
Molecular diffusion is a random motion on
a molecular scale driven by compositional
gradients (chemical potentials). Eddy diffu-
sion is also a random motion, but on a larg-
er scale and driven by turbulence. To a cer-
tain extent, eddy diffusion can also be
viewed as the superimposition of molecular
diffusion on the gross random motion of
molecules. Mechanical agitation is the bulk
or macroscopic motion of fluid elements
driven by mechanical forces. It is common-
ly called mechanical mixing, convective
mixing, or mixing.
The above discussion can be summarized
in Fig. 6-3. Note that the temporal, compo-
sitional (spatial), and thermal aspects of
thermal aspect
of mixing
temperature
distribution
Figure 6-3. The three aspects of mixing:
thermomixing
temporal, spatial, and thermal mixing.
 6.2 Fundamentals of Reactive Extrusion
mixing are described by the residence time
distribution, the compositional distribution,
and the thermal distribution, respectively. In
chemical engineering literature they are
often referred to as macromixing, micromix-
ing, and thermomixing1, respectively. In
what follows, temporal and spatial mixing
will be discussed.
Temporal Mixing
A fundamental difference between a
batch reactor and a continuous flow reactor
is that in the former the fluid elements all
experience the same length of time before
they are discharged, while different flow
elements take different lengths of time to
pass through a continuous flow reactor (res-
idence time distribution or RTD), except in
the case of an ideal plug flow reactor. There-
fore a knowledge of the RTD in a given con-
tinuous flow reactor is important for evalu-
ating its performance (extent of reaction
and/or selectivity). Danckwerts (1953,
1958) was first to introduce the concept of
the RTD as a measure of the gross quality
of mixing in a continuous flow reactor.
Today RTD has become probably the most
important aspect in the field of chemical
reaction engineering. It has been treated
largely in the standard chemical engineer-
ing literature and related textbooks (Leven-
spiel, 1972; Nauman and Buffham, 1983;
Villermaux, 1985).
The residence time distribution of parti-
cles (they can be in the form of molecules,
aggregates of molecules, etc.) is described
by what is called the residence time distri-
bution density function, f(t) dt, or the resi-
dence time distribution function, F(t).f(t) dt
is defined as the proportion or probability
1
This terminology was invented by the authors and
does not apparently exist in the literature.
355
of particles for which the residence time is
in the time interval (t, t+dt). F(t) is the pro-
portion or probability of particles with a res-
idence time less than t.
Aside from the particular features of the
numerous continuous flow reactors which
actually exist, each reactor falls into one or
a combination of the following three ideal
flow reactors: plug (or piston) flow reactor
(PLR), dispersion tubular flow reactor
(DTFR), and continuously stirred tank reac-
tor (CSTR). Their basic features are given
in Fig. 6-4.
Spatial Mixing
The performance of a continuous flow
reactor cannot be determined by the RTD
alone, except in the case of the three ideal
ones mentioned above or combinations of
them. This is because the RTD function is a
form of "black box" analysis applied to con-
tinuous flow reactors. It can be obtained
experimentally by applying a stimulus to a
continuous flow reactor at the inlet, and
monitoring the response at the outlet. The
relationship between the output and input
provides the temporal aspect of mixing of
this reactor with little information about the
mechanisms of the mixing processes. In
other words, the only information which can
be revealed by an experimentally measured
RTD concerns the various time intervals
during which the various fluid elements
have stayed in the system, ignoring the inti-
mate contact the fluid elements may have
experienced therein. This indicates that the
correspondence between the RTD and the
mixing process is unclear. A particular mix-
ing process corresponds to a particular RTD,
whereas a particular RTD may result from
various mixing processes. In order to illus-
trate this point, look at the two extremes of
the state of a mixture in a continuous flow
356 6 Fundamentals of Reactive Extrusion: An Overview

THREE IDEAL REACTORS

u
L
-Q
plug or piston flow reactor dispersion tubular flow
(PLR) continuously stirred
reactor (DTFR)
tank reactor (CSTR)
All the particles entering at a The degree of mixing of the The particles are mixed so
particular time remain particles is between that for well that there are no
associated with each other, the PLR and the CSTR, and concentration or temperature
and they can only leave as a is characterized by the Peclet gradients; all particles have
group. There is no mixing number: the same chance of leaving;
among particles that enter at D
and no particle has a greater
different times.
In other where U is the average velo- chance than any other. In
words, there is no axial city of the fluid in the axial other words, the
mixing while the mixing in direction, L the pipe length and concentration and
the radial direction is perfect. D the dispersion coefficient. temperature are the same
Pe -> oo, PLR throughout a CSTR.
Pe^O, CSTR
Pe -Pe(l-tfi)2 Figure 6-4. Basic features
= S(t~t) f(t) = 4n(t/i) At It
of three ideal flow reactors:
the plug (piston) flow reac-
tor (PLR), the dispersion
tubular flow reactor
(DTFR), and the continu-
ously stirred tank reactor
(CSTR). t is the mean resi-
dence time.

reactor (Fig. 6-5): one extreme is of course
the state of the mixture on a molecular level,
where the molecules move and collide with
each other freely (Fig. 6-5 a); the other
extreme is the state of the mixture in which
the molecules are gathered together as
aggregates (Fig. 6-5b). The aggregates are
small in size in comparison to the volume
of the reactor, for example, yet they contain
a large number of molecules. These aggre-
gates or domains of segregation may be well
mixed, but the molecules contained in a par-
ticular domain of segregation are close
together. These molecules will have spent
the same time in the continuous flow reac-
tor. The two different fluids concerned, in
terms of compositional distribution, may
well have the same RTD function. Howev-
er, because of the difference in the compo-
sitional distribution, the extent of reaction
of nonfirst order will not be the same for
these two systems. This is the reason why
the temporal aspect of mixing as character-
ized by the RTD function is also called mac-
romixing while the spatial aspect of mixing
(state of the intimate contacts between par-
ticles) is called micromixing. The former
concerns all phenomena associated with the
RTD, and the latter characterizes the inter-
actions among the fluid elements during
 6.2 Fundamentals of Reactive Extrusion 357

flow, independent of macromixing. There- State of the Mixture

fore, unless the extent of spatial mixing or
micromixing is known, the RTD and the As described earlier, there are three ideal
intrinsic kinetic data alone are not enough residence time distribution functions corre-
to predict the reaction yield except in the sponding to the three ideal continuous flow
case of first-order reactions. reactors (Fig. 6-4). For a given reactor
(batch or continuous), the state of a mixture
therein falls into one of three primary ideal
distributions: microfluid, partially segre-
Y Y gated fluid, or macrofluid (Fig. 6-6). The
state of a mixture can be quantified by two
0 I parameters (Danckwerts, 1952): the scale of
segregation and the intensity of segregation.
These two parameters are illustrated in Fig.
6-7. The scale of segregation is a measure
of the size of segregated regions, and the
a- -a intensity of segregation is the relative dif-
ference in concentration of the property of
interest between segregated regions.

6.2.3.2 Screw Extruders as Continuous

(a) (b) Flow Reactors
Figure 6-5. Two mixtures mixed on different spatial
scales having the same RTD function: (a) a mixture of A variety of single screw and twin screw
two fluids mixed at a molecular level; (b) a mixture extruders have been employed as continu-
of two fluids whose molecules are phase separated. ous flow reactors for REX processes. What-

State of fluid
Microfluid Partially segregated fluid Macrofluid
The state of the fluid is mixed The state of the fluid is The state of the fluid whose
at the molecular level. The between microfluid and molecules are gathered
molecules move and collide macrofluid. together as aggregates.
freely with each other. These aggregates may be
well mixed together.

. *

1
A mixture of a white fluid and A mixture of a white fluid and A mixture of a white fluid Figure 6-6. Definition and
a black fluid mixed at a black fluid with one being and a black fluid with one
graphical representation of
three primary fluids: micro-
the molecular level. partly miscible with the other. being completely immiscible
fluid, partially segregated
with the other. fluid, and macrofluid.
358 6 Fundamentals of Reactive Extrusion: An Overview
C
o
1 dispersive mixing
CO
I
scale of segregation
Figure 6-7. Schematic representation of scale and
intensity of segregation.
ever the nature of a reacting system or the
geometry of a particular screw extruder,
their performance is dictated by the princi-
ples described earlier concerning general
continuous flow reactors: temporal, spatial,
and thermal mixing. However, the behavior
of these three aspects of mixing in a screw
extruder may differ from that in a classical
continuous flow reactor, primarily due to the
fact that a screw extruder is designed to pro-
cess highly viscous polymeric fluids. In the
latter case, convective mixing is the only
mechanism responsible for spatial mixing.
As early as 1951, Spencer and Wiley (1951)
realized that "an efficient mixing process
must accomplish two things so as to keep
fluctuations in average composition below
some desired level: (a) subdivision of the
materials present, and (b) distribution of the
subdivided materials". This is better seen in
Fig. 6-8. The terms subdivision and distri-
bution are nowadays called dispersive or
intensive mixing and distributive or exten-
sive mixing, respectively. Dispersive mix-
ing aims to reduce the size of cohesive
agglomerates, while distributive mixing
distributive mixing
Figure 6-8. Schematic illustration of dispersive and
distributive mixing.
aims to randomize the component distribu-
tion of a noncohesive mixture. Dispersive
mixing requires stress while distributive
mixing requires strain. The quality of dis-
tributive mixing of laminar flow is often
characterized by the striation thickness or
the amount of interfacial area (Tadmor and
Gogos, 1979).
As a screw extruder constitutes the heart
of a REX process, the proper selection of an
extruder is of great importance. However,
such selection is still carried out on an
empirical basis, despite the ever-increasing
understanding of REX. A REX process
comprises various sequential operations
which are more or less coupled. While it
would be ideal to have a "universal extrud-
er" which is capable of handling all these
sequential operations regardless of the
nature of the system to be processed, so far
such an extruder does not exist. This is
because a particular REX system has partic-
ular sequential operations to performe,
while a particular extruder has certain
capacities for handling certain sequential
operations. The system to be processed and
the extruder may not match fully. Thus
selecting an extruder amounts to searching
for a compromise between the specificity of
 6.2 Fundamentals of Reactive Extrusion
the extruder and the diversity of the systems,
or the universality of the extruder and the
specificity of the system. Obviously this is
not an easy task. Nonetheless, for a given
REX application, the following general
guidelines may be useful for selecting an
extruder:
What sequential operations are the real
bottlenecks in the whole process?
Is a single screw extruder inadequate for
processing most of the REX system so
that a twin screw extruder ought to be
used?
Is a co-rotating twin screw extruder bet-
ter suited to the REX system than a coun-
ter-rotating one?
Identification of the real bottleneck in the
sequential operations is crucial, as it makes
little sense to drastically improve a particu-
lar sequential operation while other opera-
tions limit the process to a greater extent.
Although single screw extruders appear to
be of limited use in REX for the reasons to
be discussed below, under certain circum-
stances they may be able to handle simple
REX applications. If so, it would not be wise
to use twin screw extruders which are much
more expensive and mechanically less reli-
able. The capability of a co-rotating
machine for handling a given sequential
operation may also be very different from
that of a counter-rotating machine.
Single Versus Twin Screw Extruders
In relation to the numerous extruder
designs existing in the polymer and food
industries, there is a general consensus
among scientists and engineers that there is
a clear distinction between single and twin
screw extruders. Below are two fundamen-
tal differences between single and twin
screw extruders (Rauwendaal, 1986):
359
1) The difference in the transport mecha-
nism that takes place in an extruder.
Material transport in a single extruder is
a drag-induced flow, i. e., frictional drag
in the solids conveying zone and viscous
drag in the melt conveying zone. In other
words, the transport is primarily deter-
mined by the frictional properties of the
solid material in the solids conveying
zone and the viscous properties of the
molten material in the melt conveying
zone. In contrast, the transport in an
intermeshing twin screw extruder is by
a positive displacement mechanism.
This is achieved by having a geometri-
cal configuration in which the material
is more or less confined in compart-
ments formed by the two screws and the
barrel. The degree of positive displace-
ment depends primarily on the extent to
which the two screws are intermeshed,
namely, the closeness between the flight
of one screw and the opposing channel
of the other screw. The better the seal
between the flight and the channel, the
more positive will be the conveying
characteristic. The most positive dis-
placement is obtained in a counter-rotat-
ing, closely intermeshing twin screw
extruder. However, it should be noted
that there is no purely positive displace-
ment screw extruder because of mechan-
ical constraints, i.e., a twin screw
extruder cannot be designed with zero
clearances. Thus leakage flows through
clearances reduce the degree of positive
conveying mechanism that can be
achieved in a twin screw extruder.
2) The difference in the flow patterns in the
machines. The velocity, pressure, and
temperature profiles in single screw
extruders are fairly well defined and rel-
atively easy to describe. The flow situ-
ation in twin screw extruders is consid-
erably more complicated, thus the veloc-
360 6 Fundamentals of Reactive Extrusion: An Overview
ity, pressure, and temperature profiles
are much more difficult to describe. The
complexity of the problem in twin screw
extruders stems primarily from the inter-
meshing region, the centerpiece of the
twin screws. This complexity has often
been neglected in the analysis of the
flow in such a machine. However, the
mixing characteristics and the overall
performance of the machine is deter-
mined, to a large extent, by the mixing
action associated with leakage flows
occurring in the intermeshing region.
Thus results from analyses that do not
take into account the flow in the inter-
meshing region have little practical use.
Analyses that attempt to accurately
describe the flow in the intermeshing
region can easily run into great mathe-
matical complexity, which is of little use
in practice either.
The above two major differences that
exist between single and twin screw extrud-
ers can be used to explain some of the spe-
cific advantages of each type of extruder and
the field of application in which each type
of extruder dominates over the other:
1) The single screw extruder is the most
important type of extruder employed in
the polymer industry. Its key advantag-
es lie in low cost, straightforward
design, ruggedness, high throughput,
and mechanical reliability. These advan-
tages were the disadvantages of twin
screw extruders during their initial stage
of development. In particular, twin
screw extruders had a number of
mechanical problems, and the most
important one was the thrust bearing
design. The early thrust bearings were
not strong enough to give twin screw
extruders good mechanical reliability
and a high torque capacity. The modern
thrust-bearing design has made the
mechanical reliability of twin screw
extruders comparable to that of single
screw extruders. However, twin screw
extruders still do not generally have as
high a thrust-bearing rating as single
screw extruders.
2) Twin screw extruders have established a
solid position in the polymer processing
industry. Although many commercial
polymeric materials can be processed in
either single or twin screw extruders,
twin screw extruders generally outper-
form single screw extruders. The main
areas of application for twin screw
extruders are in the profile extrusion of
thermally sensitive materials (a typical
example is PVC) and speciality polymer
processing operations such as com-
pounding, devolatilization, and reactive
extrusion. As speciality polymer pro-
cessing operations have gained increas-
ing importance in the polymer process-
ing industry, the use of twin screw
extruders is expected to increase. The
fact that twin screw extruders are partic-
ularly suited to thermally sensitive
materials and/or speciality polymer pro-
cessing operations is due to their inher-
ent advantages over single screw extrud-
ers:
(i) Better feeding and positive trans-
port characteristics. This allows the
machines to handle hard-to-feed
materials (powders, slippery mate-
rials, etc.). As stated above, materi-
al transport in single screw extrud-
ers is very sensitive to the friction-
al and viscous properties of the
material. There are many materials
with unfavorable frictional proper-
ties that cannot be fed into single
screw extruders without developing
feeding problems. For instance,
ultrahigh molecular weight poly-
 6.2 Fundamentals of Reactive Extrusion
ethylene can hardly be processed in sin-
gle screw extruders. Polyamides are
also difficult to cope with using single
screw extruders as they are very viscous
when not completely melted but
become very fluid when melted. Also,
the basic functions of a single screw
extruder, such as feeding, solids con-
veying, melting, melt conveying, and
metering, are highly sensitive to chang-
es in material and mechanical charac-
teristics. Sometimes an optimized pro-
cess can malfunction because of only a
minor change in the material properties
or mechanical wear.
(ii) Better control over residence time and
residence time distribution. This is par-
ticularly important for thermally sensi-
tive materials and REX processes.
Thermally sensitive materials can only
be processed properly with a short res-
idence time and a narrow residence time
distribution. Closely intermeshing
counter-rotating twin screw extruders
best satisfy these requirements. For
REX processes, a sufficiently long res-
idence time and a narrow residence time
distribution are required in order that
the reactions proceed to the desired lev-
els and that the resulting material is as
uniform as possible in terms of chemi-
cal modification. However, a narrow
residence time is concomitant with poor
backmixing (or small leakage flows).
(iii) Better mixing and larger heat transfer
area. To enhance chemical reactions,
the chemical ingredients in question
ought to be mixed at molecular or poly-
mer segmental level. As convective
mixing (or laminar mixing) is virtually
the only mechanism that reduces the
size scale of highly viscous polymeric
fluids, how to enhance the mixing has
been the most important topic in REX.
An effective mixing along with a large
361
heat transfer area also ensure good
control over stock temperatures, there-
fore minimizing hot spots, polymer
degradation, and chemical heterogene-
ity.
(iv) Larger melting capacity. A single screw
extruder usually has a long and contin-
uous solid bed, while in a twin screw
extruder melting generally takes place
early in the extruder and over a short
screw length. This is because a twin
screw extruder has a large heat transfer
area, as mentioned above. Additional-
ly, there are special screw elements
which allow the operator to control
and/or accelerate the melting. The larg-
er melting capacity of twin screw
extruders compared to single screw
extruders leaves more screw length for
accomplishing other sequential opera-
tions. In fact, most of the sequential
operations in REX can only be per-
formed when the polymer in question is
molten. For instance, chemical reac-
tions proceed mostly in molten poly-
mers.
(v) Larger devolatilization capacity. This is
related to the fact that twin screw
extruders have higher surface/volume
ratios. Also, there is a continuous crea-
tion of new and thin surface layers on
the barrel wall and screw surfaces of a
twin screw extruder, which again
enhance reaction, mixing, and mass and
heat transfer.
(vi) Greater process flexibility. Twin screw
extruders are usually of modular
design. They have removable screw and
barrel elements. There are a variety of
screw elements available, each having
specific functions in relation to convey-
ing, melting, (dispersive or distribu-
tive) mixing capacities, etc. The screw
design can be altered by simply chang-
ing the sequence or the nature of screw
362 6 Fundamentals of Reactive Extrusion: An Overview
elements along the shafts. In this way,
almost an infinite number of screw pro-
files can be made "at will". Thus the
modular design offers enormous pro-
cess flexibility and allows careful
optimization of the screw and barrel
geometry for a particular application.
This is in contrast to single screw
extruders which usually have a poor
capacity to adapt themselves to a new
application. In this case, a specific
screw design may be necessary.
However, it should be pointed out that the
several advantages of twin screw extruders
over single screw extruders mentioned
above result from the more complicated
flow patterns in twin screw extruders. In this
sense, it is fair to say that in extrusion tech-
nology, this "complexity" dictates the qual-
ity and/or the performance. It is also due to
this complexity that extrusion in general,
and REX in particular, has been viewed
more as an art than a science. This is
because, admittedly, extrusion and REX are
still not sufficiently developed to allow rea-
sonable prediction of such processes. This
is particularly true for extrusion or REX in
twin screw extruders. It is indeed difficult
to predict the performance of a twin screw
extruder based on the extruder geometry,
thermomechanical properties of the poly-
mer, and processing conditions. Converse-
ly, it is equally difficult to predict a proper
screw geometry and processing conditions
for a given application. Interestingly, this is
one of the reasons why machine manufac-
turers fabricate their twin screw extruders
with modular designs. In this way, the per-
formance of their machines has little to do
with the fabricants, but depends entirely on
how a user plays with the modular designs.
Modular designs provide a twin screw
extruder with much greater process flexibil-
ity in order to cope with changes in the var-
ious sequential operations involved in a
REX process. At the same time, it brings
researchers an enormous challenge of how
to "pick" the design out of so many possibil-
ities that best suits a given application.
Co-Rotating Versus Counter-Rotating
Twin Screw Extruders
If there is a general consensus about the
above distinction between single and twin
screw extruders, the virtues and vices of a
co-rotating machine compared to a counter-
rotating one remain controversial. This is
due, at least in part, to a lack of in-depth
understanding about the functioning of
these two types of machine. As a result, for
a given REX application, the criteria for
selecting an extruder may not be based on
solid scientific arguments, but rather on the
user's funding level or preference. How-
ever, the fact is that nowadays co-rotating
twin screw extruders dominate overwhelm-
ingly over counter-rotating machines for
most REX applications.
6.3 Case Studies
As discussed earlier, REX is a distinct
engineering speciality at the border between
chemical engineering and polymer engi-
neering. An important feature is that a REX
process comprises a number of sequential
operations, such as feeding, solids convey-
ing, melting, mixing, reacting, venting,
pumping, and shaping. The control of a REX
process requires that the mechanism of each
individual operation be identified and its
contribution to the overall process quanti-
fied.
Considering the complications of a REX
process, in what follows are case studies that
attempt to provide some general guidelines

to selected fundamental problems raised by
REX. Specifically, they are:
How does a chemical (functional or free
radical) reaction involving polymers pro-
ceed in the molten state? What are the
main factors that govern its kinetic behav-
ior?
What are the main parameters that dictate
the performance of a screw extruder as a
continuous chemical reactor and how can
it be predicted?
How to use screw extruders as reactive
blenders (or compounders) for reactively
blending existing polymers in order to
produce new materials of high perfor-
mance with reduced costs? How to inte-
grate chemical and processing parameters
such that the overall process reaches its
best performance?
Finally, the problem of the residence time
distribution in screw extruders will be
addressed. The residence time distribution
is an important issue in REX, as it is prob-
ably the most important and fundamental
parameter that distinguishes a continuous
flow reactor from a batch one.
6.3.1 Melt Chemical Reactions
in a Batch Mixer
A basic question raised by REX is relat-
ed to the kinetic behavior of the melt chem-
istry concerned. This is why we will first
discuss the behavior of chemical reactions
Table 6-2. Examples of the reacting systems to be discussed.
Reacting fluid microfluid
Controlling factors kinetics
Example reactive polymer +
small reactive
molecule
6.3 Case Studies 363
carried out using molten polymers in the
absence of solvents, comparing where pos-
sible with that in solution. Batch reactors
will be used for this purpose because the
problem of the residence time distribution
encountered in continuous reactors is
removed. Two types of reaction based upon
functional and free radical reactivities will
be taken as examples.
6.3.1.1 Functional Reactions
Reactions based on functional reactivity
are usually better defined or "cleaner" than
those based on free radical reactivity. Thus
we will use functional reactions as exam-
ples to illustrate the behavior of chemical
reactions in the following three types of
mixture: microfluid, partly segregated fluid,
and macrofluid (Table 6-2).
In a Microfluid
When chemical reactions are carried out
in a molten polymer medium without any
solvents, the simplest situation is where the
reacting mixture is homogeneous (a micro-
fluid). In this case, the first question a chem-
ist would ask is how the behavior (mecha-
nism and kinetics) of such a reacting system
differs from that if it is run in the presence
of an inert solvent. In response to this basic
question, various model reactions have been
investigated in homogeneous polymer melts
partly segregated fluid macrofluid
kinetics + solubility interfacial area
inert polymer + reactive reactive polymer 1 +
polymer + small reactive reactive polymer 2
molecule
364 6 Fundamentals of Reactive Extrusion: An Overview
Flask reactor for solution reactions Batch mixer for melt reactions
(Hu et al., 1992 a, b, c; Hu and Lambla,
1994) using a batch mixer as a batch reac-
tor. For a better understanding of the reac-
tions occurring in the melt, they have also
been studied in solution using a classical
flask as a batch reactor (Fig. 6-9). Two
examples are given below: the transesterifi-
cation of poly(ethylene-co-vinyl acetate)
(EVA) with 3-phenyl 1-propanol (PPOH) in
solution and in a homogeneous melt using
dibutyltin dilaurate (DBTDL) as a catalyst,
and the grafting of 1-naphthylacetic acid
onto poly(ethylene-c<?-ethyl acrylate-co-
glycidyl methacrylate) (PGMA):
Example 1) The transesterification of
EVA with PPOH (Hu et al., 1993) - this
reaction can be described as
(CH )OH
t=0 a b
t>0 a(l-p) b(l-p)
where a and b denote the initial molar con-
centration of the vinyl acetate group and the
alcohol, respectively, and p is the conver-
sion in terms of the vinyl acetate group con-
centration. The overall conversion rate was
found to be (Hu et al., 1993 a)
(6-2)
Figure 6-9. Schematic diagrams of
the flask reactor and the batch mixer
used for carrying out reactions in
solution and in the melt, respectively.
with r=b/a, k{ = klc VfDBTDL] and k2=k2c
VlDBTDL] . The constants kXc and k2c are
the forward and reverse intrinsic kinetic
constants, respectively.
The conversion is shown in Fig. 6-10 as
a function of the time of this reaction at var-
ious temperatures in a solution of 1-dode-
cane and in the melt. Clearly the reaction
proceeds much faster in the melt, even
though the alcohol is not in excess in this
case (r=0.902 instead of 3.65 in solution).
Additionally, the reactions carried out in
solution and in the melt follow the same
reaction mechanism as given by Eq. 6-2 and
fit the corresponding conversion-time
curves well. More interestingly, the intrin-
-CHCH-
2 I o
II
o
H CH-C-O(CH
3 2'3
0 0
ap ap (6-1)
sic reaction rate constants, klc and k2c, dif-
fer only slightly between the solution and
the melt (Fig. 6-11). This indicates that a
faster reaction rate in the melt results sole-
ly from much higher concentrations of the
reacting species.
 6.3 Case Studies 365

80.0 -

c
o o o o o o 150 C
AAA A A 1 50C
a DO na 180C
C best fit
o
u
20.0

VA=0.170M;r=3.65;Cat = VA=1.44 M; r=0.902;

150 RPM;1-dodecane C = 0.029M; 64 RPM
200 400 600 800 20 40 60 80
Time (min) Time (min)

a b
Figure 6-10. Conversion as a function of time: (a) in solution, and (b) in the melt. VA = vinyl acetate. (From Hu
et al., 1992c. Copyright 1992, John Wiley & Sons, Inc. Reprinted by permission of John Wiley & Sons, Inc.)

o o o o o k 1ci m e l t
k1c, s o l u t i o n
D D D D a k2c, m e l t
k2c, s o l u t i o n
A r r h e n i u s law
Figure 6-11. Temperature dependence of k]c and k2c
in solution and in the melt. (From Hu et al., 1992c.
Copyright 1992, John Wiley & Sons, Inc. Reprinted
by permission of John Wiley & Sons, Inc.)
It may be somewhat surprising that the
similarity between the kinetic results from
the melt and solution experiments is not
masked, at least partly, by the five orders of
magnitude difference in viscosity between
the two reacting media. This implies that
neither the effect of viscosity nor that of
mechanical mixing is significant within the
time scale of the reaction. This finding can
be made plausible by comparing the rate
time scales of the reaction and molecular
diffusion of the reacting species tR and tD,
since both reacting systems are homogene-
ous (the alcohol concentrations are below
its solubility limit in the melt). The charac-
teristic reaction time, tR=l/(kxa), when
compared to the characteristic diffusion
time, tD = h2/D, appears to be very large.
Both the diffusion length, h, and the diffu-
sivity, D, are functions of viscosity; even in
the melt (where a and h tend to be relative-
ly large and D small) the ratio tR/tD is still
much larger than unity (> 1000).
The lack of competition for the reactant
molecules between reaction and molecular
diffusion is further confirmed by perform-
ing this reaction under different mechanical
mixing conditions: after the reacting
mixture is mixed with a rotating speed
of the rotors of 64 turns per minute (rpm)
for 3 min, it is then allowed to proceed in
three different modes: without additional
mixing, at the same rotating speed, and
at twice the rotating speed. It turns out
that this reaction proceeds with virtually
the same speed, regardless of the mechani-
366 6 Fundamentals of Reactive Extrusion: An Overview

sion rate can be described by

60.0 -
^ = k](a-bp)(l-p)-k2p (6-4)
s A
8
Shown in Fig. 6-13 is the conversion of
z
O 40.0 -
m 8 this reaction when carried out in the same
en A
batch mixer as that used in Example 1. The
LU
g acid concentrations are below its solubility
TEMPERATURE: 1 50C
20 0 A
limit in the molten PGMA. The relatively
o o o o o 54 rpm good agreement between Eq. (6-4) and the
D D D D i 28rpm experimental data indicates that the classi-
A A A A A o rpm
0.0 ^ i . . cal kinetic theories developed for chemical
0 20 40 60 80 100
TIME (min)
reactions in solution also apply to those car-
ried out in a homogeneous mixture involv-
Figure 6-12. Mechanical mixing effect on the over- ing a reactive polymer and a low molecular
all reaction rate in the melt. (From Hu et al., 1992c.
Copyright 1992, John Wiley & Sons, Inc. Reprinted
weight reagent. Apparently the mechanical
by permission of John Wiley & Sons, Inc.) mixing at 64 rpm is sufficiently good that
the diffusion length is reduced to such a
cal mixing mode (Fig. 6-12). This implies small size that the characteristic molecular
that the first 3 min mixing at 64 rpm diffusion time of the small reactive mole-
reduces the diffusion length to a sufficient- cule is much shorter than the characteristic
ly small size that no subsequent mixing is reaction time. In order to further support this
necessary. point, after an initial pre-mixing at 64 rpm
Example 2) The grafting of 1-naphthyl- for 3 min, this reaction was run using two
acetic acid onto PGMA (Hu and Lambla, different mixing modes: at the same mixing
1994) - the main reaction is expected to pro- speed, and without additional mixing. As
ceed as follows:

"CH CHCH CHCH C H CH CH-CH CH-CH CH

2 2 21 2| 2 2 2| 2|
c=o c=o
C=O C=O I I
O O oI o
CH CH
2 5
I 2
CH-OH
o
OK CH-C-0 CH^

a b 0
t>0 a-bp b(l-p) bp (6-3)

where a and b are the initial molar concen-

tration of the epoxy group of the copoly- shown in Fig. 6-14, both reaction rates were
mer PGMA and the acid, respectively, and very close.
p denotes the conversion with regard to con- The above two examples have shown that
sumption of the acid. The overall conver- when a chemical reaction is carried out in a
 6.3 Case Studies 367

The overall reaction rate is controlled by

its intrinsic kinetics.
The mechanisms and kinetics in solution
and in the homogeneous melt are identi-
cal provided that the solvent does not
interfere with the reaction pathway.
Mechanical mixing is only important for
GMA = 0.477 M
Acid = 0.391 M; the homogenization or diffusion length
64 rpm. reduction of the reacting system at the
initial stage of the reaction. Once this is
achieved, it is no longer necessary.
20 40 60 In fact, the kinetic results of the trans-
Time (min) esterification of EVA with PPOH in solution
Figure 6-13. Conversion as a function of time for the and in the melt reveal important advantages
reaction between poly(ethylene-c6>-ethyl acrylate-c<9- of polymer chemistry in the melt over poly-
glycidyl methacrylate) and 1-naphthylacetic acid in mer chemistry in solution: in addition to the
the melt. (Reprinted from Hu et al., 1997b, copyright absence of solvents and their associated ben-
1997, with kind permission from Elsevier Science Ltd,
efits, the rate of a reaction carried out in the
Kidlington, Oxford, U.K.)
melt can be much faster than it would be in
100 solution. This is because when solvents are
not employed, the concentrations of reacting
64 rpm
species can reach their ultimate values.
80- no mixing

60- In a Partially Segregated Fluid

o
40- Situations are often encountered in REX
GMA = 0.477 M; where chemical reactions are occurring in
o
o 20-
Acid = 0.391 M; the presence of other chemically inert spe-
Temperature: 140C. cies. A simple case is a mixture of three
components: a reactive polymer, a small
o* reactive molecule, and an inert polymer. If
20 40 60 80
these three components constitute a micro-
Time (min) fluid, then the kinetic problem reduces to
Figure 6-14. Mechanical mixing effect on the over- what has been discussed above. If these two
all reaction rate in the melt. (Reprinted from Hu et al., polymers are immiscible while the small
1997b, copyright 1997, with kind permission from reactive molecule is miscible with both of
Elsevier Science Ltd, Kidlington, Oxford, U.K.)
them, then the mixture is partially segregat-
ed. In this case, the small reactive molecule
microfluid (where the reacting medium is is partitioned between both polymeric phas-
homogeneous, be it in solution or in a homo- es. Consider a case where the reaction mech-
geneous melt), if the ratio of the characteris- anism is the following:
tic reaction time to the characteristic diffu-
sion time is much larger than unity (R/D > 1), reactive polymer + small reactive molecule
then the following statements are valid: <r^ new polymer product
368 6 Fundamentals of Reactive Extrusion: An Overview
If the molecular diffusion rate of the small
reactive molecule in these two polymeric
phases is really rapid, then a partition equi-
librium is established between them in terms
of this small reactive molecule concentra-
tion. Furthermore, if the characteristic dif-
fusion time is much shorter than the charac-
teristic reaction time, then the conversion
rate can be described by
At
= J Vi+(Vj/) n2p
= k{(A-Bp)(\-p)-kip (6-5)
N
where k\ and k2 are the forward and reverse
reaction rate constants, respectively; nx and
n2 denote the molar number of the function-
al group in the reactive polymer and that of
the small reactive molecule, respectively; Vj
and V, are the volume of the reactive poly-
mer and that of the inert polymer phase,
respectively; is the partition coefficient of
the small reactive molecule which is defined
as the ratio of its amount in the reactive poly-
mer phase to that in the inert polymer phase:
A=nl/[v] + (vi/)] and B = n2/[Vi + (vi/e)]. A
and B can be called the apparent initial molar
concentrations of the functional group of the
reactive polymer and that of the small reac-
tive molecule, respectively.
Note that when is infinite, or the small
reactive molecule is completely immiscible
with the chemically inert polymer phase and
is solubilized only in the reactive polymer
phase, then Eq. (6-5) reduces to Eq. (6-4).
This means that the presence of the chemi-
cally inert polymer will not interfere, in any
way, with the concerned reaction. When is
zero, or the small reactive molecule is com-
pletely immiscible with the reactive poly-
mer and is solubilized only in the chemical-
ly inert polymer phase, no reaction will
occur. Integration of Eq (6-5) gives
= (6-6)
where a= 1 ,and A=ya2- 4AB,
K'e is the equilibrium constant, which is
equal to the ratio k[lk2.
The constants k\ and k^ in Eqs. (6-5) and
(6-6) can be obtained by a minimization pro-
cess with the following objective function:
(6-7)
The main difference between the micro-
fluid and the partially segregated fluid lies
in that in the latter case the overall reaction
rate is not only affected by its intrinsic kinet-
ics but by the partition coefficient as well.
The partition coefficient is determined by
the thermodynamic properties of the two
polymers of interest.
The example given below illustrates the
situation described above. Again, it con-
cerns the grafting of 1-naphthylacetic acid
(small reactive molecule) onto PGMA
(reactive polymer) in the melt, the kinetic
behavior of which was discussed earlier. But
this time polystyrene (PS) is added as an
inert polymer, immiscible with the PGMA
copolymer. The acid has a solubility in PS
of greater than 25% by weight at 50C. Fig-
ure 6-15 illustrates the schematic morphol-
ogies of this partially segregated reacting
mixture (PGMA + PS + acid) and the homo-
geneous one (PGMA + acid).
This reaction is allowed to proceed in the
batch mixer at 160C with various propor-
tions of PS dispersed in the system: 0, 10,

(a) (b)
Figure 6-15. (a) Homogeneous mixture of PGM A +
acid, (b) Partially segregated mixture of PGMA + PS
+ acid (the acid is partitioned in both the PGMA and
the PS phases).
a Basically, the overall reaction pathway
80-
60-
o of the acid between the two polymer phas-
40-
0 0% PS
O 10% PS
o A 40% PS
20-
If 160C; V 70% PS
I Acid: 5% 70% PS
20 40 60
Time (min)
Figure 6-16. Conversion as a function of time for the
partially segregated mixture of PGMA + PA + acid
with four proportions of PS: 0, 10, 40, and 70 wt.%.
The reaction temperature was 160C, and the rotating
speed was 64 rpm for all runs except for ( ) , where
mixing was carried out at 64 rpm for only the first
3 min. (Reprinted from Hu et al., 1997b, copyright
1997, with kind permission from Elsevier Science Ltd,
Kidlington, Oxford, U.K.)
40, and 70% by weight with respect to the
total mass of the two polymers and the
weight of the acid being unchanged. The
mixing speed is 64 rpm. As shown in Fig. 6-
16, the conversion rate decreases with
increasing PS proportion due, at least in part,
to dilution of the reacting species. Addition-
ally, the conversion rate with 70% PS is
about the same under the following two mix-
6.3 Case Studies 369
ing conditions: 64 rpm for the entire reaction
time, and 64 rpm for the first 3 min only and
thereafter no more mechanical mixing. This
implies that the diffusion rate of the acid in
the PS and PGMA phases is so rapid that an
equilibrium is always established for the par-
tition of the acid between both polymeric
phases during the entire course of the reac-
tion, and the overall reaction rate is not con-
trolled by diffusion but by its intrinsic kinet-
ics and the partition coefficient of the acid.
If the overall reaction rate is indeed con-
trolled by its intrinsic kinetics alone, it is
expected that:
should be the same as that of the homo-
geneous reacting mixture (PGMA +
acid), except that the partition coefficient
es ought to be taken into account in the
kinetic analysis. In other words, Eq.
(6-6) should be able to fit the experimen-
tally obtained conversions.
The values of the forward and reverse rate
constants, k\ and k!2, should be identical
to those of the homogeneous reacting
mixture (PGMA + acid) at the same tem-
perature, regardless of the proportion of
PS added.
The constants k\ and k^ of this partially
segregated fluid at 160C are determined as
follows: introducing into Eq. (6-7) all the
conversion data obtained at the various PS
weight fractions, and then searching for the
minimum of S(k[, k^, ). As the partition
coefficient is unknown experimentally, it
is also a variable in Eq. (6-7). Obviously, the
values of k{, ^ , and obtained by this
process are valid only when they allow Eq.
(6-6) to generate conversion values that
agree with all the experimental data obtained
with the various PS weight fractions. This is
indeed the case, as shown in Fig. 6-16. The
relative closeness between the measured
370 6 Fundamentals of Reactive Extrusion: An Overview

3.6
-1.0-
\
\
-1.5-
3.2-

\
-2.0-
\
O Lnk1 without PS 2.8- O LnKe without PS
\
1
Lnk1 with PS at 160C. LnK'withPSat160C.
-2.5- , i

2.20x10'3 2.30x10'3 2.40x10' 3 2.20x10' 3 2.30x10"3 2.40x10"3

1
1/T (K" )
b
a
Figure 6-17. (a) Comparison of the forward rate constant of the reaction in a homogeneous mixture (PGMA +
acid) with that in a partially segregated mixture (PGMA + PS + acid) at 160C. (b) Comparison of the equilib-
rium constant of the reaction in a homogeneous mixture (PGMA + acid) with that in a partially segregated mix-
ture (PGMA + PS + acid) at 160C. (Reprinted from Hu et al., 1997b, copyright 1997, with kind permission
from Elsevier Science Ltd, Kidlington, Oxford, U.K.)

conversions and the solid curves also con-
firms that the reaction between the PGMA
and the acid in this partially segregated react-
ing mixture proceeds in the same manner as
that in the homogeneous reacting mixture of
PGMA and the acid. The k\ value of the par-
tially segregated reacting system at 160C is
reasonably close to that of the homogeneous
one at the same temperature (Fig. 6-17 a).
This is also true for the equilibrium constant
The above discussion concerns the kinet-
ic behavior of a chemical reaction carried
out in a partially segregated fluid. An exam-
ple has been given of a reacting mixture
composed of a reactive polymer, a chemi-
cally inert polymer, and a small reactive
molecule. These two polymers are immis-
cible while the small reactive molecule is
miscible with both of them. In other words,
the small reactive molecule is partitioned
between both polymeric phases. A kinetic
comparison with the reaction carried out in
a homogeneous mixture has shown that if
the molecular diffusion rate of the small
reactive molecule in these two polymeric
phases is so rapid that a concentration equi-
librium is always established between them,
and if tR/tD > 1, then
the overall reaction rate is only controlled
by its intrinsic kinetics and the partition
coefficient of the small reactive molecule
in these two polymeric phases;
mechanical mixing is important only for
reducing the diffusion length of the react-
ing system at the initial stage of reaction.
Once this is achieved, no more mechani-
cal mixing is necessary.
In a Macrofluid
A much greater tR than tu is possible for
polymer-small molecule reacting systems,
as seen above, but this is unlikely for poly-
mer-polymer reacting systems. This is
because, in the latter case, the mutual diffu-
sion rate is usually very slow. Moreover, due

to the fact that most polymers are immis-
cible (macrofluid), the diffusion length, h,
is also large. As such, a chemical reaction
between two immiscible polymers cannot
usually proceed to a measurable extent rely-
ing only on their mutual diffusion process.
In fact, because of the immiscibility
between two reacting immiscible polymers,
the chemical reaction should preferentially
take place at their interfaces. Thus mechan-
ical mixing plays a crucial role in acceler-
ating the overall reaction rate, as the total
interfacial area depends on the amount of
mechanical mixing applied. For example, if
a reacting system composed of two immis-
cible polymers undergoes simple shear lam-
inar flow and if the interfaces are randomly
oriented, then the ratio of the total final
interfacial area to the total initial area, A/AQ,
is one half the total strain, 7, imposed on the
system (Tadmor and Gogos, 1979).
In order to appreciate how a chemical
reaction between immiscible polymers (a
mixture of macrofluids) differs from that in
a microfluid, an example is given of the melt
transesterification between poly(ethylene-
co-methyl acrylate) (EMA) and polystyrene
that is mono-hydroxylated at the chain end
(PSOH), using DBTDL or dibutyltin oxide
(DBTO) as a catalyst (Hu and Lambla,
1995). The reaction between EMA and
PSOH forms a graft copolymer EMA-g-PS
through the following mechanism (Hu and
Lambla, 1994)
-CH-CH
2 I
C-O
+ PSCH CH OH
o CH OH
I CH
CH
t=0 a b
t > 0 a-bp b(l-p)
6.3 Case Studies 371
Here, a and b denote the initial apparent
molar concentration of the methyl acrylate
moieties in the EMA copolymer and the
hydroxyl group in PSOH, respectively. Each
is defined as the ratio of its molar number
over the total volume of the reacting mass.
The conversion p is the percentage of the
reacted PSOH with regard to its initial
amount. This reaction is reversible in nature,
as confirmed experimentally upon reacting
EMA with 3-phenyl 1-propanol (PPOH) in
a microfluid (Hu and Lambla, 1994). How-
ever, at high temperatures along with suffi-
cient mechanical mixing, it behaves as an
irreversible reaction due to fast and complete
removal of the methanol product from the
hot polymer melt (Hu and Lambla, 1994).
The reaction between EMA and PSOH is
a clean reaction involving at most three
polymers, as shown above. A quantitative
follow-up of the reaction by size exclusion
chromatography (SEC) or high performance
liquid chromatography (HPLC) is relative-
ly easy (Hu, 1990), which is rarely the case
for polymer-polymer reacting systems. As
a matter of fact, difficulty in analyzing the
extent of reaction has been the main reason
for a lack of relevant work in the literature
which addresses the behavior of chemical
reactions between immiscible polymer
melts.
If this reacting system were homogene-
ous, the overall reaction rate upon neglect-
~CH-CH~
2 I
c=o
I
3
I 2
CH
I 2
PS
0 0
bp bp (6-8)
372 6 Fundamentals of Reactive Extrusion: An Overview

ing the reverse reaction could be written as
(Hu and Lambla, 1994)
= kaw(a-bp)(l-p)
At
or
1 a-bp
k app
In
~(a-b)t \a-ap
The apparent rate constantfcappshould not
vary with reaction time for a homogeneous
reacting system if the overall reaction rate
is controlled only by its intrinsic kinetics.
This is confirmed experimentally with the
EMA/PPOH reacting system (Hu and
Lambla, 1994). This standard analysis for
homogeneous reaction kinetics cannot, a
priori, be used to treat kinetic data of heter-
ogeneous reacting systems without know-
ing the interfacial area, the solubility, and
the concentration profiles of the reacting
species at the interface. It is conceivable that
for a heterogeneous reacting system, kapp
may no longer be constant because all these
parameters vary as the reaction proceeds. If
so, the variation of &app with time may help
shed light on the kinetic behavior of a het-
erogeneous reacting system.
Selected features of the EMA/PSOH het-
erogeneous reacting system are presented
below, with some of them being general for
other similar reacting systems (Hu and
(6-9)
Lambla, 1995).
The in situ formation of the graft co-
polymer EMA-g-PS at the interface
between EM A and PS OH decreases the
apparent reaction rate constant fcapp. Plotted
in Fig. 6-18 a and (b) are the conversion and
&app as a function of time, respectively (the
number molecular weight of the PSOH used
here is 3000 g/mol, and will be denoted as
PSOH3). Such a decrease in &app is more
pronounced at a higher temperature or after
a longer reaction time. This decrease in /capp
with increasing reaction time is surprising
at first glance. This is because it is observed
experimentally that as the reaction pro-
ceeds, this heterogeneous reacting system is
becoming more and more homogeneous,
driven by the formation of the amphiphilic

75 0.04-

-A
0.03-

0.02-
o 180C
Q. 200C
2 0.01- & 220C
EMA: 35 g o
PSOH3: 15 g -o_Q
DBTO: 0.4 g
Mixing speed: 64 rpm
0.00-
10 15 20 25 10 15 20 25 30
Time (min) - Time (min)

(a) (b)
Figure 6-18. (a) Conversion as a function of time for the EMA/PSOH3 system, (b) Apparent rate constant k.dpp
vs. time for the EMA/PSOH3 system. (From Hu and Lambla, 1995. Copyright 1995, John Wiley & Sons, Inc.
Reprinted by permission of John Wiley & Sons, Inc.)

graft copolymer EMA-g-PS. Thus k.dpp is
expected to increase. A moment's reflection
will show that the decrease in kapp with time
is explicable: on the one hand, formation of
the EMA-g-PS graft copolymer at the inter-
face increases the miscibility of this heter-
ogeneous reacting system; on the other
hand, because of the fact that the EMA-g-
PS copolymer is formed and located prefe-
rentially at the interface, it tends to separate
the two reacting species EMA and PSOH3,
therefore obscuring their interfacial contact.
This effect, called the interfacial screen
effect, can be illustrated by Fig. 6-19; for
thermodynamic reasons, the two parts
(skeleton and grafts) of the EMA-g-PS
copolymer formed at the interfaces pene-
trate preferentially into their respective
polymer phases. By this mechanism, the
graft copolymer serves to reduce the inter-
facial tension, helps strengthen the adhesion
at the phase boundary, and thus stabilizes
the morphology of the mixture. In fact, more
often than not, the volume fraction of such
a copolymer near the interfaces can be close
to unity (Shull and Kramer, 1990). If this
perception is true, it will mean that the func-
EMA-g-PS
Figure 6-19. Occlusion of the functional moieties of
two polymers by a graft copolymer located at the inter-
face. (From Hu and Lambla, 1995. Copyright 1995,
John Wiley & Sons, Inc. Reprinted by permission of
John Wiley & Sons, Inc.)
6.3 Case Studies 373
tional moieties of the two polymers are
totally excluded from the interfacial region
by the in situ formed graft copolymer. As a
result, instead of increasing the overall reac-
tion rate, the graft copolymer assisted com-
patibilization of the reactive mixture would
decelerate the overall reaction rate.
Adding the EMA-g-PS graft copolymer
to the EMA and PSOH reacting system
decreases kapp, which is in agreement with
the above discussion. For example, when
2 wt.% of a preformed EMA-g-PS copoly-
mer with regard to the total mass of EMA +
PSOH3 is added, the conversion obtained
after 20 min of reaction at 180C decreases
from the original value of 33% down to
19%. This phenomenon, not reported before
in the literature, confirms the above-men-
tioned interfacial screen effect caused by the
occupation of the interfaces by the graft
copolymer.
Mechanical mixing promotes the overall
reaction rate. This is clearly shown in Fig.
6-20 a, in which the conversion is plotted as
a function of time at 64, 90, and 128 rpm.
When the conversion-time curves in Fig.
6-20 a are converted to conversion-rotating
speed curves (Fig. 6-20b), it is seen that con-
version increases almost linearly with
increasing rotating speed. If it is assumed
that the laminar mixing theories apply to the
present reacting system and that the appar-
ent shear rate exerted on a fluid in a batch
mixer is proportional to the rotating speed of
the rotors, then the interfacial area genera-
tion rate A/Ao is proportional to the rotating
speed of the rotors. Thus the conversion is
proportional to the interfacial area genera-
tion of the EMA/PSOH3 system. This
implies that the overall reaction rate is con-
trolled by the interfacial area generation rate.
An increasing interfacial area also helps
decrease the areal chain density of the
copolymer "brush", thus reducing the inter-
facial screen effect (Norton et al., 1995).
374 6 Fundamentals of Reactive Extrusion: An Overview

70
o 64 rpm 60- A

60- 90 rpm
A 120 rpm 50-
50- o
g40-
40-
c
I
0) 3 0 -
|
0)
30-

o10min
o 20- 8 2- O
n I5min
EMA: 35 g A 20 min
PSOH3: 15 g 10-
10-
DBTO: 0.4 g
Temperature: 180C
n-
10 15 20 25 60 70 80 90 100 110 120 130
Time (min) Mixing speed (rpm)

a
Figure 6-20. (a) Conversion as a function of time at three different rotating speeds, (b) Conversion as a func-
tion of rotating speed for three different reaction times. (From Hu and Lambla, 1995. Copyright 1995, John
Wiley & Sons, Inc. Reprinted by permission of John Wiley & Sons, Inc.)

Another way to understand the impor-
tance of mechanical mixing is based upon
the diffusion time scale. The characteristic
diffusion time, tD, is of the order of h2/D. In
order to shorten tD, D should be increased or
h reduced. Mechanical mixing does not
increase D but reduces h. The diffusion
length of the above reacting system, as
revealed by scanning electron microscopy,
is roughly 10 |um after 3 min of mixing at 64
rpm. It reduces to a point where it is too small
to estimate as the reaction proceeds further.
If D for PSOH3 is taken as l.OxKT 14 m2/s,
tD will be in a range between several and sev-
eral dozens of minutes. This time range is of
the same order of magnitude as the charac-
teristic reaction time for the EMA/PSOH3
system. Thus this reaction is likely to be con-
trolled both by its intrinsic kinetics and dif-
fusion. This statement is also supported by
the fact that the value of app for the
EMA/PSOH3 system at 180C and 64 rpm
is 0.0086 JVT1 min"1, which merely amounts
to half that for the EMA/PPOH homogene-
ous system (0.019 M"1 min"1) under the
same conditions in terms of reaction temper-
ature, mixing speed, and concentration of
the catalyst (DBTO).
Adding minor amounts of a common sol-
vent increases the overall reaction rate. When
2 wt.%rc-hexadecaneor 1,2,4-trichloroben-
zene is added to the EMA/PSOH3 system, a
dramatic increase in the overall reaction rate
is found (Fig. 6-21). This may be due to an
accrued solubilization of PSOH3 in the mol-
ten EMA and an enhanced diffusion coeffi-
cient of these two reactive polymers, which
reduces the diffusion time. In fact, it has been
shown experimentally (Duda et al., 1982)
that the presence of a few percent of a sol-
vent may enhance the diffusivity of a melt
polymer by up to 2-5 orders of magnitude.
The pronounced effect of adding a solvent
is also observed for mono-hydroxylated PS
of different molecular weights (1700 and
8000 g/mol, denoted as PSOH1 and PSOH8,
respectively). Shown in Fig. 6-22 is the
effect of adding 2.0 wt.% n-hexadecane on
the conversion of three PSOHs of different
molecular weight. When no solvent is
present, the conversion decreases with
increasing molecular weight of PSOH.
 6.3 Case Studies 375

75- o without solvent PSOH1 is insignificant. This also seems to

o 2.0 wt.% trichlorobenzene^ be true for PSOH8 in terms of the absolute
A 2.0 wt.% hexadecane value, but its conversion is almost tripled.
60-
The minor difference in the conversion with
or without the solvent for PSOH1 implies
45 that PSOH1 is more miscible with the mol-
ten EMA copolymer, thus the effect of the
:30 solvent assisted solubilization of the
O
EMA: 35 g PSOH1 in the molten EMA is no longer as
15-
PSOH3:15 g relevant as for PSOH3 or PSOH8.
DBTO: 0.4 g
Temperature: 180C
Mixing speed: 64 rpm
10 15 20 25 6.3.1.2 Free Radical Grafting
Time (min) of Monomers onto Polymers
Figure 6-21. Effect of solvents on the conversion for
the EMA/PSOH3 system. (From Hu and Lambla,
Free radical reactions are usually more
1995. Copyright 1995, John Wiley & Sons, Inc. "messy" than functional reactions. Further-
Reprinted by permission of John Wiley & Sons, Inc.) more, the state of the mixture is not as
easily identified as in the examples of func-
70
tional reactions presented above. One of
60
the most important free radical reactions
explored by REX is the free radical grafting
50 of vinyl monomers onto polymer backbones.
Its underlying chemistry generally involves
40 the generation of primary free radicals from
the thermal decomposition of a peroxide, the
0) 30
formation of polymeric free radicals result-
20 ing from hydrogen abstraction from the poly-
mer backbones, and the grafting of vinyl
10 monomers onto the macromolecular free rad-
0without solvent
with 2.0 wt.% n-hexadecane ical sites along the backbones. As the reac-
2000 4000 6000 8000 tivity of polyolefins stems from the hydro-
Mn of PSOH (g/mole) gen atoms along the hydrocarbon skeleton
Figure 6-22. Effect of solvents on the conversion for
that are subjected to free radical attack, aside
three different molecular weights of PSOH. (From Hu from the desired grafting, crosslinking or
and Lambla, 1995. Copyright 1995, John Wiley & degradation may occur. Due to the various
Sons, Inc. Reprinted by permission of John Wiley & and interdependent reactions involved, some
Sons, Inc.) of which are largely unknown, the overall
process of melt free radical grafting is diffi-
When 2 wt.% n-hexadecane is added, the cult to predict. Here are some qualitative
conversions of all three PSOHs are guidelines to such processes:
increased. A closer look at this plot shows
that the magnitude of increase is very sig- The solubility of peroxides and mono-
nificant for PSOH3. The conversion mers can be low in molten polymers.
increases from the original value of 33% up As the temperatures used for free radical
to 63%. But the increase in conversion for grafting are usually high (>150C), the
376 6 Fundamentals of Reactive Extrusion: An Overview
decomposition of classical peroxides is
very rapid and their half-life times are
extremely short (<100 s).
Due to the high formation rate of primary
free radicals, free radical grafting usual-
ly proceeds rapidly (<100 s).
Because of the short half-life times and
sometimes low solubility of peroxides,
the initiator efficiency is also low (<0.3).
This latter is also related to an accrued
cage effect caused by the high viscosity
of molten polymers.
As the initiator efficiency is low, the
grafting yield is usually much below
100%. In other words, there are always
unreacted monomers left in the system.
CH
I 3
-CC + RO*
I
H
Grafting
1'
CH
1 3
~C*
H
R
\
RO
Grafting is concomitant with other side
reactions (chain degradation, crosslink-
ing, polymerization of monomers, color-
ing, etc.).
In order to have a clearer idea about free
radical grafting, two examples are given
below: the melt free radical grafting of
maleic anhydride (MA) and glycidyl
methacrylate (GMA) onto polypropylene
(PP) in a batch mixer. The common objec-
tive of these two systems is to obtain the
highest grafting yield possible while mini-
mizing free radical induced degradation of
the PP. As discussed above, the underlying
chemistry can be described as follows (Flat,
1991; Sunetal., 1995 a, b):
(a) Primary free radical formation from
the decomposition of the peroxide 2,5-
dimethyl-2,5-di(ter-butylperoxy)-hexane
(DHBP)
R-O-O-R heat
)2RO* (6-10)
(b) Hydrogen abstraction, grafting, and
degradation
+ ROH
B-Scission (6-11)
CH
1 3
+ CH=C
(c) Homopolymerization
(6-12)
Note that the macroradicals, once formed
on the polymer backbone, will undergo
either degradation or grafting. Furthermore,
due to the high instability of tertiary macro-
radicals, the chain degradation process is
extremely fast at elevated temperatures.
Thus effectively stabilizing and/or consum-
ing macroradicals in favor of grafting are
almost the only means of reducing chain

degradation under melt processing condi-
tions.
Example 1. Melt Free Radical Grafting
of MA onto PP
It is well known that MA is chemically
sluggish towards free radical attack due to:
a strong steric hindrance associated with
the substitution of the two adjacent car-
bonyl groups at positions 1 and 2 of the
double bond;
a deficiency of electrons surrounding the
double bond of MA due to the electron-
attracting nature of the carbonyl groups;
the symmetry of the double bond and the
electron cloud.
Three alternative methods were devel-
oped to chemically activate the double bond
of MA in order to increase the grafting yield
with reduced PP degradation (Flat, 1991):
(1) the addition of an electron-donating
monomer such as styrene which is
capable of forming a charge transfer
complex (CTC) with MA;
(2) the addition of a diene that is capable of
forming an adduct product of type
Diels-Alder with MA, which can fur-
ther decompose into an activated MA;
-110000
-100000
-60000
introduced (phr)
6.3 Case Studies 377
(3) the substitution of one of the hydrogens
of MA by a strong electron-donating or
-attracting group such as bromine.
Presented below is the activation of the
MA double bond by method (1). Experi-
mental details can be found elsewhere along
with the results of the other two methods
(Flat, 1991).
The low free radical reactivity of MA
alone onto PP is illustrated by Fig. 6-23, in
which are plotted the grafting yield of MA
and the weight average molecular weight,
respectively, as a function of the added
amount of MA. The grafting yield goes
through a maximum when the added MA
amounts to about 4 wt.% with respect to the
PP resin (or 4 phr), and then decreases. This
observation is explained by the fact that with
increasing MA content, the PP/MA mixture
changes from a single phase to a two-phase
system with MA droplets dispersed in the
molten PP, therefore reducing the effective
concentrations of MA and peroxide (Hogt,
1988). The low grafting yields are concom-
itant with severe PP degradation, as the ter-
tiary PP radicals that are not used for the
grafting undergo /J-scission.
The limited grafting yield and severe PP
degradation are caused by the low reactivity
of MA towards free radicals and its low sol-
Figure 6-23. Grafting yields and weight-aver-
age molecular weights of MA modified PP in
the mixer. Temperature = 215-220C; rotating
speed = 64 rpm; reaction time = 15 min; per-
oxide (DHBP) = 0.5 phr. (From Hu et al.,
1993b. Reprinted by permission of Hiithig and
Wepf Publishers, Zug, Switzerland.)
378 6 Fundamentals of Reactive Extrusion: An Overview

14U-
BrMA / St J^
H 120-
o MA/St s ^
T MA/aMeSt y ^
V MA/NVP ^ sS*
H H
MA/TMVS iT ^ ^ ^
+ 100- A MA/MMA / y/s*
H H MA/MAC y y*C^
CC MA/0L12 # / / ^
80 - MA/IBVE / <// / ^
O=C o=c N o MA / VCH //IT X
o7 X 60-
Figure 6-24. Schematic representation of the charge
transfer complex (CTC) formation between MA and 40-
styrene. (From Hu et al., 1993 b. Reprinted by per-
mission of Hiithig and Wepf Publishers, Zug, 20-
Switzerland.)
OC
0
14:1 2 3 4 5 6
Concentration of electron-donating monomer [D] (M)

ubility in the molten PP. As stated above, the
low reactivity of MA is inherently due to its
structural symmetry and an electron defi-
ciency in the double bond. It is conceivable
that the presence of a monomer capable of
donating electrons could activate MA by
rendering its structure unsymmetrical and its
n bond of radical-anion character. For exam-
ple, the styrene monomer (ST) is a good elec-
tron-donating monomer, and its interaction
with MA can be represented as in Fig. 6-24.
This complex is called the charge transfer
complex (CTC). In this study, *H NMR was
used to select various monomers as poten-
tial electron-donating species. This tech-
Figure 6-25. Chemical shifts (AH) for various MA
(or BrMA)/D systems as a function of the concentra-
tion of D in CDC13 at 22C. BrMA: bromomaleic
anhydride; OL12: 1-dodecene; ocMeST: oc-methyl
styrene; MMA: methyl methacrylate; TMVS: tri-
methoxyvinylsilane. (From Hu et al., 1993b. Reprint-
ed by permission of Hiithig and Wepf Publishers, Zug,
Switzerland.)
o.u-
2.5- MA alone
A St
A /

nique allowed quantification of the interac- A cxMeSt /

2.0- MMA /
tion between MA and an electron-donating Q- 0L12
ifted (

monomer using the chemical shift of the pro- 1.5-

O VAC y
T NVP / /
tons of the double bond of MA. The differ- B

ence in the chemical shift with and without 1.0-

/
VIAJ

an electron-donating monomer (D), AH, ^VA ^^

iy-
measures the degree of interaction (Hu et al. 0.5-
1993 b). As shown in Fig. 6-25 for the Delta -~5^r
values in the presence of various monomers, f
0.01 r
styrene is the monomer with which MA 0 2 4 6 8 10

interacts the most. Additional results show MA introduced (phr)

that the stability of the CTC complex
between MA and ST decreases only slight-
ly with increasing temperature (the activa-
tion energy is as low as -5 kJ/mol). About
25% styrene is in the CTC form at 120C.
Figure 6-26. Grafting yields at various initial
concentrations of MA with or without a second
potentially electron-donating monomer. Molar ratio
[MA]/[D] = 1; reaction conditions the same as in Fig.
6-23. (FromHuetal., 1993 b. Reprinted by permission
of Hiithig and Wepf Publishers, Zug, Switzerland.)

150000
D MA alone
140000- A MA/St
MA/MMA
130000- MA/OL12
A MA/NVP
120000-
J>
110000-
& 100000-
^ 90000-
80000-
70000-
60000
4 6 8 10
MA introduced (phr)
Figure 6-27. Weight average molecular weights of
the modified PP samples. The reaction conditions are
the same as in Fig. 6-23. (From Hu et al., 1993b.
Reprinted by permission of Hiithig and Wepf Publish-
ers, Zug, Switzerland.)
As shown in Fig. 6-26, the magnitude of the
grafting yield corresponds exactly to the
degree of interaction between MA and
the monomer with the exception of NVP
(N-vinylpyrrolidone). In fact, this latter
simply serves as a free radical scavenger, as
also confirmed by the high molecular
weights of the PP products (Fig. 6-27).
Example 2. Melt Free Radical Grafting
of GMA onto PP (Sun et al., 1995 a)
Similar to MA, the free radical reactivity
of GMA alone onto PP is weak and the PP
chain degradation significant. For example,
when a mixture of 5.8 phr GMA, 0.24 phr
DHBP, and 100 phr PP is mixed at about
200C for 15 min, the grafting yield of GMA
is 0.38 phr, i.e., only 7% of the total GMA
is grafted. When the concentration of DHBP
is raised to 0.44 phr, 9% of the total GMA
is grafted.
6.3 Case Studies 379
0.5 1.0 1.5
[St]/[GMA]i (mole/mole)
Figure 6-28. Grafting yields of GMA and styrene
as a function of the initial molar ratio of [ST]/
[GMA]j. [GMA]i=6.0 phr, [DHBP] =0.20 phr, tem-
perature = 200C, rotating speed =64 rpm, reaction
time =15 min. (From Sun et al., 1995 a. Reprinted by
permission of Hiithig and Wepf Publishers, Zug,
Switzerland.)
Interestingly, when styrene is added as a
second monomer, the grafting yield of
GMA is greatly improved. This is better
seen in Fig. 6-28, in which the grafting
yields of GMA and styrene as a function of
the initial molar ratio of [ST]j over [GMA]j
are plotted. The grafting yield is 0.38 phr
without styrene and it is increased to
1.8 phr when [ST]j/[GMA]j is 1.5 mol/mol.
Compared to the case where styrene is not
added, the number^ and weight-average
molecular weights, Mw and M n , of the mod-
ified PP samples are also increased, but to
a lesser extent than the grafting yield
(Fig. 6-29).
The significant contribution of the pres-
ence of styrene to the GMA free grafting is
surprising. This is because, unlike the
MA/styrene system, there is no reason, a pri-
ori, to expect the formation of a CTC in the
GMA/styrene system. In fact, both nuclear
magnetic resonance (NMR) and electron
paramagnetic resonance (EPR) do not detect
380 6 Fundamentals of Reactive Extrusion: An Overview
350
Mwi
300-
Mw
250
.5P 200-
3 150-
Mni
100- D Mn
50
0.0 0.5 1.0 1.5
[St]/[GMA]j (mole/mole)
Figure 6-29. Mw and Mn of the reacted PP as a func-
tion of the initial molar ratio of [STytGMAJj. Mwi
( ) and Mni ( ) denote the Mw and Mn of the PP alone
after 15 min of mixing in the mixer. (From Sun et al.,
1995 a. Reprinted by permission of Hiithig and Wepf
Publishers, Zug, Switzerland.)
any interaction between GMA and styrene
between room temperature and 120C. At
the present time, detailed mechanisms
explaining the contribution of styrene to the
GMA free radical grafting remain unknown.
It is plausible that when styrene is present
the dominating grafting mechanism is that
styrene reacts with the PP macroradicals to
form more stable styryl macroradicals.
These latter then react with GMA to form
GMA-grafted PP. The rate of this reaction
is much greater than that between the PP
macroradicals and GMA.
The kinetics of the free radical grafting of
a mixture of GMA and styrene at about
200C are shown in Fig. 6-30. The free rad-
ical grafting of the mixture of GMA and sty-
rene is a rapid reaction, as the grafting yields
reach a plateau within two or three minutes
of mixing time. This very fast grafting speed
is due primarily to the fast decomposition
rate of the peroxide into primary free radi-
cals (the half-life time of DHBP is about
6 s at 200C). The short half-life time of the
0.0
4 8 12
Reaction time (min.)
Figure 6-30. Grafting yields of GMA and styrene as
a function of mixing time in the batch mixer at 200C.
[DHBPJ^O.20 phr, [GMAj-6.0 phr, [STytGMAJj
= 1.0 mol/mol. (From Sun et al., 1995 a. Reprinted by
permission of Hiithig and Wepf Publishers, Zug,
Switzerland.)
peroxide is also responsible for the exis-
tence of a plateau for the grafting yield. This
is because the concentration of primary free
radicals is very high at the beginning of the
grafting, but depletes quickly at longer
times. As a result, the grafting process ceas-
es after a few minutes.
The grafting yield of GMA or styrene
always increases with increasing peroxide
concentration (Fig. 6-31). This indicates
that the final grafting yield of GMA is dic-
tated by the effective concentration of the
primary free radicals. Note that the ratio of
the concentration of the monomers to that
of the peroxide, [GMA + STytROOR];, for
the grafting is between 40 and 150, which
is almost of the same order of magnitude as
for a typical polymerization. On the other
hand, the conversion of GMA or styrene is
far less than 100%, i.e., between 10 and
40%. As the efficiency of a classical initia-
tor is about 0.5-0.7, which is enough to con-
vert monomers completely into polymers by
a typical polymerization in solution, it is

2.5
2.0-
1-5-
1.0-
[GMA] g withDHBP
0.5- n [St]g with DHBP
[GMA]gwithDIPP
[Stlg withDIPP
0.0 O
0.0 0.1 0.2 0.3 0.4 0.5
Peroxide concentration (phr)
Figure 6-31. Grafting yield vs. the concentration of
DHBP (O) or l,3-bis(ter^butylperoxy-isopropyl)-
benzene (DIPP) at 200C for 15 min. [GMA]j
= 6.0 phr; [ST]j/[GMA]j = 1.5 mol/mol. (From Sun et
al., 1995 a. Reprinted by permission of Hiithig and
Wepf Publishers, Zug, Switzerland.)
estimated that the initiator efficiency for the
free radical grafting of GMA onto PP in the
molten state is 3-10 times lower, say
between 0.1 and 0.3. A much lower initia-
tor efficiency in the molten PP medium is
due to the high viscosity of the medium and
a fast decomposition rate of the peroxide.
As a result, the cage effect is very impor-
tant.
In addition to the basic features illustrat-
ed by these two free radical grafting systems,
i.e., maleic anhydride (MA) and glycidyl
methacrylate (GMA) onto polypropylene
(PP), it is important to note that the most
important result, from the chemistry view-
point, is that the presence of styrene as a
comonomer greatly improves the grafting
yield of MA or GMA. Furthermore, the
mechanism by which styrene contributes to
the free radical grafting appears to be differ-
ent. In the case of MA, the formation of a
charge transfer complex (CTC) between MA
and styrene is important because it activates
the otherwise sluggish double bond of MA.
6.3 Case Studies 381
As for GMA, it is very possible that the dom-
inating mechanism is that styrene reacts first
with the very unstable tertiary macroradicals
of PP at a much greater rate than GMA form-
ing more stable styryl radicals. The GMA
then reacts with these styryl radicals leading
to the grafted GMA moieties. More detailed
discussion on this subject can be found else-
where (Hu et al., 1997 a).
6.3.2 Screw Extruders as Continuous
Flow Reactors
So far we have discussed the behavior of
the polymers in the molten state using
selected representative chemical systems.
Below we examine these systems using the
screw extruder type of continuous reactor.
The goal of analyzing the behavior of a con-
tinuous chemical reactor is to be able to pre-
dict the extent of reaction under given chem-
ical and processing conditions. However,
the ability to do so is still weak. This is
because the three aspects of mixing (tempo-
ral, compositional and thermal) in a practi-
cal REX process are usually largely
unknown. Moreover, chemical reactions are
often ill-defined. As a screw extruder
behaves more closely to a tubular laminar
flow reactor, the Taylor-Aris axial disper-
sion model (Taylor, 1953; Aris, 1956) is
expected to be able to describe the perfor-
mance of this continuous reactor.
The axial dispersion model is a simple
mathematical description of a flow travel-
ling through a tube in which both con-
vection and diffusion are important (Fig.
6-32). In the one-dimensional case, it is
usually written as a partial differential
Q. Q
N L N
Figure 6-32. Sketch of a flow passing through a tube.
382 6 Fundamentals of Reactive Extrusion: An Overview
equation
(6-13)
dt dz dz2
or in a dimensionless form
(6-14)
d6 dx dx2
where C=C(t, z), z the axial coordinate, u
the axial velocity, D the axial dispersion
coefficient, R the reaction rate, 6=tlt-utlL,
and x-zlL. This model contains three
parameters: the mean residence time t, the
Peclet number, Pe=uL/D (micromixing),
and the reaction rate R. The first two param-
eters can be evaluated from the residence
time distribution function of the flow in the
tube, and the third one is determined by the
kinetics of the reaction. In a steady state
reacting system, Eq. (6-14) reduces to an
ordinary differential equation
1 d2C dC
(6-15)
Pe dx2 dx
6.3.2.1 Functional Reactions
in a Microfluid
Below we examine the applicability of the
axial dispersion model for a co-rotating,
self-wiping, twin screw extruder. As a REX
process usually involves feeding, solids
conveying, melting, mechanical mixing,
reacting, and pumping, and some of these
are difficult to evaluate, an experimental
validation of the axial dispersion model
requires that the screw and temperature pro-
Figure 6-33. Screw profile used for the reaction between PGMA and 1 -naphthylacetic acid.
files be simple and the chemical reaction
well defined.
The chemical reaction chosen as an exam-
ple is the functional grafting of 1-naphthyl-
acetic acid onto an ethylene-ethyl acrylate-
glycidyl methacrylate copolymer (PGMA)
in the melt. The kinetics of this reaction in
a microfluid were presented earlier (see
Example 2 in Sec. 6.3.1.1). This PGMA
copolymer has a number molecular weight
of 10000 g/mol with a melting temperature
ranging from 36 to 86C. Thus it can be pro-
cessed in an extruder at relatively low tem-
peratures, e.g., 110C. Its viscosity is also
much lower than that of most polymers.
1-Naphthylacetic acid has a melting temper-
ature of about 130C.
A Werner and Pfleiderer ZSK-30 co-
rotating, self-wiping, twin screw extruder is
used. The screw diameter is 30 mm with a
length-to-diameter ratio LID of 42. The
screw profile is composed primarily of
right-handed conveying screw elements
(Fig. 6-33). In this way, the flow can be
approximated to the flow in a tube. A knead-
ing block is placed near the feeding point in
order to ensure rapid and complete melting
and homogenization of the reacting system.
In other words, this kneading block tends to
reduce the first zone (between the hopper
and the kneading block) for solids convey-
ing and melting, and to decrease the inten-
sity and scale of segregation. Obviously, the
location of this kneading block depends on
the thermomechanical properties of the
reacting system. It should be as close to the
feeding point as possible so that the resi-
 6.3 Case Studies 383

Table 6-3. Comparison between experimental conversions and calculated onesa by the axial dispersion model.

Speed Experimental Microtracer Macrotracer Experimental Microtracer Macrotracer

170C 170C 170C 190C 190C 190C

30 rpm 54.5 57.8 53.3 76.0 74.6

50 rpm 49.7 51.2 47.9 71.2 71.0 70.8
70 rpm 46.9 41.4 43.0 66.5 65.9 64.8

a The conversions have the units %.

Table 6-4. Comparison between experimental conversions and calculated ones by the combined axial dispersi-
on + fiCSTR model.

Speed Experimental Microtracer Macrotracer Experimental Microtracer Macrotracer

170C 170C 170C 190C 190C 190C

30 rpm 54.5 59.1 54.6 76.0 73.5

50 rpm 49.7 45.2 49.2 71.2 67.8 70.1
70 rpm 46.9 41.7 43.8 66.5 65.7 64.5

dence time in the solids conveying and melt-
ing zones can be neglected with respect to
the overall residence time. Two flat barrel
temperature profiles are used: 170 and
190C. The residence time distributions
under these reaction conditions are meas-
ured using two different tracers, both being
sensitive to ultraviolet: a micro-molecule
and a macromolecule containing the former.
The kinetics generated from the batch
mixer (Hu et al., 1997b) and the residence
time distributions in the screw extruders
measured under the reaction conditions
allow the conversions to be calculated using
Eq. (6-15). As shown in Table 6-3, the cal-
culated conversions agree reasonably well
with the experimentally measured ones for
both tracers despite some differences in the
Peclet number. This indicates that the axial
dispersion model is indeed capable of
describing the performance of this screw
extruder with this homogeneous reacting
system. Considering the fact that a pressure
flow exists near the die, a combined axial
dispersion + ftCSTR model is also used to
predict the conversions at the exit of the die.
Apparently, there is only a slight improve-
ment with this combined model (Table 6-4).
This is because the length of a CSTR in
series is found to be relatively short com-
pared to the total length of the screw extrud-
er (< 15%).
From the above discussion, it can be said
that the ZSK-30 twin screw extruder with
the chosen screw profile and reacting
system behaves as a tubular chemical reac-
tor. More generally, it can be said that for a
chemical reaction of a homogeneous mix-
ture whose kinetics are not controlled by dif-
fusion but by its intrinsic reactivity, the axial
dispersion model should be capable of pre-
dicting the conversion upon coupling the
kinetics and the residence time distribution
with good accuracy.
6.3.2.2 Free Radical Grafting
of Monomers onto Polymers2
Owing to the various complications
involved in melt free radical grafting of
2
Sunetal. (1995b).
384 6 Fundamentals of Reactive Extrusion: An Overview
monomers onto polymers discussed earlier,
the performance of a screw extruder as a
flow chemical reactor for such a reaction is
difficult to evaluate. Nevertheless, it can be
said that, qualitatively, the behavior of a free
radical grafting carried out in a screw
extruder is the same as that in a batch mixer:
the grafting rate is very high due to the
short half-life times of classical initiators
(organic peroxides) at elevated tempera-
tures (>150C);
the initiator efficiency is usually low due
to its limited solubility in molten poly-
mers and the cage effect exerted on the
primary free radicals;
the grafting rate and yield are determined
by the effective concentration of the pri-
mary free radicals.
The particular feature of a screw extrud-
er as a continuous flow reactor for free rad-
ical grafting is that its performance cannot
be determined by the overall residence time
distribution, but by a local residence time
distribution. This latter is in turn related to
the half-life time and efficiency of the initia-
tor used.
In order to have a better feel about the
above statements, we again take as an exam-
ple the melt free radical grafting of glycidyl
methacrylate (GMA) onto polypropylene
(PP) in the ZSK-30 co-rotating, intermesh-
PP + monomers + peroxide
Sampling Sampling
i l l i Ml nn ' ii
\7 Pt ^7
H
11/ f i 17 1 iZ
200C - 230C
Figure 6-34. Screw and temperature profiles for the free radical grafting of GMA onto PP. (From Sun et al.,
1995b. Copyright 1995, John Wiley & Sons, Inc. Reprinted by permission of John Wiley & Sons, Inc.)
ing, twin screw extruder. Shown in Fig.
6-34 are the screw and temperature profiles.
As shown in Fig. 6-35, the grafting yield
reaches a plateau after traveling a certain
screw length downstream: more than 70%
of the final grafting yield is already achieved
by the first sampling point (36% of the total
screw length downstream from the hopper
or Z/D = 15.5); almost 100% of the final
grafting yield is obtained by the second sam-
pling point (half-way downstream from the
hopper or LID-21). In other words, the first
half of the screw is long enough for the reac-
tion to reach its limit, including accomplish-
ing solids conveying and melting. Note also
that the ultimate grafting yield is far below
100%: 24, 33, and 50% corresponding
respectively to 0.30, 0.50, and 0.70 phr of
the peroxide introduced. This shows that the
ultimate grafting yield is dictated by the
concentration of the peroxide or primary
free radicals. This latter decreases consid-
erably along the screw length because the
temperature in the first zone between the
feeding point and the first sampling point is
high (200C), and the corresponding half-
life time of the peroxide is about 6 s.
The decrease in the concentration of the
primary free radicals should be more abrupt
beyond the first screw zone. This is because
the temperature between the second sam-
pling point and the die (the second zone) is
Venting
LDljE
JMliMSS
11 f ] iT ^
240C Sampling

[DIPP],:
A 0.70 phr
0.50 phr
o 0.30 phr
0.0
10 20 30 40
L/D
Figure 6-35. Grafting yields along the screw length.
[GMA]; = 3.0 phr; [ST]i/[GMA]i = 1.40 mol/mol;
(2 = 3.5 kg/h; JV=150 rpm. The peroxide (DIPP):
1,3-bis(terr-butylperoxy-isopropyl)benzene. (From
Sun et al., 1995b. Copyright 1995, John Wiley &
Sons, Inc. Reprinted by permission of John Wiley &
Sons, Inc.)
raised to 240C, and the corresponding half-
life time of the peroxide is reduced to 0.3 s.
As a result, most of the free radical grafting
has taken place in the first zone. This implies
that free radical grafting in a screw extruder
may not necessarily be characterized by
the overall residence time distribution
(between the hopper and the exit of the die),
but by the one that corresponds to the zone
where the primary free radicals exist. The
length of this zone is determined by the rate
of decomposition or roughly the half-life
time of the peroxide under the processing
conditions. Put another way, for a particular
zone of interest, if the concentration of the
primary free radicals at the exit of this zone
is literally greater than zero, the grafting
yield of GMA will be affected by the resi-
dence time distribution therein. By contrast,
if the primary free radicals are totally deplet-
ed before the exit of this zone, the ultimate
grafting yield may no longer be affected by
a variation in the residence time distribution
6.3 Case Studies 385
in this particular zone. Thus the half-life time
and the initiation efficiency of the peroxide
under the free radical grafting conditions are
the two critical parameters that govern the
performance of a particular melt free radical
grafting system. Unfortunately, these two
parameters are usually difficult to evaluate
under practical grafting conditions.
An alternative way to overcome the lim-
ited GMA grafting yield due to the short
half-life time of the peroxide may be to add
the peroxide to the extruder further down-
stream, as well as at the first and/or the sec-
ond sampling points, for example. Howev-
er, this alternative may not be ideal as it
makes the process more complicated.
The above results indicate that the behav-
ior of the free radical grafting of GMA in
the twin screw extruder is very similar to
what is observed in a batch mixer (see
Example 2 in Sec. 6.3.1.2). The major fun-
damental difference is that in the batch
mixer the grafting yield varies as a function
of time, while in the twin screw extruder it
changes along the screw length.
As the local residence time associated
with the half-life time of the efficiency of a
peroxide is important for the grafting yield,
a variation in screw speed (N) or feeding rate
(<2) should alter the grafting yield as well.
This is shown in Figs. 6-36 and 6-37; an
increase in N or Q decreases the grafting
yield of GMA due to a reduced residence
time in the first screw zone between the hop-
per and the first sampling point (L/D = 15.5).
On the other hand, mixing does not seem to
be important because an increase in N
enhances mixing whereas an increase in Q
reduces mixing. Thus the equivalence in
terms of the grafting yield between N and Q
can only be conciliated through the resi-
dence time distribution in the first screw
zone. The effects of N and Q on the free rad-
ical grafting are exerted mainly through
changes in the residence time distribution,
386 6 Fundamentals of Reactive Extrusion: An Overview

0.5
It was suggested above that it is through
the residence time distribution that Q or N
0.4 affects the grafting yield. Spatial mixing
appears to be unimportant, probably due to
sufficient solubility of the monomers and
0.3-
peroxide in the PP melt. In order to further
support these two statements, the effect of
the specific throughput (Q/N) is examined.
0 = 5.6 kg/h The specific throughput is defined as the
150 rpm ratio of throughput to screw speed, Q/N,
o 240 rpm with the units kg/rpm. As discussed else-
where (Hu, 1994), Q/N measures, to some
O.OO extent, the pumping capacity of a particular
30 40
twin screw extruder: the amount of materi-
al each turn of the screw can pump. It also
Figure 6-36. Grafting yield of GMA along the screw
length at two different screw speeds (150 and 240 rpm)
characterizes the degree of fill of a twin
for a given throughput of PP (5.6 kg/h). (From Sun et screw extruder in partly filled zones. The
al., 1995 b. Copyright 1995, John Wiley & Sons, Inc. reverse of this ratio, N/Q, has the units
Reprinted by permission of John Wiley & Sons, Inc.) rpm/kg. It can be viewed as being the
number of screw turns a unit amount of
material has experienced before it exits from
the extruder. Thus it measures the intensity
of mixing the material has experienced in
the partly filled zones. If the pressure flow
in a twin screw machine due to the die resis-
tance and/or other pressure consumers is
N = 90 rpm unimportant, then Q/N and N/Q character-
A2.1 kg/h ize the degree of fill and the intensity of
n3.4 kg/h mechanical mixing in the whole machine,
o5.6 kg/h respectively. If this is true, unlike a change
in Q or N which affects not only the resi-
dence time but also the axial mixing, varia-
0.0 tions in both Q and N for a particular Q/N
30
will only affect the residence time distribu-
tion. This was confirmed experimentally.
Figure 6-37. GMA grafting yield along the screw For example, shown in Fig. 6-38 a is the res-
length at various feed rates of PP for a given screw
speed (90 rpm). (From Sun et al., 1995b. Copyright idence time distribution density function
1995, John Wiley & Sons, Inc. Reprinted by permis- f{t) as a function of time for a given
sion of John Wiley & Sons, Inc.) Q/N (=1/43 kg/h/rpm) and three different
throughputs and screw speeds. The corre-
and variations in mechanical mixing are sponding dimensionless residence time
apparently unimportant. This latter may distribution density function /(T) as a func-
imply that the mixing imposed on our free tion of dimensionless time r iz=t/t with
radical grafting is good enough under all the t being the mean residence time) is shown
processing conditions. in Fig. 6-38b. The/0) curve is shifted to a
 6.3 Case Studies 387

0.016

A 5.6 kg/h 240 rpm

5.6 kg/h; 240 rpm A o 3.5 kg/h, 150 rpm
o 3.5 kg/h; 150 rpm 2.0-
0.012
A 2.1 kg/h; 90 rpm
A2.1 kg/h; 90 rpm
i
1.5-
O
A
, 0.008
A
1.0-

0.004 * O
0.5-
e
o \
0.000
150 300 450 600 750
0.0-
0.0
s
0.5 1.0 1.5 2.0 2.5 3.0
Time (s) ^

a b
Figure 6-38. Residence time distribution density function as a function of time for three different throughputs
and screw speeds with a particular QIN (1/43). Polymeric fluid: polystyrene (2 = 3.5 kg/h). (a) f(t) versus /; (b)
/(T) versus T. (From Sun et al., 1995b. Copyright 1995, John Wiley & Sons, Inc. Reprinted by permission of
John Wiley & Sons, Inc.)

short time domain when Q and N are

increased (Fig. 6-38a). Interestingly, the
three/(0 curves in Fig. 6-38 a superimpose
well when they are converted to/(r) curves
(Fig. 6-38b). This means that when QIN
is fixed, an increase in Q with a concomi-
tant increase in N shortens the residence
time only, while the axial dispersion
remains almost the same. Thus the observed
decrease in the grafting yield (Fig. 6-39)
with increasing Q and N for a given QIN is
related only to a decrease in the residence
time.
It is also found that the specific energy,
the energy that is imparted to a unit amount
of material, is not a measure of the perfor-
mance of this melt free radical grafting by
reactive extrusion. This is shown in Fig.
6-40: the grafting yield of GMA decreases
when U increases. In other words, as
opposed to what might be expected, the
higher the energy that is imparted to the
system, the worse the grafting yield. This
apparent paradox can only be explained by
A 90 rpm
150 rpm
o 240 rpm
Q/N= l/27(kg/h)/rpm
o.o
30 40
Figure 6-39. Grafting yield of GMA at a given spe-
cific throughput (Q/N=l/43) with three correspond-
ing screw speeds and throughputs. (From Sun et al.,
1995b. Copyright 1995, John Wiley & Sons, Inc.
Reprinted by permission of John Wiley & Sons, Inc.)
the fact that the residence time is the criti-
cal parameter. An increase in specific ener-
gy for a given QIN is concomitant with a
decrease in the residence time.
388 6 Fundamentals of Reactive Extrusion: An Overview
0.5-
at L/D = 42 (die)
M 0.3-
atL/D= 15.5
0.1 -
500 600 700 800
U(kW/kg)
Figure 6-40. Grafting yield of GMA as a function
of the specific energy for a given specific throughput
(g/N=l/43). (From Sun et al., 1995b. Copyright
1995, John Wiley & Sons, Inc. Reprinted by per-
mission of John Wiley & Sons, Inc.)
6.3.3 Screw Extruders
as Reactive Blenders (Compounders)
for the In Situ Compatibilization
of Immiscible Polymer Blends
by One-Step Reactive Extrusion
Multiphase polymer blends are of great
importance in the development of new syn-
thetic materials. A usable polymer blend
requires the interfacial tension and the inter-
facial adhesion in the blend to be properly
controlled, due to their role in governing the
blend morphology and its associated
mechanical properties. This can be achieved
by adding to an immiscible polymer blend
appropriate interfacial agents (compatibi-
lizers) like block and graft copolymers that
locate preferentially at the interface. As a
result, the interfacial tension is reduced,
the interfacial adhesion strengthened, and
coalescence minimized (Guegan et al.,
1994). However, if a particular interfacial
agent had to be synthesized separately for a
particular pair of immiscible polymers, then
"polymer blend" would have been nothing
but an academic term. This is due to diffi-
culties in designing and synthesizing inter-
facial agents that should be satisfactory for
the industrial production of polymer blends.
Furthermore, only part of a compatibilizer
added to an immiscible polymer blend goes
to the interface due to thermodynamic rea-
sons (micelle formation, preferential mis-
cibility with one polymeric phase, etc.),
and/or dynamic reasons (dispersion of the
compatibilizer by diffusion or a convective
mixing mechanism is not always easy).
900 Recent years have seen increasing efforts
towards the in situ compatibilization of
immiscible polymer blends by reactive
extrusion (Lambla and Seadan, 1993; Liu et
al., 1993): instead of synthesizing interfa-
cial agents as a separate step, they are creat-
ed during extrusion through interfacial reac-
tions between selected functional polymers.
This is also called reactive blending. Com-
pared to separately synthesized compatibi-
lizers, in situ formed compatibilizers are
expected to be more effective at compatib-
ilizing the corresponding blends as they are
formed at the interface. However, not all
polymers contain functional groups. When
a polymer bearing functional groups is to be
mixed with another polymer which is chem-
ically inert with respect to these functional
groups, this latter ought to be functional-
ized. Free radical grafting of a vinyl
monomer bearing desired functional groups
is employed the most for functionalization.
In this case, two reactive blending process-
es are conceivable: (a) the polymer is func-
tionalized as a separate extrusion step, and
the functionalized polymer is then blended
with the functional polymer as a second
extrusion step; (b) both the functionaliza-
tion and blending steps are executed in the
same extrusion process. For example, func-
tionalization can be carried out in the first
part of the extruder followed by subsequent
interfacial reaction between the functional

and functionalized polymers. Process (a) is
called the in situ compatibilization of
immiscible polymers by two-step reactive
extrusion and process (b) one-step reactive
extrusion. To some extent, it can be said that
one-step reactive extrusion is technologi-
cally more difficult to control but more eco-
nomical than two-step reactive extrusion.
While the in situ compatibilization of
immiscible polymer blends has been the most
important application of REX, it is also the
most complicated process compared to other
REX processes. This is because the presence
of chemical reactions interferes with other
sequential operations, and vice versa. The
morphological development of the blend is
affected by the twisted chemistry and extru-
sion process. As there are so many factors
involved in the process, not many general
conclusions have so far been generated.
In what follows, we will address two
important points: (1) an individual sequen-
HO-
6.3 Case Studies 389
tial operation such as devolatilization may
become a bottleneck in the whole process;
and (2) the performance of a reactive blend-
ing process may be determined by the tem-
poral aspect of mixing, the spatial aspect of
mixing or both, depending upon the relative
importance of both aspects of mixing. In
order to address both points in a limited
space, an example is taken of the in situ com-
patibilization of PP and poly(butylene
terephthalate) (PBT) by one-step reactive
extrusion. The main reason to choose this
system is that the underlying chemistry has
already been described in the preceding par-
agraphs. It involves the free radical grafting
of GMA onto PP (free radical reactivity) fol-
lowed by interfacial reaction between the
functionalized PP and the carboxylic group
of the PBT (functional reactivity):
(a) Grafting of GMA onto PP (function-
alization) (Eq. 6-16).
(b) Interfacial reaction between the func-
tionalized PP and PBT (Eq. 6-17).
+ ROH
(6-16)
~co (6-17)
PBT
390 6 Fundamentals of Reactive Extrusion: An Overview
6.3.3.1 De volatilization:
A Critical Sequential Operation
It has been shown that the grafting yield
of GMA onto PP is far below 100%. As a
matter of fact, there are three types of epoxy
group in the process: grafted GMA, poly-
merized GMA, and residual GMA. Thus
aside from the desired reaction between the
GMA-grafted PP and the functional groups
of the PBT, the residual and possibly poly-
merized GMA are also expected to react
with the PBT and probably at a greater rate.
Therefore the residual GMA monomer
should be removed efficiently from the
system to reduce these unwanted reac-
tions.
PP + Reagents PBT
Solids conveying, Mixing and reaction
melting and reaction
PP + Reagents
Solids conveying, PBT melting
melting and reaction
PP + Reagents
Solids conveying, Devolatilization
melting and reaction
Figure 6-41. Three different screw configurations used for the in situ compatibilization of the PP/PBT system.
In order to show that devolatilization is an
important operation (Hu et al., 1996 a), three
different screw configurations (Fig. 6-41)
were chosen to process a mixture of PP/PBT
(70/30) in the presence of the same amounts
of low molecular reagents as the compatib-
ilizer precursor (initial concentrations of the
small molecule reagents: [GMA]j=3.0 phr,
[STV3.0 phr, [DIPP]i=0.3 phr):
The performance of the in situ compati-
bilization of these three screw configura-
tions is evaluated in terms of the elongation
at break and the impact strength of the result-
ing blends. As shown in Fig. 6-42a and (b),
screw configuration A2 (Fig. 6-41) yields
better compatibilization than Al in terms of
the elongation at break and impact strength.
Devol - Pumping
atilization
Al
Mixing and reaction Devol - Pumping
atilization
A2
PBT melting Mixing and reaction Pumping
A3

300-
250
2 200
150 +
I 10 +
WO
50
I
Mech.
n
Al A2 A3 PP PBT
Figure 6-42. Comparison of various materials in terms of (a) the elongation at break according to the falling
weight test ISO 6603/2 and (b) the impact strength according to ASTM 638-71 A. Mech: mechanical blend PP/PBT
(70/30); Al, A2, and A3: compatibilized blends PP/PBT (70/30) obtained from screw profiles Al, A2, and A3,
respectively.
Screw configuration A3 gives the best com-
patibilization as the elongation at break and
impact strength of the corresponding blend
are the highest. Bear in mind that the main
difference between screw configurations A1
and A2 and the associated processing con-
ditions for blending lies in the manner of
feeding the components involved in the
blend. In the case of screw configuration A1,
all components (PP, GMA, styrene, perox-
ide, and PBT) are fed through the same hop-
per; and in the case of screw configuration
A2, PBT is fed further downstream, separ-
ate from the other components. Screw con-
figuration A.I allows for easier feeding than
screw configuration A2, and it is largely
used intuitively for reactively blending
polymers. The real impact of the difference
in feeding between screw configurations Al
and A2 on the compatibilization results from
the difference in the physical environment
for the underlying chemistry. With screw
configuration Al, the free radical grafting
of GMA onto PP is disturbed by the pres-
ence of PBT: this latter dilutes the concen-
trations of GMA and PP, therefore reducing
the grafting rate; more importantly, aside
6.3 Case Studies 391
30 T
l20+
I
n . II
Mech. Al A2 A3 PP PBT
from the desired free radical grafting of
GMA onto PP with a subsequent interfacial
reaction with PBT, the free GMA monomer
also reacts with PBT (mostly with the car-
boxylic acid group at its chain end). In fact,
GMA may react with PBT much faster than
PP-g-GMA (grafted PP) due to its greater
mobility. The downstream feeding of PBT
using screw configuration A2 circumvents
these problems in favor of the formation of
the amphiphilic copolymer PP-g-PBT.
As pointed out earlier, the three types of
epoxy group in the system: GMA grafted
onto PP [GMA]g, unreacted GMA [GMA]r,
and homopolymerized and/or copolymer-
ized GMA (when styrene is present)
[GMA]p, are capable of reacting with PBT.
The first reaction is desirable, whereas the
other two reactions are not. Thus it is impor-
tant to evaluate the amounts of these three
types of epoxy group under our blending
conditions. Such a quantitative evaluation is
not feasible with screw configuration Al
due to the presence of PBT. However, it is
possible with screw configuration A2 prior
to the feeding point of PBT. Experimental-
ly, the amounts of the three different GMA
392 6 Fundamentals of Reactive Extrusion: An Overview
structures were measured with various
initial amounts of GMA introduced to the
PP. The results are shown in Fig. 6-43. With
increasing initial concentration of GMA
([GMA]j) the amounts of the three different
GMA structures, [GMA]g, [GMA]r, and
[GMA]p, increase. Apparently, the residual
GMA ([GMA]r) increases faster than the
grafted GMA ([GMA]g). Within the
initial concentration range of [GMA]j
(1.4-7.0 phr), [GMA]r is 2 - 7 times higher
than [GMA]g. This means that [GMA]r is
four times higher than the concentration of
the terminal carboxylic group of the PBT
(f-COOH]) when [GMAJ^l.4 phr. It can
be as high as seventeen times [-COOH]
when [GMA]i = 7.0 phr. This clearly shows
the need to remove [GMA]r effectively from
the system before the PBT is fed, in order
to promote the desired reaction between
PP-g-GMA and PBT-COOH.
o within the screw machine, but also by the
[GMA]i (phr)
Figure 6-43. Amounts of grafted, polymerized, and
residual GMA, [GMA]g, [GMA]p, and [GMA]r, as a
function of the amount of GMA introduced, [GMAjj,
during the free radical grafting of GMA onto PP by
reactive extrusion with screw configuration A2. The
data were collected prior to the feeding point of PBT.
The PBT contains 0.040 eq./kg of carboxylic group.
(From Hu et al., 1996 a. Reprinted by permission of
Society of Plastics Engineers.)
The merit of screw configuration A3
compared to A2 is that the devolatilization
zone, which in screw configuration A2 is
placed prior to the pumping zone, is shifted
upstream to just after the first kneading
block. Moreover, the devolatilization length
is increased. Therefore the unreacted GMA
can be removed more efficiently from the
extruder before the PBT is fed.
6.3.3.2 Effects of Processing
Parameters 3
As described earlier, the free radical
grafting of GMA onto PP and the interfacial
reaction between the grafted PP and the car-
boxylic group of the PBT are carried out in
a consecutive manner: basically, the first
part of the screw length (as demarcated by
the first kneading block) is assigned primar-
ily for the free radical grafting, while the
second part is made available for the inter-
facial reaction between the GMA-grafted
PP and the carboxylic acid group of the PBT.
The morphology of the blend starts devel-
oping in the second part of the screw length.
The final morphology of the blend as well
as its associated mechanical properties are
affected not only by the temporal, spatial
(compositional), or thermal mixing history
the mixture of PP/PBT has experienced
rate and amount of formation of the PP-g-
PBT copolymer at the interface. In other
words, any processing parameter that influ-
ences the temporal, spatial, or thermal mix-
ing history, and/or the rate of formation and
amount of PP-g-PBT copolymer has an
impact on the final morphology of the blend
as well as its associated mechanical proper-
ties. Thus it is important to understand and
to quantify the contribution a particular pro-
Huetal. (1996b).
 6.3 Case Studies 393

cessing parameter has to each of these var-
ious aspects, so that its overall effect can be
evaluated. Unfortunately, in most practical
situations, these various aspects are so inter-
twined that their individual contributions to
the overall effect of a particular processing
parameter are difficult to identify and/or
quantify.
It has been found that, similar to the free
radical grafting of GMA onto PP carried out
in the same extruder (Sun et al., 1995b), the
fundamental physics that dictates the effects
of these processing parameters (Q, AT, QIN)
on the performance of the in situ compati-
bilization of the PP/PBT blend is the resi-
dence time (macromixing). Mechanical
mixing per se (micromixing), on the other
hand, is so good with the screw profile cho-
sen that it is not a critical parameter for such
processes. Thus it is expected that the elon-
gation at break and the impact strength will
decrease with increasing Q ox N due to a
reduced residence time. Interestingly, they
decrease virtually linearly with Q or N.
When both Q and TV increase proportional-
ly for a given specific throughput {QIN),
these mechanical properties also decrease,
almost linearly [Fig. 6-44 a and (b)].
Similar to the free radical grafting of
GMA onto PP in this co-rotating twin screw
extruder, the specific energy is not a meas-
ure of the effectiveness of this in situ com-
patibilization process either. This is clearly
shown in Fig. 6-45: the impact strength of
the compatibilized PP/PBT blend decreases
when [/increases, as opposed to what might
be expected, i.e., the higher the energy that
is imparted to the blend, the better its impact
strength. Again, this apparent paradox can
only be explained by the fact that the resi-
dence time is the critical parameter. An
increase in the specific energy for a given
QIN is concomitant with a decrease in the
residence time.

160- 25- Q/N = constant

\ Q / N = 1 / 30
> 20-
120- N
strengtJ

X> 15-
\
n
80-
10-
Q/N = 1/19
o 5-
40-

1 0-
50 100 150 200 250 60 120 180 240

N(rpm) N(rpm)

a b
Figure 6-44. (a) Variation of the elongation at break and (b) the impact strength of the compatibilized PP/PBT
blend as a function of the screw speed for two particular specific throughputs (Q/N=l/30 and 1/19). Impact test
temperatures in Fig. 6-44b: ( ) 0C; ( O ) - 2 0 C ; ( ) 0C; ( ) - 2 0 C . (From Hu et al., 1996b. Copyright
1996, John Wiley & Sons, Inc. Reprinted by permission of John Wiley & Sons, Inc.)
394 6 Fundamentals of Reactive Extrusion: An Overview
400 500 600 700 800
U(kW.h/kg)
Figure 6-45. Variation of the impact strength of the
compatibilized PP/PBT blend as a function of the
corresponding specific energy (/); ( ) Q/N=l/30,
0C; (O) Q/N=\/30, -20C; ( ) Q/N=l/\9, 0C;
(n)Q/N=l/\9,-20C.
6.3.4 Residence Time Distributions in
Screw Extruders: A Statistical Theory
The residence time distribution (RTD) in
a screw extruder is an important parameter
for extrusion processes, as it characterizes
the temporal aspect of mixing. This is par-
ticularly the case when chemical reactions
are occurring during extrusion (see Sees.
6.3.2 and 6.3.3). Optimization of such a pro-
cess requires an in-depth understanding of
the RTD function for each of the sequential,
yet dependent, zones (feeding, solids con-
veying, melting, mixing, chemical reaction,
devolatilization, pumping, etc.). However,
access to these individual RTD functions is
often difficult experimentally. Flow analy-
sis may be useful but only qualitative for
most practical situations, because (1) the
flow path and the thermomechanical histo-
ry of polymers for a reactive extrusion pro-
cess (often in a twin screw extruder) are
complicated, (2) polymer fluids are highly
viscous and non-Newtonian, and (3) the var-
ious sequential zones are separated physi-
cally by mixing and/or pressure consuming
elements, and flow at the boundaries
between these zones is very complicated.
Consequently, a number of models for the
RTD in a screw extruder have been devel-
oped during the last two decades with lim-
ited use. Todd used the Taylor-Aris axial
dispersion model to fit RTD curves to an
intermeshing counter-rotating twin screw
extruder (Todd, 1975). This model was also
used recently by Zuilichem et al. (1988).
Other authors tried to develop theoretical
models through flow mechanism analysis.
Most of these models only hold for the RTD
in the part of the extruder where the flow
pattern is relatively simple. For example,
Matsubara developed models for a T-die and
a coat-hanger die (Matsubara, 1983); Pinto
and Tadmor developed a model for the RTD
for a single screw extruder (Pinto and Tad-
mor, 1970); Kemblowski and Sek present-
ed a model for the mean residence time and
the variance of the RTD in a single screw
extruder (1981); Potente and Lappe studied
the effect of different tracers on the accura-
cy of RTD measurement and proposed a
mathematical model for the mean and min-
imum residence time in a single screw
extruder (1986); Kao and Allison studied
the effects of some selected process param-
eters, and the results were explained by the
flow mechanism in a partly filled channel
(1984).
A notable model was developed by Jans-
sen et al. (1979) for the RTD in an inter-
meshing, counter-rotating, twin screw
extruder. The extruder was treated as C-
chambers (the geometric configuration of a
single screw turn through which fluid pass-
es resembles a C-shape) connected in series,
along with two important assumptions: the
leakage flows in the solids conveying, melt-
ing, and partly-filled zones are unimportant,
and the C-chambers in the last fully filled

zone are perfect mixers. Foster and Lindt
treated the screw elements of a noninter-
meshing, counter-rotating, twin screw
extruder as perfect mixers in series (1990).
However, it is well known that a single C-
chamber is far from a perfect mixer, and the
calender leakage flow is significant even in
partly filled screw channels.
In order to search for an alternative solu-
tion, we have examined the applicability of
a statistical theory for the RTD in an extrud-
er. The fundamental basis of this theory
(Nauman and Buffham, 1983; Chen and Hu,
1993; Chen et al., 1993) is that for a flow
passing through a closed system composed
of two closed elements in series, if fluid par-
ticles leaving the first element have the same
probability of occupying a particular posi-
tion at the entrance of the second element,
the RTDs in these two elements are statisti-
cally independent of each other. Then the
RTD of the whole system can be calculated
from the RTDs of the individual elements
using a statistical method. For a closed
system consisting of n closed and statistical-
ly independent elements connected in series,
whose residence time density functions are
fx(t),f2(t), to/(*), respectively (Fig. 6-46),
the overall/(0 function is related to those of
the individual elements in the time domain
by the following n-fold convolution
3T
J
For a closed system composed of two
closed elements, Eq. (6-18) reduces to
(6-19)
element 1 element 2 element n-1
fl(t) f2 fn-lW
6.3 Case Studies 395
The individual f(i) functions in Eqs.
(6-18) and (6-19) are interchangeable since
they are independent of each other. The sta-
tistically independent RTDs in elements in
series physically imply that perfect mixing
exists at the junction or the boundary
between any two adjacent elements, so that
fluid particles at this location are totally ran-
domized. Of course, the individual elements
should be closed systems: fluid particles
enter the system only one time; once they
have left the system they will never return.
The validity of this statistical theory was
examined experimentally using two combi-
nations: (1) a die and a single screw, and (2)
a die and a twin screw. Specifically, a sin-
gle screw extruder (Haake Rheomix 254;
screw diameter: 19 mm; length-to-diameter
ratio: 25) and a laboratory conical, inter-
meshing, counter-rotating, twin screw
extruder (Haake Rheomix TW-100, tip-
screw diameter: 19.7 mm; screw length:
331.78 mm) were chosen as the extruders.
A small die (Fig. 6-47 a) was used as an
adapter to measure the RTDs of these two
screws (the length of the adapter was so
small that the residence time in it could be
neglected). A large die (Fig. 6-47b) having
a long cylindrical channel (L = 114mm)
with a diameter of D=19 mm was used to
(6-18)
measure the RTDs in these two combina-
tions of die and screw. Polystyrene was cho-
sen as the polymer fluid and 1-aminoanthra-
element n
Figure 6-46. n elements
fn(t) connected in series.
396 6 Fundamentals of Reactive Extrusion: An Overview
Figure 6-47. Dies used for RTD measurements: (a)
small die used for the RTD of the screw; (b) large die
for the RTD of the combination of the screw and the
die.
quinone incorporated with the polystyrene
as the tracer. RTD runs were carried out at
190C.
H e r c / ^ 0 is denoted as the RTD in the
screws and/ 2 (0 as that in the large die. This
latter for the fully developed laminar flow
of a Newtonian fluid is given by
fo t<tQ
t>t0
t3
with
nD2L (6-20)
As shown in Fig. 6-48 a and (b), the
experimental RTD results and those predict-
ed by Eq. (6-19) agree well with the experi-
mental ones for both combinations, indicat-
ing that flow at the junction between the
large die and the single or twin screw is suf-
ficiently mixed radially that the RTD in the
large die and that in the single or twin screw
are practically independent statistically.
Considering the degree of mixing the flow
has experienced at the above junctions, it
appears that this statistical theory is useful
for obtaining RTDs in the various sequen-
tial zones of an extrusion process where
staged operations are demarcated by strong
mixing and/or pressure consuming elements
(kneading discs, calender gaps, etc.). In fact,
0.010
Experiment (single screw
Calculation by Eq. (6-19)
Experiment (twin screw + large die)
0.008
Calculation by Eq. (6-19)
0.006-
, 0.004-
0.002-
0.000
200 400 600 800 1000 1200 1400 1600
Time (s)
Figure 6-48. Comparison between the RTD predict-
ed by Eq. (6-19) and the experimental results.
this theory has also been confirmed for mod-
erately concentrated polymer solutions
passing through a multi-staged, counter-
rotating, nonintermeshing, twin screw
extruder (Chen et al., 1995). It has also been
used to develop a predictive RTD model for
an intermeshing, counter-rotating, twin
screw extruder with success (Chen et al.,
1993). Other applications of this theory to
REX are under investigation.
6.4 Conclusions
Reactive extrusion (REX) has already
become a distinct multi-disciplinary engi-
neering speciality in the framework of poly-
mer engineering and science and chemical
engineering and science. Nonetheless, the
scientific understanding of REX is still poor
due to the various, highly coupled sequen-
tial operations involved (feeding, solids
conveying, melting, mixing, reaction, vent-
ing, pumping, and shaping). The first part
of this chapter was devoted to introducing
the historical background and basic features
of REX, and to reviewing selected funda-

mental aspects of this multi-disciplinary
engineering speciality. In the second part,
selected examples were given in order to
provide some general guidelines to some of
the fundamental problems encountered in
REX including:
the kinetic behavior of functional and free
radical reactions in the molten state;
the performance of screw extruders as
chemical reactors for functional and free
radical reactions;
the performance of screw extruders as
reactive blenders;
the residence time distribution in screw
extruders.
The first example was aimed at describ-
ing the kinetic behavior of functional chem-
ical reactions carried out in three different
bulk media (microfluid, partially segregat-
ed fluid, and macrofluid). The advantage of
using functional reactions is that they are
chemically cleaner than free radical ones.
When a chemical reaction is carried out in
a microfluid (the reacting medium is homo-
geneous, be it in solution or in a homoge-
neous melt), if the ratio of the characteris-
tic reaction time to the characteristic diffu-
sion time is much larger than unity
(tR/tD > 1), then the overall reaction rate is
controlled by its intrinsic kinetics. More-
over, it is expected that the mechanisms and
kinetics in solution and in the homogeneous
melt are identical provided that the solvent
does not interfere with the reaction pathway.
On the other hand, mechanical mixing is
only important for the homogenization or
diffusion length reduction of the reacting
system at the initial stage of the reaction.
Once this is achieved, no more mechanical
mixing is necessary.
The kinetic behavior of a chemical reac-
tion carried out in a partially segregated fluid
was discussed by taking as an example a
reacting mixture that was composed of a
6.4 Conclusions 397
reactive polymer, a chemically inert poly-
mer, and a small reactive molecule. These
two polymers are immiscible, while the
small reactive molecule is miscible with both
polymers. In other words, the small reactive
molecule is partitioned between both poly-
meric phases. In this case, if the molecular
diffusion rate of the small reactive molecule
in these two polymeric phases is so rapid that
an equilibrium is established between them
in terms of concentration and if tR/tD > 1,
then the overall reaction rate is only con-
trolled by its intrinsic kinetics and the parti-
tion coefficient of the small reactive mole-
cule in these two polymeric phases. Here
again, mechanical mixing is important only
for reducing the diffusion length of the react-
ing system at the initial stage of reaction.
Once this is achieved, mechanical mixing is
no longer needed.
As for the chemical reaction between
immiscible polymer melts (macrofluid), its
kinetic behavior is expected to be similar to
that in a microfluid in terms of the effects
of temperature and the nature and concen-
tration of the catalyst. However, as opposed
to a reaction in a microfluid, mechanical
mixing and the presence of minor amounts
of solvent are two additional and critical
means to control the overall kinetic behav-
ior of chemical reactions between immis-
cible polymer melts. Mechanical mixing
increases the reaction rate since it generates
an interfacial area and reduces the diffusion
length. Adding a small amount of an inert
solvent may increase the overall reaction
rate greatly due to increased interfacial mix-
ing and diffusion. The formation of a block
or graft copolymer at the interfaces between
the immiscible polymers reduces the inter-
facial tension and increases the miscibility
of the reaction mixture. However, its occu-
pation of the interfaces reduces contact
between the reactive moieties, thus decreas-
ing the overall reactivity.
398 6 Fundamentals of Reactive Extrusion: An Overview
The melt free radical grafting of mono-
mers onto polymer backbones has been
taken as an example to appreciate the kinet-
ic behavior of free radical reactions. In gen-
eral, the kinetic behavior of a melt free rad-
ical grafting is more difficult to evaluate
than a functional reaction due to the low sol-
ubility of peroxides and monomers in mol-
ten polymers, the very short half-life time
and low efficiency of peroxides, the very
high grafting rates, and side reactions (chain
degradation, crosslinking, polymerization
of monomers themselves, coloring, etc.).
These features are seen clearly from the fol-
lowing two examples: the free radical graft-
ing of maleic anhydride (MA) and glycidyl
methacrylate (GMA) onto polypropylene
(PP). The most important result, from the
chemistry viewpoint, is that the presence of
styrene as a comonomer greatly improves
the grafting yield of MA or GMA. More-
over, the mechanism by which styrene con-
tributes to the free radical grafting appears
to be different. In the case of MA, the for-
mation of a charge transfer complex (CTC)
between MA and styrene is important
because it activates the otherwise sluggish
double bond of MA. As for GMA, the dom-
inating mechanism is that styrene reacts
with the very unstable tertiary macroradi-
cals of PP at a much greater rate than GMA,
so forming more stable styryl radicals.
GMA then reacts with these styryl radicals
leading to the grafted GMA moieties. A
kinetic study reveals that the free radical
grafting of GMA onto PP ceases within
2 - 3 min at 200C. For a given concentra-
tion of GMA, its final grafting yield is dic-
tated primarily by the half-life time and the
efficiency of the peroxide used.
A ZSK-30 co-rotating, intermeshing,
twin screw extruder was used to appreciate
the basic features of using a screw extruder
as a chemical reactor. When the screw pro-
file is simple and composed mostly of con-
veying elements, this extruder behaves as a
tubular chemical reactor. When processing
a chemical reaction of a homogeneous mix-
ture whose rate is controlled only by its
intrinsic kinetics, the axial dispersion model
is capable of predicting the conversion upon
knowing the kinetics and the residence time
distribution.
The performance of the ZSK-30 extruder
as a chemical reactor is more difficult to
evaluate quantitatively for the free radical
grafting of monomers onto polymers. But
basically, the chemical aspect of the prob-
lem is similar to what is expected in a batch
mixer. For example, when GMA is to be
grafted onto PP at 200C, the grafting reac-
tion almost ceases somewhat half-way
downstream of the extruder. At a given
GMA concentration, the grafting yield is
directly related to the concentration of the
peroxide. On the other hand, it is the local
residence time distribution in the zone
where primary free radicals exist that con-
trols the grafting process. The effects of
screw speed, throughput, and specific
throughput are exerted mainly through the
residence time distribution. By contrast, the
specific energy is not a proper parameter for
characterizing the performance of the
extruder.
Two important points have been exam-
ined concerning the use of extruders as reac-
tive blenders: an individual sequential oper-
ation such as devolatilization may become
a bottleneck in the whole process; the per-
formance of a reactive blending process
may be determined by the temporal aspect
of mixing, the spatial aspect of mixing, or
both, depending upon the relative impor-
tance of both aspects of mixing.
Devolatilization may be an important
sequential operation in the in situ compati-
bilization of an immiscible polymer blend
by one-step reactive extrusion, because the
grafting yield of a monomer is usually far

below 100%. In other words, there is always
a certain amount of unreacted monomer left.
Thus aside from the desired reaction
between the functionalized polymer and the
functional polymer, the unreacted and pos-
sibly polymerized functional monomer also
reacts with the functional polymer and prob-
ably at a greater rate. Therefore, the residu-
al monomer should be removed efficiently
from the system to reduce those unwanted
reactions. In the case of PP and poly(buty-
lene terephthalate) (PBT), when the func-
tional polymer (PBT) is fed downstream
separately from the inert polymer (PP), and
the residual monomer (GMA) is removed
prior to the feeding point of PBT, the result-
ing blend displays much better mechanical
properties in terms of elongation at break
and impact strength than the one obtained
upon feeding all the components together
and removing the residual monomer down-
stream near the die. Upstream devolatiliza-
tion of residual monomers reduces by-reac-
tions (i.e., reaction between the functional
monomer and the functional polymer,
homo- and/or copolymerization of the resid-
ual monomer), therefore favoring formation
of the desired grafted amphiphilic copoly-
mer at the interface.
The fundamental physics that dictates the
effects of processing parameters (screw
speed and feeding rate) are the residence
time and the residence time distribution
(macromixing) for the in situ compatibiliza-
tion of the PP/PBT blend using GMA as the
functional monomer. This is because it is the
rate and amount of the PP-g-PBT amphi-
philic copolymer that govern the morpho-
logical development of the blend. The spa-
tial mixing per se (micromixing) provided
by a few kneading blocks characteristic of
this type of screw machine is not critical as
it is high enough to promote the chemical
reaction. Moreover, the mechanical mixing
induced morphology development is much
6.4 Conclusions 399
less important than that induced by the
chemistry. The specific energy, i.e., the
energy that is supplied to a unit amount of
material, is not a good measure of the effec-
tiveness of in situ compatibilization by one-
step reactive extrusion.
The residence time distribution (RTD) is
an important parameter for extrusion pro-
cesses as it characterizes the temporal
aspect of mixing. Moreover, when a chem-
ical reaction is occurring during extrusion,
optimization of such a process requires an
in-depth understanding of the RTD function
for each of the sequential, yet more or less
independent, zones. In this chapter, the
applicability of a statistical residence time
distribution theory in screw extruders has
been examined. The fundamental basis of
this statistical residence time distribution
theory is that for a flow passing through a
closed system composed of two closed ele-
ments in series, if fluid particles leaving the
first element have the same probability of
occupying a particular position at the
entrance of the second element, then the
RTDs in these two elements are statistical-
ly independent of each other. Physically this
means that perfect mixing exists at the junc-
tion or the boundary between these two adja-
cent elements so that fluid particles at this
location are totally randomized. Then, the
RTD of the whole system can be calculated
from the RTDs of the individual elements
using a statistical method. The validation
experiments have shown that the intensity
of mixing required for this theory to hold
can be satisfied relatively easily at various
locations in a twin screw extruder. This sta-
tistical theory has also been used to devel-
op a predictive RTD theory for a counter-
rotating, intermeshing, twin screw extruder
with success.
Finally, a few words to end this chapter.
Despite how much we have learnt about
REX so far, there are still numerous prob-
400 6 Fundamentals of Reactive Extrusion: An Overview
lems to be solved or raised. If this chapter
helps readers understand REX better, lead-
ing them to new solutions, and if it brings
criticism and comments to us, then it has
been worthy of our effort in writing it.
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Hu, G.-H. (1990), Ph.D. Thesis, Universite Louis Pas-
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Hu, G.-H. (1994), Short courses on "Reactive Extru-
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Hu, G.-H., Lambla, M. (1994), Polymer 35, 3082.
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Matsubara, Y. (1983), Polym. Eng. Sci. 23, 17.
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7 Network Formation
Karel Dusek

Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Prague,

Czech Republic

List of Symbols and Abbreviations 402

7.1 Introduction 403
7.2 Classification of Crosslinking Reactions 403
7.3 General Features of Network Formation 405
7.4 Kinetics of Network Formation 407
7.4.1 General Features 407
7.4.2 Diffusion Control and Reaction Rates 408
7.5 Description of Network Structure 412
7.5.1 Pre-gel Region 412
7.5.2 Post-gel Region 413
7.5.3 Inhomogeneities in Networks 414
7.6 Outline of Network Formation Theories 415
7.6.1 Factors Determining the Growth of Network Structures 416
7.6.2 Classification of Network Formation Theories 416
7.6.3 Calculation of Structural Parameters 417
7.6.4 Recommendations for Selection of Theory 419
7.7 Examples of the Most Important Crosslinking Reactions 419
7.7.1 Polyester Networks 420
7.7.2 Polyurethane Networks 421
7.7.3 Cured Epoxy Resins 422
7.7.3.1 Epoxy-Amine Networks 422
7.7.3.2 Curing with Polyphenols 424
7.7.3.3 Ionic Mechanisms of Network Build-up 424
7.7.4 Network Obtained by Crosslinking Reactions Involving
Silicon-Containing Groups - Sol-Gel Reactions 425
7.8 Conclusion 426
7.9 References 426

Materials Science and Technology

Copyright WILEY-VCH Verlag GmbH & Co KGaA. All rights reserved.
402 7 Network Formation

List of Symbols and Abbreviations

D diffusion coefficient; coefficient of segmental mobility
Do constant
Ea activation energy
/ functionality
/v fractional free volume
/vg fractional free volume at the gel point
^app apparent rate constant
k rate constant for chemical kinetics controlled reaction
kc rate constant for chemical kinetics controlled reaction
kD rate constant of diffusion-controlled formation of the activated complex
k_v rate constant for diffusion-controlled dissociation of the activated complex
kc XY rate constant for chemical kinetics controlled reaction of molecules characterized
by composition X and Y
rate constant of diffusion into the activated complex of molecules characterized by
composition X and Y
rate constant of diffusion out of the activated complex of molecules characterized
by composition X and Y
Mn number-average molecular weight
Mw weight-average molecular weight
Ngf number of unreacted groups
Pw,Pn degree of polymerization
R gas constant
T temperature
Tg glass transition temperature
t time
vx volume fraction of solvent
xp degree of polymerization

(Xf expansion coefficient of the free volume

% molar conversion of functional groups
T relaxation time

DC dangling chain
EAC elastically active crosslink
EANC elastically active network chain
RT recursive theory
TPB theory of branching processes
 7.2 Classification of Crosslinking Reactions
7.1 Introduction
Crosslinked polymers or polymer net-
works include a wide range of polymeric
materials with specific processing and
materials properties. The crosslinked mate-
rials range from vulcanized elastomers, to
thermosetting materials, and a considerable
number of adhesives and coatings, soft gels,
polymeric sorbents, etc. The advantages of
crosslinked polymers are well known: their
dimensional stability, higher thermal and
chemical resistance, reversible rubber elas-
ticitiy (see Chapter 8 in Volume 12 of this
series), and generally their ability to store
information characterizing their birth and
growth processes.
The fact that some, or practically all con-
stituent units are covalently bonded into an
"infinite" three-dimensional structure is the
main common feature of polymer networks.
The passage from a collection of molecules
of finite size to an infinite network proceeds
through the "gel point" at which the infinite
network structure appears in the system for
the first time. This is another characteristic
feature of network formation. In a wider
sense, physical or temporary polymer net-
works, the network formation and network
structure of which are determined by the
existence of (strong) interactions between
polymer segments, also feature among the
group of polymer networks, and their for-
mation and properties, which exhibit simi-
lar features (Clark and Ross-Murphy, 1987).
Gelatin crosslinked through strong spe-
cific interactions, solutions of long-chain
hydrocarbon crosslinked by formation of
crystallites, or gel-like (concentrated) solu-
tions of higher-molecular-weight polysty-
rene "crosslinked" by relatively weak inter-
actions, can serve as examples. Whether the
bonds are permanent or transient can be
determined by the time-scale of experiment.
However, here we will limit ourselves to the
403
discussion of covalently crosslinked poly-
mer networks.
Common polymer networks are com-
posed mainly of organic constituent units.
Equally interesting are inorganic networks
formed by the sol-gel process (hydrolytic
and condensation reactions of metal alkox-
ides) and corresponding organic-inorganic
hybrids (Hench and West, 1990).
This chapter addresses the conditions of
network formation and the main common
features of the network formation process;
it gives examples of formation of the most
common polymer networks and briefly
deals with the specifics of reaction kinetics.
The characterization of structural changes
during network build-up and of the final net-
work structure will also be discussed in this
chapter.
7.2 Classification
of Crosslinking Reactions
Linear polymers are formed by linking
bifunctional monomers. If one of the reac-
tion components has functionality higher
than two, an infinite structure (network) can
be formed. Functionality higher than two for
at least one of the components is a neces-
sary, but not sufficient, condition for the for-
mation of an infinite network. In order for
an infinite structure to exist, a certain (crit-
ical) number of bonds has to be formed.
Network formation is influenced by sev-
eral factors. The main ones are (1) the mech-
anism and kinetics of the crosslinking reac-
tions, and (2) the functionality of the start-
ing components.
By classifying according to the reaction
mechanism and kinetics, one can distin-
guish three cases.
(a) Bond formation by stepwise reactions.
All unreacted functional groups can take
404 7 Network Formation
part in the reaction irrespective of
whether they are bonded to monomers
or polymeric products. Polycondensa-
tion with elimination of a low-molecu-
lar-weight product or stepwise polyad-
ditions (such as the formation of poly-
urethanes by reactions of isocyanate
with hydroxyl groups, or the curing of
epoxy resins by reaction of amine
groups with epoxy groups) can serve as
examples. In this case, the molecular
weight of the products grows gradually
and the molecular weight distribution
becomes continuously wider,
(b) Initiated bond formation with fast prop-
agation (chain mechanism). Long mul-
tifunctional chains are already formed at
the beginning of the reaction. Free-rad-
ical chain crosslinking (co)polymeriza-
tion of poly vinyl monomers is a typical
example. In the case of a monovinyl
monomer, a polymer of a relatively high
molecular weight, dissolved in the
monomer, can be already formed at the
beginning of the reaction. In the case of
crosslinking polymerization, this grow-
ing "primary" chain carries a large num-
ber of pendant vinyl groups. They also
take part in copolymerization, so that
many intramolecular crosslinks are
formed just at the beginning of polymer-
ization. This special chain mechanism
feature gives rise to the formation of
compact, internally crosslinked struc-
tures.
Sometimes, the distinction between
the two groups is not clear. There are
initiated reactions with stepwise propa-
gation (ionic polymerizations) where
the structure of products resembles more
that of group (a), and (rarely) stepwise
bond formations with a so-called posi-
tive substitution effect where the reac-
tivity of one group is increased by the
reaction of a neighboring group. Then,
the structure growth resembles more that
of group (b).
(c) Control of bond formation by chemical
reactivity or mobility (diffusion) of
reacting groups is another important fac-
tor affecting network build-up. A large
number of systems obey the convention-
al chemical kinetics with Arrhenius tem-
perature dependence of the rate con-
stants). Diffusion control of bond for-
mation can occur for several reasons:
The overall diffusion control of all reac-
tion steps sets in as a result of increas-
ing glass transition temperature due to
bond formation and the probability of
encountering two groups is then con-
trolled by segmental diffusion. Specific
diffusion control is characteristic of fast
reaction steps and depends, for instance,
on translational diffusion of reacting
species. The Trommsdorff (gel) effect
can serve as an example: in free-radical
copolymerization, the termination by
recombination of two free radicals is the
first step to be controlled by translation-
al diffusion of the macroradicals. We
will see later that in free-radical cross-
linking copolymerization, the diffusion
control is very important. Diffusion con-
trol is always important for aggregation
steps in network formation, as in the for-
mation of silica gel networks.
Classification according to functionality
is another possible criterion:
(a) Components with high functionality:
Crosslinking (vulcanization) of primary
chains is a typical example; usually each
monomeric unit can become crosslinked
with another monomeric unit. There-
fore, for high-functionality components
the fraction of crosslinked units neces-
sary to reach the gel point is very low.
In functional copolymers (copolymers
in which monomeric units of one kind
 7.3 General Features of Network Formation
carry functional groups), the functional-
ity can be varied by changing the com-
position as well as the molecular weight.
The chain crosslinking polymerization
may somewhat resemble vulcanization
in that long "primary" chains are already
formed in the beginning,
(b) Components with low functionality
(usually 2, 3, 4, 6): This group includes
usual monomers like di-, tri- and oligo-
isocyanates, diols, triols, tetrols, di-
amines, diepoxides, etc. Telechelic
polymers carrying terminal functional
groups are also included in this catego-
ry.
7.3 General Features
of Network Formation
The courses of various crosslinking reac-
tions have several common features, despite
possible large differences in their network-
formation mechanisms and final network
structures.
In the first stage of the crosslinking reac-
tions, the molecular weights of the system,
as well as the polydispersity, increase. At
the gel point, an "infinite" gel structure
appears in the system for the first time. The
term "infinite" means that the size of the
largest molecule becomes commensurable
with the dimensions of the reaction vessel,
i.e., it spans the vessel walls. A common
reaction vessel can be considered statistical-
ly infinite. When the reaction volume
becomes very small, gelation can be consid-
ered to occur at conversions lower than
those characteristic of a macroscopic ("infi-
nite") system. It can be shown that latex par-
ticles are still too large to exhibit a measur-
able decrease in the gel point conversion.
However, it may be not so, for instance, in
a system with dispersed filler particles
where the interparticle distances are of the
405
order of a few nanometers. The assumption
of infiniteness is definitely not valid for
microgels which are formed in some
systems as intermediate products.
At the gel point, the number-average
molecular weight remains finite, whereas
the weight average and averages derived
from higher moments of the distribution
diverge. Therefore, the polydispersity
MJMn also diverges. Beyond the gel point,
the fraction of material in the infinite struc-
ture - called gel - also increases by linking
finite molecules to it. The assembly of finite
molecules is called "sol" because the finite
molecules are soluble and can be extracted
from the system. The average molecular
weights of the sol decrease with increasing
conversion and the polydispersity of sol
molecules becomes lower. Also, the struc-
ture of the gel changes. More and more
groups bonded to the gel mutually react and
the gel becomes more densely crosslinked.
Therefore, it can better resist mechanical
deformation. The retractive force of a net-
work in rubbery state is proportional to the
number of sequences (strands) between
branch points that are elastically active.
These sequences are called elastically active
network chains (EANC) (see below).
An example of changes in some structu-
ral parameters is given in Fig. 7-1 a, b.
In spite of the qualitative similarity of the
changes of many structural parameters,
there are considerable quantitative differ-
ences in the position of the gel point and in
the shape of the conversion dependences.
For instance, the gel point conversion can
range from 10~3 to near unity. The increase
in Mw before the gel point and the increase
in the gel fraction beyond the gel point can
vary in steepness. The variation in the con-
centration of elastically active network
chains (EANC) can be more complex. In
exceptional cases, the concentration of
EANCs in the gel can pass through a maxi-
406 7 Network Formation

mum; for instance, if the bi- or monofunc-

tional monomers are incorporated into the
gel (due to reactivity reasons) at the end of
eg
the network formation process. Figures
7-1 a, b show the influence of the increasing
or decreasing reactivity of functional groups
if the neighboring groups have reacted.
Formation of a macroscopic network -
macronetwork - can sometimes be more
0.2 0.4 0.6 0.8 1 complex and proceed via formation of
micronetworks. Silica-gel networks are a
typical example (Fig. 7-2). Depending on
initial conditions (pH), either compact
micronetworks or dendritic structures are
formed which are then linked together to
form the macronetworks.
Networks formed by free-radical cross-
linking copolymerization (at higher concen-
trations of the polyfunctional monomer)
represent another example of the macro-
0.8 1.0 network-from-micronetwork mechanism
Fig. 7-1. Changes in the number-average (Pn) and (Dusek, 1982). Firstly, compact, internally
weight-average (Pw) degree of polymerization, gel crosslinked (possibly microgel-like) mole-
fraction (wg) and number of elastically active network cules are formed. These molecules are grad-
chains (EANCs) per monomer unit in the gel (Neg) for
polycondensation of tetrafunctional monomer: (a)
ually linked together by newly forming
positive substitution effect, (b) negative substitution molecules, as shown in Fig. 7-3.
effect; - - gel point conversion. Dependence on con- Also, the structure of networks prepared
version of functional groups. in several stages can be quite complex.
Silica aerogel Cab-O-Sil

Fig. 7-2. Silica-gel micro- and macronet-

works (Klems and Posselt, 1988).

Outer shell
Free radical Inner core
Free
radical
Monochain
Monomers
microgel
Fig. 7-3. Schematic representation of network formation by free-radical copolymerization via microgelation
(Dusek, 1985).
7.4 Kinetics
of Network Formation
7.4.1 General Features
Polymer networks are formed by reac-
tions between functional groups which are
bonded to molecules of various sizes. In
organic chemistry, the rate at which the
respective groups react depends on their
reactivity and concentration. The intensity
of the reaction is given by the rate con-
stant k, the temperature dependence of
which is described by the Arrhenius equa-
tion. The question arises whether the rate
constant depends on the size and structure
of the molecules to which the reacting
groups are bonded. This is an important
issue for polymers, and particularly for
polymer networks where the increase in the
size of the reacting molecules is very large.
When a dependence on the molecule size
7.4 Kinetics of Network Formation 407
Two-chain
microgel
Pre-gel
clusters
appears, it is not due to a change in the elec-
tronic structure of the group but rather to a
change in mobility - diffusion - of the whole
molecule or its segments. General problems
of reactivity and reaction rates have been
discussed by Jenkins and Ledwith (1974),
and Allen and Patrick (1974).
Diffusion control of chemical reactions is
a well-known (but not so well understood)
phenomenon in polymer science. It governs
certain stages of free-radical polymeriza-
tions, ion recombinations, photochemical
and photophysical processes, reactions in
solid polymers, etc. (Horie and Mita, 1989).
Whether a given chemical reaction is con-
trolled by diffusion depends on the relative
rates of the diffusion process (translational
diffusion, or segmental diffusion) and
intrinsic chemical reaction. For instance, in
the case of bond formation, the two respec-
tive groups must diffuse into a "reaction vol-
ume" to form an activated complex and this
408 7 Network Formation
activated complex is either transformed into
a stable bond, or the two groups can diffuse
out of the complex without forming any
bond. If the transition in and out of the acti-
vated complex is much more frequent than
the transition into the stable bond, the reac-
tion is controlled by chemical kinetics.
When the frequencies of these transitions
are comparable, or the transition into the
stable complex is faster, the reaction is con-
trolled by diffusion. The diffusion control
can be specific or non-specific (overall dif-
fusion control).
To what extent are polymerization and
network-formation reactions diffusion-con-
trolled? We will first consider the case in
which the segmental rate control is absent
(weak), i.e., at temperatures well above the
glass transition temperature.
There is abundant experimental evidence
to show that the majority of stepwise linear
polymerizations obey conventional chemi-
cal reaction kinetics. The rate constants are
independent of the degree of polymerization
and their temperature dependence obeys
Arrhenius dependence (Flory, 1953; Jenkins
and Ledwith, 1974). The same is true for
stepwise network build-up until high cross-
linkitfg densities are reached and the reac-
tion is slowed down (Rozenberg, 1985;
Dusek, 1986). The passage through the gel
point where the macroscopic flow ceases
does not have any marked influence on the
reaction rate.
On the contrary, some steps in chain poly-
merizations are known to be diffusion-con-
trolled. Best known is the Trommsdorff, or
gel effect in free-radical copolymerizations
when the termination by recombination of
macroradicals becomes dependent on their
degree of polymerization. In concentrated
systems (at high conversions), even the
propagation rate is diffusion-controlled.
The specific diffusion control is much more
important for crosslinking free-radical
polymerizations because the gel effect
already sets in in the vicinity of the gel point.
A schematic representation of structural
changes during chain crosslinking copol-
ymerization is shown in Fig. 7-3. The pre-
gel conversion region can be very narrow.
Moreover, this type of network build-up is
known to proceed inhomogeneously and not
only the specific, but also the overall (seg-
mental) diffusion control is operative
(Kloosterboer, 1988).
Overall (segmental) diffusion control is
characteristic of all systems in and below the
glass transition region where the segmental
motion is considerably slowed down. It is
also characteristic of densely crosslinked
systems. One should not forget that the onset
of the segmental diffusion control is taken
relative to the bond formation rate, and that
free-radical propagation is by several orders
of magnitude faster than step reactions.
The overall diffusion control is typical of
thermosets where the glass transition tem-
perature increases during network forma-
tion by several tens of kelvin. The onset of
this diffusion control results in a drastic
decrease in curing rate and eventually in an
undercured system.
An example of curing a diepoxide with a
diamine (Dusek and Havlicek, 1993) is
given in Figs. 7-4 and 7-5. The increase in
Tg with conversion slows down the reaction
rate until the curing is practically stopped.
Several other experimental and theoretical
papers deal with this problem (Horie et al.,
1968; Huguenin and Klein, 1985; Rohr and
Klein, 1988; Rohr and Klein, 1990; Matsu-
oka et al., 1989; Sanford and McCollough,
1990; Wisanrakkit and Gillham, 1990).
7.4.2 Diffusion Control
and Reaction Rates
There have been many attempts to corre-
late quantitatively the diffusivities of mole-
 7.4 Kinetics of Network Formation 409

cules or segments with reaction rates. The internal structure of the reactants (e.g., com-
problem is outlined below. position and symmetry of the molecule). In
According to the theory of absolute reac- the general case,
tion rates, the formation of a stable product
proceeds via formation of an activated com- [X)A-B(Y)Y
plex. Let us consider formation of bonds
A - B between reactants A(X) and B(F)
where the vectors X and Y characterize the -(X)A-B(Y) (7-1)
where []* is the activated complex, fcD and
k_D are rate constants for diffusion-con-
I 1 1 1 trolled formation and dissociation of the
400 -
activated complex, and kc is the rate con-
Tg,K stant for the transformation of the activated
complex into a stable product. These rate
constants generally depend on the vectors X
and Y. The reaction scheme (7-1) is
350 described by an infinite set of differential
equations which can be regarded as gener-
i alized Smoluchowski (1918) coagulation
equations, and the rate constants represent
the kernels of these equations. The transfor-
/
300 - mation rates for the molecules are propor-
tional to the concentrations of the reacting
molecules, and the kernels are a function of
the number and kind of unreacted function-
al groups in the molecule. Under the condi-
tions of the diffusion control (translational
or segmental), kD,XY, k_r>XY<kCXY, the dif-
1 1 1 1
0.2 0.4 0.6 0.8 g fusion rate into the complex becomes the
rate-controlling step. If the encounter of the
Fig. 7-4. Dependence of Tg of the system diglycidyl
ether of bisphenol A (DGEBA) - 1,3-diaminopropane
reacting groups is controlled by translation-
(DAP) on conversion of epoxy groups % (Dusek, and al diffusion by reptation, the collision rate
Havlicek, 1993). is proportional to (D(X) + D(Y)) and D(X)

Fig. 7-5. Dependence of conversion of

epoxy groups on time for various curing
temperatures. The same system as in
Fig. 7-4.
50 100 150 t, min
410 7 Network Formation
is roughly proportional to x p 2 , where xp is
the degree of polymerization of the mole-
cule.
In the case of chemical kinetics control,
the kernels are proportional to the numbers
(monomolecular reaction), or products of
numbers (bimolecular reactions) of the
respective functional groups. A different
functional dependence can account for dif-
fusion control, steric hindrances, etc., (Hen-
dries et al., 1983; Dusek and Somvarsky,
1992). The solution to the general Smolu-
chowski equations can be obtained by
Monte Carlo simulation (Somvarsky and
Dusek, 1994a, b).
Specific diffusion control is characteris-
tic of dilute solutions where there are few
overlaps and weak interactions affecting
diffusion of individual molecules. In con-
centrated solutions and melts, the diffusion
of reactive groups into the activated com-
plex becomes rather nonspecific and con-
trolled by segmental mobility irrespective
of the sizes of the molecules (parts of the
network structure) to which they belong.
Thus, the characteristic situation for over-
all diffusion control is a dependence of the
rate constants not on particular values of the
components of vectors X and Y but only on
their average values, for instance on the
average molecular weight. Then, Eq. (7-1)
can be rewritten as follows:
o-A + B - o =^ [ o - A - B - o ] *
(7-2)
where the structure of - o need not be spec-
ified. The infinite number of equations
having an infinite number of rate constants
(7-1) then degenerate to Eq. (7-2).
The overall diffusion control is governed
by segmental mobility, which is associated
with the glass transition. However, one
should realize that:
(a) Not all changes of motion in the poly-
mer are associated with the main transi-
tions; there are secondary transitions
determined by smaller scale mobilities.
(b) Small species (monomers) can still
move deeply below Tg. For example,
Kloosterboer (1988) observed that the
rate of monomer consumption in cross-
linked polyacrylates in the glassy state
obeyed the Williams-Watts function,
i.e., it was proportional to exp(-/r)/3),
where /3<1, somewhere 100 K below Tg.
(c) Some reactions (even on the polymer
backbone) do not require large spatial
rearrangements, so that they can proceed
deep in the glassy state (e.g., cis-trans
isomerizations, splitting of bonds and
recombination of the respective free rad-
icals) (Eisenbach 1980).
Within these limitations, one can corre-
late the reaction rate with segmental mobil-
ity in the glass transition region using the
free-volume theory or an alternative theory,
e.g., that of Adam and Gibbs (1965). Within
the free-volume concept, the diffusion-con-
trolled reaction rate can then be taken pro-
portional to exp [(Tc-Tg)/(TC-Tg + c2)],
where Tc is the temperature of cure and c2
is the constant in the Williams-Landell-
Ferry (WLF) equation. If Rabinowitch's
(1937) assumption about the steady state
concentration of the activated complex
d [AB*]/d = 0 is used, one gets from
Eq. (7-2)
d [AB]/dt=[kckD/(kc +
= * app [A][B] (7-3)
which gives the apparent rate constants of a
bimolecular reaction in terms of kc, kD and
(Vkc)(k_D/kD) (7-4)
or
(7-5)
 7.4 Kinetics of Network Formation 411

It can be seen that k.dpp = k'c for kD>k'c
and kapp = kD for kD<k'c. For slow reactions
in mobile systems, the condition kD>k'c is
usually fulfilled, but for fast reaction and
low mobilities kD<k'c is valid.
Since kD depends on local mobility and
the mobility, in turn, depends on structural
changes, and the structural changes depend
on conversion, fcapp is no longer a constant
but is conversion dependent under the con-
ditions of diffusion control.
The temperature dependence of k'c is
given by the Arrhenius equation
kQ = kCQQxp(-EJRTc) (7-6)
where Ea is the activation energy of the
chemical reaction. The "constant"fcDcan be
related to the coefficient of segmental
mobility, D, through one of the theories of
glass transition
k k D(T E v ) (7-7)
where kD0 is a constant, is degree of con-
version of functional groups, and vx is the
volume fraction of the possibly present dil-
uent. The free-volume theories (e.g., Turn-
bull and Cohen, 1961) offer
where
An example comparing the predicted and
experimental rate constants for curing
diglycidyl ether of bisphenol A with 1,3-
propanediamine (Dusek and Havlicek,
1993) is shown in Fig. 7-6.
The sharp fall in the rate constant starting
in the vicinity of Tg predicted by the theory
is also found in experiments.
In addition to segmental mobilities asso-
ciated with the glass transition, the reaction
kinetics can be affected by two other fac-
tors:
(a) sub-r g mobilities already discussed in
this section,
(b) physical ageing which accompanies cur-
ing and becomes considerable over long
curing times (final curing stages in
undercured systems). Volume relaxation
has a dual effect on the reaction rate: it
assists the reaction by a density increase,
but makes the glass denser and its inter-
nal motion slower.
1 I I 1
log k
T
cure
O |9
70 c O ^ 3 <j vD
60 QLl \
-1 - > *
40 u*-

and Do and bD are constants,/ v and/ vg are

fractional free volumes at temperatures T
C

X
-2 -
and 7 g , respectively, ccf is the thermal expan-
sion coefficient of the free volume. The
denominator fv in Eq. (7-8) has the same 9
form as in the WLF equation and determines o
i
the fall of mobility with increasing Tg, i.e., -3 -
with conversion.
1 1 i
To predict the dependence of the rate 0.2 0.4 0.6 0.8 ^
constant on conversion, it is necessary to
Fig. 7-6. Comparison of the rate constant k as a func-
determine the conversion dependence of Tg tion of conversion of epoxy groups for curing of
and the kinetic law governing the curing DGEPA with DAP calculated and measured. The same
reaction in the absence of diffusion control. system as in Fig. 7-4.
412 7 Network Formation
Of great importantance is the amount of
free volume locked in by vitrification
during the course of the curing. The locked-
in free volume is the higher the faster the
reaction and the lower the vitrification c
onversion which determines the potential
reaction contraction. The conversion depen-
dence of the rate constant at various temper-
atures can vary due to the interplay of
locking-in free volume and volume relaxa-
tion.
7.5 Description
of Network Structure
In this section, the topological structure
which develops during the crosslinking pro-
cess will be characterized. In contrast to lin-
ear polymers, the description of branched
and crosslinked structures needs more infor-
mation. The topological structure is simpler
than the spatial structure; a given topologi-
cal structure can assume many forms in
space.
The topological structure of molecules
and of the network composed of units which
are interconnected by bonds can formally be
described as "adjacency" or "incidence"
matrices. Also, the bonds can be sequential-
ly numbered according to the chronological
order in which they were formed. In this
way, structures determined by history
effects of any possible complexity can be
described. However, the laws of network
formation are usually relatively simple and,
also, experimental characterization meth-
ods cannot differentiate between fine details
of structures.
7.5.1 Pre-gel Region
The distribution of molecules before the
gel point can be characterized by their
degree of polymerization or molecular
weight, and by their symmetry. The molec-
ular weight distribution can be obtained by
chromatographic separation methods, and
by the molecular weight averages obtained
by various physical methods such as
osmometry, light scattering, and ultracen-
trifugation.
Molecules of the same molecular weight
can have different shapes which differ in
the radii of gyration. For instance, a 17-mer
of a tetrafunctional monomer (without
cycles) can be symmetric, composed of 17
(=1+4+4x3) monomeric units with four
reacted functional groups and 36 (4x3x3)
end units with one reacted functional group;
or linear, composed of 15 units with two
reacted groups and two end units with one
reacted group (Fig. 7-7).
In general, symmetry or asymmetry of the
structures are given by the distribution of
the number of bonds issuing from the units.
Any tree-like structure composed of N units
(of functionality j) is connected by AM
bonds; N-\ bonds correspond to 2{N-\)
reacted functional groups out of TV/* groups.
Therefore, the number of unreacted groups,
Ngf is given by the relation
Ngf=Nf-2(N-l) = N(f-2) + 2 (7-9)
For a/-functional monomer, a fully sym-
metric tree-like structure can be construct-
ed from N units issuing Nf bonds and N(f-2)
+ 2 units with one reacted and/-I unreact-
ed groups. Alternatively, when N units with
two reacted groups and/-2 unreacted ones
form a linear chain terminated by two units
with one reacted and/-I unreacted groups.
The number of branch points in the mole-
cule in the former case is N9 in the latter zero.
So, increasing polydispersity of the distri-
bution of building units in a molecule with
respect to the number of bonds they are
engaged in means increasing sphericity of
the molecule.

Wiv
7.5.2. Post-gel Region
Beyond the gel point, the molecules in the
sol can be characterized in the same way as
before the gel point. The infinite molecule
- the gel - can be characterized by various
substructures: elastically active junctions
(crosslinks), elastically active chains, and
dangling chains (Fig. 7-8).
These substructures differ in the connec-
tivity of units - characterized by the num-
ber of bonds with infinite continuation. A
bond with infinite continuation is defined as
one through which, looking out of the unit,
one can reach the (infinitely distant) surface
of the sample. For a tree-like structure, the
classification is simple.
Elastically active crosslinks (EACs,
structure A in Fig. 7-8) are represented by
units issuing three or more bonds with infi-
nite continuation.
Elastically active (network) chains
(EANCs, structure B in Fig. 7-8) are com-
posed of units that have two and only two
bonds with infinite continuation.
Dangling chains (DCs) are composed of
units that issue only one bond with infinite
continuation. They are bonded either to an
EANC (structure C in Fig. 7-8), or EAC
(structure D in Fig. 7-8).
7.5 Description of Network Structure 413
Fig. 7-7. Schematic representation
of symmetric (top) and asymmet-
ric structures of the same degree of
polymerization composed of tetra-
functional monomer units.
Fig. 7-8. Part of a system crosslinked beyond the gel
point. A: elastically active crosslinks; B: units in elas-
tically active network chains (EANCs); C, D: units in
dangling chains; E: units in sol; > bonds with infi-
nite continuation.
Further from the gel point, the gel always
contains a nonnegligible number of cycles
(circuits). Some of these are large and involve
several elastically active crosslinks and
chains (circuits) (Fig. 7-9 a). Their formation
is considered uncorrelated with the proper-
ties of the connecting chains. However, some
of them can be smaller (Fig. 7-9 b), and their
formation is definitely determined by the
properties of the connecting chains. Gener-
ally, this is a very complicated problem
described in fully by the adjacency matrix.
However, in order to be still able to apply
the above criteria on classification of units
414 7 Network Formation

gation; spatial inhomogeneity during cross-

A B
Fig. 7-9. Example of cyclic structures in a network
(gel); (a) circuit with elastically active crosslinks and
network chains, (b) elastically inactive crosslink and
elastically inactive loop.
with respect to the number of their bonds
with infinite continuation, a redefinition of
"infinite continuation" is necessary. The
units will be distinguished according to the
number of bonds with independent contin-
uations to infinity. However, beyond the gel
point, where closed circuits exist, some of
the paths must be dependent. Examples are
shown in Fig. 7-9. In Fig. 7-9 a, the cyclic
path passes through many active branch
points before it comes back. The given bond
will have continuation to infinity irrespec-
tive of whether such a circuit exists or not.
This circuit closing does not affect, in any
practical sense, the probability of the bond
continuation from a given unit to infinity.
Small cycles cause bonds with infinite con-
tinuation to be dependent. Examples are
given'in Fig. 7-9. Structure B is just a dan-
linking enhances topological heterogeneity.
The inhomogeneity can eventually result in
phase separation and induce formations of
interphase boundaries. In this section, only
those topological inhomogeneities in multi-
component systems that arise from statisti-
cal arrangements of units will be discussed.
These arrangements are affected by differ-
ences in reactivities and by special reaction
mechanisms (Dusek and Somvarsky, 1996).
Figure 7-10 shows a part of the network
formed in a three-component system where,
for instance, two components having the
same groups but differing in some property
(e.g., molecular weight) are crosslinked
with a common substance. Such a case cor-
responds, for instance, to a polyurethane
network formed from a long chain diol (soft
unit) and a low-molecular-weight triol (hard
unit) crosslinked with a diisocyanate (hard
unit) (Dusek, 1989), where clusters of
"hard" triol-diisocyanate units exist within
the soft diol-diisocyanate "matrix".
The size of these clusters increases with
increasing hard-unit content and conver-
Macrodiol (soft)
Y Triol (hard)

gling cycle which is elastically inactive. o-o Diisocyanate (hard)

Also, partly double-chained EANCs can
exist. The mechanical behavior of these
more complex structures can be quite com-
plicated.

7.5.3 Inhomogeneities in Networks

Hard cluster
Polymer networks can be topologically
and spatially inhomogeneous. However,
spatial and topological inhomogeneity can
be interdependent: topological inhomogene- Fig. 7-10. Schematic representation of a hard cluster
ity may cause physical association or segre- formed in the system macrodiol-diisocyanate-triol.
 7.6 Outline of Network Formation Theories
sion. Cluster formation is also enhanced by
higher relative reactivity of OH groups in
the triol with respect to that of those in the
diol. Some calculated dependences are
shown in Fig. 7-11 (Dusek and Ilavsky,
1979).
In certain cases, the structure of hard clus-
ters can become continuous. This corre-
sponds to a percolation threshold of hard
clusters within the soft matrix. This perco-
lation threshold is reached after the macro-
scopic gelation in which the diol bridges
also take part. For the random system shown
in Fig. 7-11, the percolation threshold is just
reached at 100% conversion.
Microgel-like types of inhomogeneities
are typical of chain crosslinking copolym-
erizations as mentioned in Sec. 7.2, Fig.
7-3. In this case, the chain mechanism is
mainly responsible for inhomogeneous net-
work formation.
7.6 Outline of Network
Formation Theories
The network formation theories describe
development of branched and crosslinked
415
Fig. 7-11. Calculated average degrees
of polymerization P of hard clusters in
the gel for a stoichiometric system
macrodiol - diisocyanate - triol.
Stoichiometric system, no substitution
effect, initial ratio of OH groups in
macrodiol and triol is 1. One-stage
and two-stage processes. Subscripts:
s - in sol, g - in gel; % conversion.
structures and substructures as a function of
the relative numbers of formed bonds dif-
fering in type. These relative numbers are
related to conversions of the respective
functional groups.
The input information needed to apply the
theories includes: initial composition of the
system in terms of type and functionality of
the components, and mechanism and kinet-
ics of the bond formation or bond scission
reactions. The mechanism and kinetics
information determines the time (conver-
sion) sequences in which bonds between
component units are formed.
Reaction time or conversion(s) of func-
tional groups are the independent variables.
The kinetics information includes the histo-
ry of network formation (in one or several
stages).
The output information includes:
- molecular-weight and compositional dis-
tributions, and averages of the branched
polymers before the gel point,
- averages of radii or gyration of these
molecules, or other parameters character-
izing the symmetry of molecules,
- the gel point time or gel point (critical)
conversion,
416 7 Network Formation
- fractions of sol and gel,
- molecular-weight averages of the sol,
- information about the gel structure in
terms of dangling chains, elastically
active network chains, elastically active
crosslinks, topological inhomogeneities,
etc.
All this information is important for
understanding and predicting various pro-
cessing and materials properties, like the
development of viscosity and viscoelastic
properties, equilibrium elasticity, swelling,
etc.
7.6.1 Factors Determining the Growth
of Network Structures
Of the factors affecting structure devel-
opment in polymer network, the following
are the most important (Dusek and Som-
varsky, 1993):
(a) short-range "chemical" effects - rules of
making (or breaking) bonds between
constituent units determined by reaction
paths (mechanism) and their kinetics,
(b) long-range connectivity (time, history)
correlations by which the structure
"remembers" the sequential orders of
units and bonds in the structure devel-
oped in time,
(c) long-range spatial correlations affecting
the reaction probabilities through
cyclization, unequal accessibility of
groups bonded to molecules of different
size and symmetry (excluded-volume
effect), or diffusion control of certain
reaction steps.
7.6.2 Classification of Network
Formation Theories
The existing network formation theories
can be grouped into three categories:
(1) Statistical theories, by which the struc-
tures are built up from monomeric units
(or other fragments) differing in reaction
states. The reaction state is described by
the number of reacted functional groups
and types of bond they are engaged in.
The connections between such units
occur at random, but differences
between bond types are respected. The
generation of structures occurs at any
extent of reaction, so that any correla-
tion with the history of bond sequences
formation is lost. These theories are
mean-field, so that time and space cor-
relations can be taken into account only
by some (perturbation) approximations.
The Flory-Stockmayer theory, the
branching processes (cascade) theory, or
the "recursive" theory of Miller and
Macosko are included in this category.
(2) Kinetic (coagulation) theories, in which
the existing structure of reacting mole-
cules is kept intact. The structure growth
is described by a (infinite) set of diffe-
rential equations for the time evolution
of numbers (concentrations) of distin-
guishable molecules. The rate constants
for reactions of molecules depend on the
number and reactivities of their func-
tional groups. Physical effects on the
growth rates of molecules can be incor-
porated. The approach is mean-field, but
time correlations are taken into account
exactly. Space correlations can be dealt
with as an approximation, but the rate
constants for reactions between func-
tional groups in a molecule, or between
a pair of molecules, can be made depen-
dent on their structure and mobility. In
the case of incorporation of physical
effects, the kinetic equations are of the
type of generalized Smoluchowski
coagulation equations.
(3) Simulation in space is performed in
finite systems by computer. The most
 7.6 Outline of Network Formation Theories
frequent simulations are based on lattice
percolations which can be either random
(Stauffer et al., 1981) or kinetic (initiat-
ed) (Boots et al., 1985). Off-lattice sim-
ulation (Leung and Eichinger, 1984)
have some advantages. The simulations
in space are non-mean-field and can take
into account time and space correlations.
The classic percolation methods suffer
from the rigidity of the lattice corre-
sponding to a complete diffusion control
of the network-forming reaction. The
diffusivity of the molecules can be taken
into account by different statistical
weightings for reactions of molecules of
different sizes and at different distances
(see e.g., Gupta et al., 1991).
For simulating aggregation, there are var-
ious models of diffusion-controlled pro-
cesses (ballistic, diffusion-limited aggrega-
tion, and other models) (Family and Lan-
dau, 1984). Network-formation simulations
have not yet advanced for enough as to be
able to take into account the effect of phys-
ical interactions on the transformation rates
of molecules during network formation.
7.6.3 Calculation of Structural
Parameters
Network-formation theories differ not
only in their rigor of treatment of long-range
correlations but also in their ability to cal-
culate various structural parameters when
applied to real systems. The theories of
group (1) are easy and require minimum
information; the possibility of characteriz-
ing details of the infinite gel structure (elas-
tically active network chains, pendant
chains and their distributions, elastically
active crosslinks, lengths of various
sequences having a certain property, etc.) is
their great advantage for finding and pre-
dicting structure-property correlations.
417
The solution using the kinetic (coagula-
tion) theory is less simple but manageable.
Only in the simplest cases, does the infinite
set of differential equations of chemical
kinetics have an analytical solution. Most
frequently, these equations are solved by the
moment method, in which differential equa-
tions for the time evolution of the moments
of the distributions (degrees of polymeriza-
tion, molecular weights, composition, etc.)
can be derived. The values of the moments
of distributions are calculated numerically
(Kuchanov and Povolotskaya, 1982; Galina
and Szustalewicz, 1990). This approach has
also been used for modeling free-radical
copolymerizations (Tobita and Hamielec,
1988, 1989; Mikos et al., 1986).
In more complex cases, a Monte-Carlo
simulation of the process as described by the
differential equations can be used (e.g.,
Mikes and Dusek, 1982; Somvarsky and
Dusek, 1994 a, b). The random-number gen-
erator selects a given pair of molecules for
reaction; the probability of finding a mole-
cule is weighted by its "reaction ability",
which is given by the numbers and reactiv-
ities of the unreacted functional groups of
the given molecule and its reaction partner.
As the size of the system increases, the dif-
ference between the molecular weight of the
largest and the second-largest molecules
rapidly increases when a certain conversion
is surpassed, and diverges when the system
size approaches infinity at the gel point. The
mass fraction of the largest molecule
becomes equal to the gel fraction.
The difference between the statistical and
kinetic network-formation theories are
schematically shown in Figs. 7-12 a, b.
If the branched and crosslinked structures
are built up from monomeric units, the input
information is the distribution of monomer-
ic units in different reaction states. The reac-
tion state of a monomeric unit is character-
ized by the number of reacted bonds and type
418 7 Network Formation
(a)
Fig. 7-13. Four reaction states of a trifunctional
monomeric unit; unreacted (o) and reacted () func-
tional groups.
of bonds the reacted groups are engaged in.
In the simple case shown in Fig. 7-10 a, there
is only one type of groups and bonds: the tri-
functional monomer unit exists in four reac-
tion states with zero, one, two, and three
reacted functional groups (Fig. 7-13). The
number fractions (probabilities of finding) of
these units, p0, pu p2, and p3 are the input
information for the application of the theory.
In polycomponent systems, distinguish-
ing between various types of units and bonds
makes it possible, for example, to calculate
the distribution of hard clusters (Sec. 7.5.3).
This can be achieved by taking into account
only bonds connecting hard units.
The distribution of units in different reac-
tion states in the whole system determines the
distribution of units already bonded to other
units with respect to the number of addition-
Fig. 7-12. Schematic representation
of network build-up; (a) from mono-
meric units in different reaction states
by the statistical theories, (b) by kinet-
ic theories.
al bonds. This distribution expresses the abil-
ity of the structure to propagate along bond
sequences and determines the molecular
weight distribution and condition for the gel
point. Beyond the gel point, this distribution
also determines the so-called extinction prob-
ability, i.e., the probability that a certain bond
starts a sequence which will become extinct,
i.e., one without infinite continuation.
In the case of kinetic theories, the build-
up rate is a function of the concentrations of
the two reacting molecules, the number and
type of unreacted functional groups in each
of them, and their reactivities.
There are a number of approximate meth-
ods enalbing us to take into consideration
the effects of long-range correlations (see,
e.g., Dusek and Somvarsky, 1993).
Treatment of specific systems and the
corresponding mathematical relation for
calculating structural parameters can be
found in various publications, e.g. the
review of percolation treatment by Stauffer
et al. (1981), or two monograph chapters
dealing with the theory of network build-up
in the case of polyurethane and epoxy res-
ins (Dusek, 1986; Dusek, 1989).
 7.7 Examples of the Most Important Crosslinking Reactions
7.6.4 Recommendations for Selection
of Theory
Anyone wanting to use a theory to
describe network formation in a given
system and develop a predictive theoretical
approach is often faced with the problem of
which type of theory to start with. The
answer is not simple; it depends, firstly, on
how much and in what sense the real system
deviates from the ideal one (without time
and space correlations); secondly, whether
the entire conversion region should be cov-
ered, or whether one is interested in the
detailed description of the critical region;
and, thirdly, what hardware is available.
Many systems of practical importance
can be described with satisfactory accuracy
by the modern versions of statistical theo-
ries - either the theory of branching process-
es (TBP) (cascade), or the recursive theory
(RT). They are exact in the absence of long-
range time and space correlations, and both
groups of theories give identical results.
TBP uses the generating-function formal-
ism to describe distributions, which is a def-
inite advantage if more complex cases
(initial distributions, complex reaction
mechanism, combination of kinetic theories
with statistical theories) are treated.
Systems formed by stepwise reactions
where cyclization is weak, can be treated
very well by these theories. To treat weak
cyclization, perturbation methods have
been developed. The description of the gel
structure in terms of the various elements
discussed in Sec. 7.5.2 is easy.
If long-range time correlations are impor-
tant, statistical approaches cannot be used.
This is often the case with complex reaction
mechanisms, particularly for those based on
initiated structure growth (chain mecha-
nism). Living polymerization-type build-up
or multistage network formation can serve
as examples. Although more complex, the
419
formulation of the kinetic equations is not
difficult and, in the absence of space corre-
lations, their solution using the moments
method is feasible. Limited information on
the post-gel state is a disadvantage of the
kinetic treatment at present.
Long-range space correlations (cycliza-
tion, steric and thermodynamic excluded-
volume effects, diffusion control) and their
combination with long-range time correla-
tions, represent the most difficult problem.
Spatial simulations (percolation tech-
niques) or kinetic differential equations
based on generalized Smoluchowski equa-
tions, combined with Monte-Carlo solu-
tions, are the current approaches. This group
of theories is being developed with the aim
of finding efficient ways to model various
types of space correlations as well as simu-
lation methods.
7.7 Examples
of the Most Important
Crosslinking Reactions
Almost all reactions between groups pro-
ducing bonds can be used for the prepara-
tion of polymer networks. The condition is
that some of the constituent units must par-
ticipate in three or more bonds by which
they are linked to neighboring units. This
condition can be fulfilled by the presence of
units carrying more than two functional
groups. Alternatively, branching can also be
produced if the reaction between two groups
yields a new reactive group (etherification
following epoxy-amine reaction, or alloph-
anate formation following isocyanate -
hydroxyl reaction).
If is not the aim of this chapter to review
chemical ways of synthesizing covalent
polymer networks, but simply to show some
typical examples of various build-up
420 7 Network Formation
mechanisms and their implications for the
choice of theoretical strategies used for
modeling network formation. The theoreti-
cal approaches to specific problems are not
discussed here in any detail, but references
are made to the relevant publications. Due
to the limited size of this chapter, only a few
examples will be briefly discussed.
7.7.1 Polyester Networks
Conventional methods of making ester
bonds are reactions of carboxyl groups with
hydroxyl or epoxy groups, and the reaction
of hydroxyl or epoxy groups with a cyclic
(or polymeric) anhydride
-COOH + H O - ^ - C O O - + H2O
-COOH + - C H - C H 2 > -COOCH 2 -CH(OH)-
-OH + COZCO -OCOZCOOH
V
-CH-CH 2 + COZCO -OCHCHoOCOZCO-
V V
The condensation reaction (7-10) is not
suitable for making bulk objects due to the
elimination of water. It has been employed
in the preparation of branched saturated
functional polyester precursors earring OH
or COOH groups. A triol or tetrol (e.g., tri-
methylolpropane or pentaerythritol) are
added as branching agents. Alternatively,
diols, unsaturated cyclic anhydrides, and
saturated diacids and monoacids are core-
R'COOCH^CHR 2
\ I
O OH
Rl COOCHo - CHR 2 + HOCH 9 - CHR 2
acted to yield unsaturated polyesters where
the double bonds are functional groups
active in crosslinking by copolymerization
with another monomer.
Epoxide-carboxyl reactions produce
hydroxyester groups, whereas cyclic an-
hydride-epoxide reactions only produce
diester groups. The epoxy group appears to
be monofunctional in its reaction with a
carboxyl group, but bifunctional when it
reacts with the anhydride. Therefore, a die-
poxide and a dicarboxylic acid give primar-
ily a linear poly(hydroxyester), whereas
from a diepoxide and a cyclic anhydride a
crosslinked product is formed (Dusek,
1986).
(7-10)
(7-11)
(7-12)
(7-13)
Since these reactions can be considered
stepwise, statistical theories can be used. Of
great importance is the tendency of the
hydroxyester group towards transesterifica-
tion, which has a considerable effect on net-
work build-up. For example, equimolar
quantities of diepoxide and a dicarboxylic
acid initially produce a linear hydroxypol-
yester. As a result of transesterification, a
diester and a glycol are formed
(7-14)
1
OCOR OH
 7.7 Examples of the Most Important Crosslinking Reactions 421

Transesterification causes a redistribu- reactions of polyisocyanate compounds.

tion of the number of bonds by which the
epoxy unit is bonded to the carboxyl unit.
In hydroxyester, the epoxy unit is mono-
functional but, as a result of transesterifica-
tion, is converted into equimolar quantities
of bifunctional diester and non-functional
glycol. In the case of a dicarboxylic acid and
diepoxide, the change in functionality / of
the diepoxide to yield a distribution / = 0 to
4, causes gelation which has been proved
theoretically and experimentally (Dusek
and Matejka, 1984).
In the diepoxide-cyclic anhydride reac-
tions, the diepoxide unit is tetrafunctional
and the anhydride unit difunctional.
7.7.2 Polyurethane Networks
The group of polyurethane networks
includes a variety of systems obtained by
The urethane, urea, and isocyanurate groups
are the most frequent types of stable bonds
used in network formation; allophanates
and biurets are less stable. Since the isocya-
nate group is very reactive, a variety of prod-
ucts can be formed as shown in Fig. 7-14
(Saunders and Frisch, 1962; Reegen and
Frisch 1971).
Simple polyurethane networks with units
connected by urethane bonds can be pre-
pared from diisocyanates and polyols
(triols, tetrols) or from diols and polyisocya-
nates. These networks have also been wide-
ly studied as model networks for the verifi-
cation of network formation and rubber
elasticity theories (Dusek, 1989; Ilavsky
etal., 1993;Stepto, 1982).
The reaction of diisocyanates with poly-
ether or polyester triols and tetrols in the
easiest way of preparing these networks.
Tris(4-isocyanatophenyl) thiophosphate (I)

-N N-

-NCO
(uretedione)
(isocyanate)

H0-

/CO
-NH2 NHCOO -N N-
(amine) (urethane) CO CO

I + OCN-
tl OCN-
(isocyanurate)
-NHCONH- NCOO
(urea)
CONH
+ OCN- (allophanate)

-NCONH- Fig. 7-14. Most important

reaction paths of isocyanate
CONH- groups in polyurethane for-
(biuret) mation.
422 7 Network Formation
can most conveniently be used as a source
of polyisocyanate branch points.
NCO
S=P NCO
NCO
In preparing these simple networks, one
should avoid an excess of isocyanate
groups. If the NCO groups are in excess and/
or traces of water are present, other "side"
reactions set in as shown in Fig. 7-14.
Somewhat more complicated are three-
component poly urethane networks prepared
from a diisocyanate, a polyether or poly-
ester diol, and a low-molecular-weight
polyol (e.g., trimethylolpropane or penta-
erythritol). The structure of these networks
can be more complicated because of clus-
ters of hard units (Sec. 7.5.3 and Fig. 7-10).
The size of the clusters depends on wheth-
er the network is prepared in one or two stag-
es. If preparation occurs in one stage, all
hydroxyl groups react from the very begin-
ing and, if the reactivity of OH groups of the
polyol is higher than that of the macrodiol,
hard cluster formation is enhanced. In a two-
stage process, the macrodiol and diisocya-
nate react in the first stage. A distribution of
NCO terminated oligourethanes is formed
and part of the free diisocyanate remains in
the system. In the second stage, the NCO
groups react with the polyol and the free di-
isocyanate contributes to cluster formation.
When isocyanate groups are in excess,
more types of bonds are formed, as shown
in Fig. 7-14. The bifunctional groups
already formed (urethane, urea) can react
with isocyanate groups, and trifunctional
allophanate and biuret, as well as a stable
trifunctional triomer (isocyanurate), can be
formed (Saunders and Frisch, 1962; Reegen
and Frisch 1971). As a result of this addi-
tional crosslinking, even a system prepared
from a diisocyanate and a diol can gel and
form a network. If the composition is
described in terms of the respective frag-
ments (urethane, urea, allophanate, biuret,
uretedione, isocyanurate), the network for-
mation can be described quantitatively
(Dusek et al., 1990).
Cyclotrimerization of urethane end-
capped oligomers (polyethers, polyesters,
polybutadienes, etc.) is a convenient way
of manufacturing crosslinked polyure-
thanes. Cyclotrimerization is catalyzed,
for instance, by carboxylates or tertiary
amines. Every diisocyanate participates in
the formation of two trifunctional cross-
links. The contribution of a fully reacted
diisocyanate unit to the number of cross-
links is 2x(l/3).
Related to polyisocyanurates are poly-
cyanate networks (polycyanurates) obtain-
ed by polycyclotrimerization of dicyanates.
Aromatic polycyanurates are technically
valuable products (Shimp, 1994) and also
an interesting object for gelation studies.
7.7.3 Cured Epoxy Resins
7.7.3.1 Epoxy-Amine Networks
Networks prepared by reaction of poly-
epoxides with polyamines represent the
most important group of cured epoxy resins
(May, 1988). Of the other important curing
reactions, acid curing (reactions with poly-
carboxylic acids and cyclic anhydrides)
has already been discussed briefly in
Sec. 7.4.1. Curing with polyphenols and
ionic polymerizations will be mentioned in
the next section. The basic aspects of net-
work formation and its relation to the struc-
ture and properties of cured products were
reviewed in a monograph (Dusek, 1985
1986).
 7.7 Examples of the Most Important Crosslinking Reactions 423

The basic reaction between an epoxy group and a primary amine proceeds in two steps:

\ /
o OH

+ R 2 CH-CH 2 R1N(CH2CH(OH)R2)2 (7-16)

I \ /
OH O
Hydroxyl groups are formed which, in an
excess of epoxide groups, can react and start
a polyether sequence. Therefore, polyether-
ification is a reaction initiated by the formed
OH group. However, the polyetherification
process is in reality more complicated than
that shown - a simple stepwise polyaddition
of epoxide groups initiated by the OH
groups of the reaction products of Eqs.
(7-15) and (7-16). Splitting-off of the initiat-
ing species and reinitiation are the main
complicating features (Berger and Lohse
1985; Matejka etal. 1992).
The epoxide-amine addition is controlled
by the relative reactivities of hydrogens in
the primary and secondary amino groups. If
the reactivity of the hydrogen in the secon-
dary amino group is lower than that of the
primary amino group, chain extension is
preferred to branching and gelation is
delayed on the conversion scale. As with
other networks formed by alternating addi-
tion mechanisms, the crosslinking density is
very much affected by off-stoichiometry. If
the excess of an amine (with excess epox-
ide, crosslinking is complicated by etherifi-
cation) is high enough, the so-called critical
molar ratio is reached and the network is not
formed at all. The critical molar ratio is an
important guideline for the preparation of
still liquid and soluble epoxy-amine
adducts. In amine curing, diepoxide is
CH9CHCH0
CH 2 CHCH 2
V
difunctional and diamine tetrafunctional.
The fragments necessary for network build-
up are represented by a distribution of di-
epoxide and diamine units with different
numbers of reacted functional groups (0, 1,
2 for diepoxide, and 0, 1,2, 3,4 for diamine)
(Fig. 7-15; Dusek, 1986).
The epoxide-amine addition is as simple
as that shown in Fig. 7-15 only for certain
classes of resins, such as those based on the
diglycidyl ether of bisphenol A (DGEBA)
(II). However, the mechanism of addition
of amines to some other epoxy resins is
much more complicated. Curing the difunc-
tional Af iV-diglycidylamine (III) or the
tetrafunctional MMA^TV'-tetraglycidyl-
4,4/-diamino-diphenylmethane (IV) with
amines is complicated by dependent reac-
tivities of glycidyl groups bonded to the
same nitrogen atom and extensive formation
of small cycles (Matejka et al., 1995). For a
theoretical build-up of the polymer network
many more fragment types are necessary
(Matejka and Dusek, 1995).
CH 2 CHCH 2 O OCH2CHCH2
0 0
II
CH 2 CHCH 2
V III
CH 2 CHCH 2
V
CH9CHCH0
IV
V
CH 2 CHCH 2
V
424 7 Network Formation
Diamine units
X
Diepoxide units
O, Q unreacted; # , reacted functionalities
7.7.3.2 Curing with Polyphenols
The phenolic group is a much stronger
proton donor than an aliphatic hydroxyl
group. The reaction with phenolic hydro-
xyl can initiate polyetherification. Diphe-
nols are bifunctional and are often used as
chain extenders. Usually, polyphenols, such
as reaction products of phenols and formal-
dehyde (novolacs), are used as curing agents
to give thermally stable epoxy resins. In the
description of network build-up, the func-
tionality distribution of polyphenols has to
be taken into account.
7.7.3.3 Ionic Mechanisms
of Network Build-up
Anionic as well as cationic polymeriza-
tions are widely employed for curing epoxy
resins and a great number of catalysts have
been used (May, 1988). From the point of
view of polymerization mechanisms, these
polymerizations involve several types of
transfer and termination reactions. The net-
work build-up should be considered as an
Fig. 7-15. Diamine frag-
ments used for statistical
build-up of epoxy-amine
networks (Dusek, 1986).
initiated process and, therefore, a simple
statistical approach is not adequate.
Polyetherification in the presence of basic
catalysts involves several reaction steps of
which the splitting-off of the initiating spe-
cies is very important, so that polyether
chains formed are usually very short (Vaz-
quez et al. 1990). Network formation has
been treated by combining kinetic and sta-
tistical branching theories (Dusek et al.,
1991).
Cationic polymerization is used for fast
curing. The most widely used catalysts are
complexes of BF3 with amines, or some
other proton donors (May, 1988). The reac-
tion scheme is even more complicated than
that suggested for the anionic mechanism
(Matejka et al., 1993). From the point of
view of the theoretical description of net-
work build-up (Matejka et al., 1997), the
degradative termination represents quite a
difficult problem. The ether groups in the
existing chains are attacked by an active end
and a part of the attacked chain is split off
and the other part is recombined with the
attacking species.
 7.7 Examples of the Most Important Crosslinking Reactions 425

7.7.4 Network Obtained called the sol-gel process).

by Crosslinking Reactions Involving
I I
Silicon-Containing Groups - - S i - O R + H2O -Si-OH + ROH
Sol-Gel Reactions I I
(7-19)
Poly(dimethylsiloxane) networks have
been one of the most frequently studied I I I I
-Si-OH + H O - S i - - > - S i - O - S i - + H 2 O
model networks. Two main reactions of I I I I
silicon groups have been employed. (7-20)
One involves formation of - S i - O - S i - I I I I
bond by crosslinking hydroxy-terminated -Si-OH + RO-Si- -Si-O-Si-+ROH
poly(dimethylsiloxanes) with polyfunc- I I I I
(7-21)
tional alkoxysilanes, e.g., with tetraethoxy-
silane:

O-Si(CH 3 ) 2 O-
2 HO-[Si(CH3)2O]IISi(CH3)2OH + Si(OEt)4 * -OSi(CH 3 ) 2 O-Si-O-Si(CH 3 ) 2 O-
I
O-Si(CH 3 ) 2 O-
(7-17)
The reaction by which a Si-H group is added to a double bond, for instance to an allyl
group, is called hydrosilylation:

3H-[Si(CH3)2O],zSi(CH3)2H + 2Y(CH2CH = CH2)3

Si(CH 3 ) 2 OSi(CH 3 ) 2 -
(CH2)3 (7-18)
-Si(CH 3 ) 2 OSi(CH 3 ) 2 CH 2 CH 2 CH 2 -Y
(CH2)3
Si(CH3)2OSi(CH3)2-

According to the above equations, both

crosslinking reactions are simple stepwise
(a + b) alternating reactions. However, in
reality, the crosslinking is not so simple
since these reactions suffer from side reac-
tions. Condensation crosslinking is compli-
cated by self-condensation of the alkoxysi-
lane. Hydrosilylation may exhibit approxi-
mately 10% side reactions at higher conver-
sions.
More complicated is the catalyzed
hydrolysis-condensation of alkoxysilanes,
titanates, etc., in the presence of water (also
The formation of Si-O-Si bonds is a
result of consecutive reactions with substi-
tution effects. The substitution effect and
overall structure growth depends on pH,
presence of complexing agents, etc. At low
pH, the substitution effect on the hydrolysis
reaction is negative, so that the increase in
the number of bonds per monomeric unit is
slow and units with a high number of bonds
(four) are not numerous. Therefore, the
increase in molecular weights of the struc-
tures is slow and the structures are more
426 7 Network Formation
open. At high pH, there is a positive substi-
tution effect in the condensation reaction, so
that large, bulky structures are formed even
at low conversions (Hench and West, 1990;
Marketal., 1995).
However, formation of siloxane clusters
is complex and cannot be described by sim-
ple statistical or chemical kinetics network
formation theories. Physical interactions
and diffusion control are operative, partic-
ularly in the case of formation of condensed
structures at high pH. Therefore, the struc-
ture growth must be simulated in three-
dimensional space as a diffusion-limited
aggregation process, or modeling can be
attempted by the generalized Smoluchovski
coagulation equations.
7.8 Conclusion
At present, there are a number of theoret-
ical methods enabling the description of the
structural changes which occur when mul-
tifunctional monomers react. When select-
ing an appropriate method, the mechanisms
and kinetics of basic bond formation reac-
tions should be respected. Therefore, suffi-
ciently extensive information on "chemis-
try" is a necessary prerequisite for model-
ing network build-up. In certain cases, stat-
ic and dynamic interactions may strongly
affect the evolution of the structures. The
application of network formation theories
and their comparison with experiments,
results not only in the development of pre-
dictive methods, but also helps to verify the
possible assumptions made about the mech-
anism and kinetics of bond formation. It also
helps in elucidating the role of physical
effects on network build-up.
7.9 References
Adam, G., Gibbs, J.H. (1965), J. Chem. Phys. 43,
139.
Allen, P.E.M., Patrick, C.R. (1974), Kinetics & Mech-
anisms of Polymerization Reactions. Application of
Physico-Chemical Principles. Chichester: E. Hor-
wood.
Berger, J., Lohse, F. (1985), Eur. Polym. J. 21, 435.
Boots, H.M.J., Klosterboer, J.G., van de Hei, G.M.M.,
Pandey, R.B. (1985), Br. Polym. J. 17,219.
Clark, A.H., Ross-Murphy, S.B. (1987), Adv. Polym.
Sci. 83, 57.
Dusek, K. (1982), Development in Polymerisation,
3rd ed. Barking, U. K.: Applied Science Publishers.
Dusek, K. (1985), in: Physics of Finely Divided
Matter: Boccara, N., Daoud, M. (Eds.). Berlin:
Springer, p. 107.
Dusek, K. (1985-1986), Epoxy Resins and Compos-
ites, Vols. 1-4, Adv. Polym. Sci., Vols. 72, 75, 78,
80. Berlin: Springer.
Dusek, K. (1986), Adv. Polym. Sci. 78, 1.
Dusek, K. (1989), in: Telechelic Polymers. Boca
Raton: CRC Press, pp. 289-361.
Dusek, K., Havlicek, I. (1993), Prog. Org. Coat. 22,
145.
Dusek, K., Ilavsky, M. (1979), Polym. Eng. Sci. 19,
246.
Dusek, K., Matejka, L. (1984), Adv. Chem. Ser. 208,
27.
Dusek, K., Somvarsky, J. (1993), in: Synthesis, Char-
acterization and Theory of Polymeric Networks and
Gels. New York: Plenum Press, p. 283.
Dusek, K., Somvarsky, J. (1996), Faraday Discuss.
Chem. Soc. 101, \\1.
Dusek, K., Spirkova, M., Havlicek, I. (1990), Macro-
molecules 23, 111 A.
Dusek, K., Somvarsky, J., Ilavsky, M., Matejka, L.
(1991), Comput. Polym. Sci. 1, 90.
Eisenbach, CD. (1980), Ber. Bunsenges. Phys. Chem.
84, 680.
Family, E, Landau, D.P. (1984), Kinetics of Aggrega-
tion and Gelation. Amsterdam: Elsevier.
Flory, P.J. (1953), Principles of Polymer Chemistry.
Ithaca: Cornell University Press.
Galina, H., Szustalewicz, A. (1990), Macromolecules
23, 3833.
Gupta, A.M., Hendrickson, R.C., Macosko, C.W.
(1991), J. Chem. Phys. 95, 2027.
Hench, L.L., West, J.K. (1990), Chem. Rev. 90, 33.
Hendrics, E.M., Ernst, M.H., Ziff, R.M. (1983),
/. Stat.Phys.31, 519.
Horie, K., Mita, I. (1989), Adv. Polym. Sci. 88, 11.
Horie, K., Mita, I., Kambe, H. (1968), J. Polym. Sci.
Al, 6, 2663.
Huguenin, EG.A., Klein, M.T. (1985), Ind. Eng.
Chem., Prod. Res. Dev. 24, 166.
Ilavsky, M. Somvarsky, J., Bouchal, K., Dusek, K.
(1993), Polym. Gels Networks 1, 159.

Jenkins, A.D., Ledwith, A. (1974), Reactivity, Mech-
anism and Structure in Polymer Chemistry. London.
Wiley.
Klems, J.K., Posselt, D. (1988), Random Fluctuations
and Pattern Growth: Experiments and Models.
Dordrecht: Kluwer Academic, p. 7.
Kloosterboer, J.A. (1988), Adv. Polym. Sci. 84, 1.
Kuchanov, S.I., Povolotskaya, E.S. (1982), Vysoko-
mol. Soedin.A24, 2179.
Leung, Y.K., Eichinger, B.E. (1984), /. Chem. Phys.
80, 3877, 3885.
Mark, J.E., Lee, C.Y., Bianconi, P.A. (1995), Hybrid
Organic-Inorganic Composites, ACS Ser. Vol. 585.
Washington, D.C.: American Chemical Society.
Matsuoka, S., Quan, X., Bair, H.E., Boyle, D.J.
(1989), Macromolecules 22, 4093.
Matejka, L., Dusek, K. (1995), /. Polym. Sci., Pt. A:
Polym. Chem. 33, 473.
Matejka, L., Podzimek, S., Simonsick, W.J.Jr., Spacek,
P., Dusek, K. (1992), /. Poly. Sci., Pt. A: Polym.
Chem. 30, 2109-2120.
Matejka, L., Chabanne, P., Tighzert, L., Pascault,
J.-P. (1993), J. Poly. Sci., Polym. Chem. Ed. 32,
1447.
Matejka, L., Podzimek, S., Dusek, K. (1995),
J. Polym. Sci., Pt. A: Polym. Chem. 33, 461.
Matejka, L., Dusek, K., Chabanne, P., Pascault, J.-P.
(1997),/. Polym. Sci., Polym. Phys. Ed. 35, in press.
May, C.A. (1988), Epoxy Resins. Chemistry and Tech-
nology. New York: Marcel Dekker.
Mikes, J., Dusek, K. (1982), Macromolecules 15, 93.
Mikos, A.G., Tsakoudis, G.C., Peppas, N.A. (1986),
Macromolecules 19, 2174.
Rabinowit, E. (1937), Trans. Faraday Soc. 33, 1225.
Reegen, S.L., Frisch, K.C. (1971), Adv. Polyurethane
Sci. Technol. 1, 1.
Rohr, D.F., Klein, M.T. (1988), Ind. Eng. Chem. Res.
27, 1361.
Rohr, D.F., Klein, M.T. (1990), Ind. Eng. Chem. Res.
29, 1210.
Rozenberg, B.A. (1985), Adv. Polym. Sci. 75, 113.
Sanford, W.M., McCollough, M.L. (1990), J. Polym.
Sci, Polym. Phys. 28, 973.
Saunders, J.H., Frisch, K.C. (1962), Polyurethanes
Chemistry and Technology, Vols. 1 and 2. New
York: Wiley-Interscience.
7.9 References 427
Shimp, D. (1994), Polym. Mater. Sci. Eng. 71, 623.
Smoluchowski, M. (1918), Z. Phys. Chem. 92, 129.
Somvarsky, J., Dusek, K. (1994a), Polym. Bull. 33,
369.
Somvarsky, J., Dusek, K. (1994b), Polym. Bull. 33,
311.
Stauffer, D., Coniglio, A., Adam, M. (1981), Adv.
Polym. Sci. 44, 103.
Stepto, R.F.T. (1982), in: Developments in Polymer-
isation 3. London: Applied Science Publishers,
p. 81.
Tobita,H.,Hamielec, A.E. (\988),Makromol. Chem.,
Macromol. Symp. 20/21, 501.
Tobita, H., Hamielec, A.E. (1989), Macromolecules
22, 3098.
Turnbull, D., Cohen, M.H. (1961), J. Chem. Phys. 34,
120.
Vazquez, A., Matejka, L., Spacek, P., Dusek, K.
(1990), /. Polym. Sci., Polym. Chem. Ed. 28, 2305.
Wisanrakkit, G., Gillham, J.D. (1990), /. Appl. Polym.
Sci. 41, 2885.
General Reading
Aharoni, S.M. (1993), Synthesis, Characterization
and Theory of Polymeric Networks and Gels.
New York: Plenum Press.
Boccara, J., Daoud, M. (1985), Physics of Finely
Divided Matter. Berlin: Springer.
Cohen-Addad, J.-P. (1996), Physical Properties of
Polymeric Gels. New York: Wiley.
Dusek, K. (1985-1986), Epoxy Resins and Com-
posites, Vols. 1-4; Adv. Polym. Sci., Vols. 72, 75,
78, 80. Berlin: Springer.
Dusek, K. (1986), Adv. Polym. Sci. 78, 1.
Family, E, Landau, D.P. (1984), Kinetics of Ag-
gregation and Gelation. Amsterdam: Elsevier.
Flory, P.J. (1953), Principles of Polymer Chemistry.
Ithaca, NY: Cornell University Press.
Goethals, J. (1989), Telechelic Polymers. Boca Raton,
FL: CRC Press.
May, C.A. (1988), Epoxy Resins. Chemistry and
Technology. New York: Marcel Dekker.
Stauffer, D., Coniglio, A., Adam, M. (1981), Adv.
Polym. Sci. 44, 103.
8 Reactive Processing of Polymer Blends:
Polymer-Polymer Interface Aspects
Takashi Inoue and Philippe Marechal

Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Tokyo,

Japan

List of Symbols and Abbreviations 430

8.1 Introduction 433
8.2 Polymer-Polymer Interfaces: Theoretical Background 433
8.2.1 Interfacial Thickness and Interfacial Tension 433
8.2.2 Interfacial Segregation 436
8.2.3 Interfacial Properties 437
8.3. Interfacial Activity of Block and Graft Copolymers 437
8.3.1 Thermodynamics of Interfaces with Block Copolymers 437
8.3.2 Reduction of the Interfacial Tension with Block Copolymers 440
8.3.3 Mechanical Properties of Interfaces Modified by Block Copolymers
(BCPs) and Graft Copolymers (GCPs) 441
8.4 Interfaces in Reactive Blends 444
8.4.1 In Situ Formation of Block and Graft Copolymers by Reactive Blending . . . 444
8.4.2 Effects of Chemical Modification on Morphology Development 448
8.4.3 Kinetics of the Interfacial Reaction 451
8.4.4 Pre-Made Versus In Situ Formed Block Copolymers 455
8.4.5 Search for Optimal Reactive Molecules 456
8.4.6 Morphology, Interfaces, and Properties 457
8.5 Concluding Remarks 458
8.6 References 460

Materials Science and Technology

Copyright WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
430 8 Reactive Processing of Polymer Blends: Polymer-Polymer Interface Aspects

List of Symbols and Abbreviations

b the Kuhn segment length
c local composition in a blend
ca, CR compositions of the two coexisting phases in a binary blend
d particle diameter
D length of periodicity in a lamellar domain
D^ equilibrium interfacial thickness between two amorphous polymers of infinite
molecular weight
/ free energy density
/o free energy in the absence of a gradient
Gc interfacial toughness; fracture energy
h thickness of a brush of adsorbed molecules
k, kB Boltzmann constant
/ interfacial thickness
L thickness of a brush
N number of statistical segments of a polymer
Nw number of molecules in the system considered
p viscosity ratio
S total interfacial area in the system considered
Sc surface area covered by BCP molecule
S sp specific interfacial area
So surface area covered by a BCP molecule at saturation of the interface
t time
T absolute temperature
V volume of the system considered
We Weber number (or capillary number)
x coordinate perpendicular to the interface (x = 0 is the middle point of the inter-
face)
z distance from the middle of an interface
Zf excess concentration of BCP at an interface, relative to the equilibrium con-
centration in the homopolymer phases

a, J3 symbols for the coexisting phases in a binary blend

y shear
y shear rate
A energy gain on adsorption
0, c surface coverage
r/b viscosity of the blend
?7 d viscosity of the dispersed phase
T] m viscosity of the matrix
K interfacial gradient energy coefficient
A interfacial thickness
/u chemical potential
ve entanglement density
 List of Symbols and Abbreviations 431

correlation length measured by light scattering

Po number density
a interfacial tension
surface coverage (= 1/5C)
surface coverage of BCP at saturation (= l/5 0 )
concentration of BCP in the PS homopolymer phase
volume fraction of blend components (d for dispersed phase, m for matrix
phase)
the Flory interaction parameter

AA acrylic acid
ABS acrylonitrile butadiene styrene copolymer
AN acrylonitrile
APS y-aminopropyl triethoxysilane
A,B components of a binary blend
A/B blend of polymers A and B where A is the major component
A-BBCP block copolymer consisting of polymers A and B
A-B-A triblock copolymer
A-g-MA a polymer with maleic anhydride grafted on it
A-r a polymer terminated by a group r
BA butyl acrylate
BCP block copolymer
BTTT brittle-ductile transition temperature
C1PE chlorinated polyethylene
cmc critical micelle concentration
CTBN poly(butadiene-co-acrylonitrile)
CTBR a,o>carboxy terminated poly (butadiene)
J-PS deuterated polystyrene
DMA dynamic mechanical analysis
EA ethyl acrylate
EP ethylene propylene copolymer
EPDM ethylene propylene diene monomer rubber
EPMA ethylene propylene copolymer functionalized with maleic anhydride
EPR ethylene propylene copolymer rubber
EPX reactive rubber
FRES forward recoil spectroscopy
GCP graft copolymer
GPC gel permeation chromatography
LS light scattering
MA maleic anhydride
MAA methacrylic acid
NBR poly(acrylonitrile-butadiene-acrylic)acid
NR neutron reflectivity
NS neutron scattering
432 8 Reactive Processing of Polymer Blends: Polymer-Polymer Interface Aspects

PA polyamide
PB polybutadiene
PC polycarbonate
PCL -caprolactone
PDMS poly(dimethylsiloxane)
PE polyethylene
PEO poly(ethylene oxide)
PET poly(ethylene terephthalate)
PMMA poly(methylmethacrylate)
PP polypropylene
PPO poly(dimethyl phenylene oxide)
PS polystyrene
PS AN poly(styrene-c<9-acrylonitrile)
PVP poly(vinyl pyridine)
SAN styrene-acrylonitrile copolymer
SANS small angle neutron scattering
SEBS hydrogenated SBS (styrene-butadiene-styrene) triblock copolymer
SEM scanning electron microscopy
SMA styrene-maleic anhydride copolymer
TEM transmission electron microscopy
THF tetrahydrofuran
VA vinyl acetate
 8.2 Polymer-Polymer Interfaces: Theoretical Background
8.1 Introduction
Most polymer blends are phase-separated
systems with some dispersion of one poly-
mer in the other. The properties of the poly-
mer blends deeply depend on the morphol-
ogy. Generally some 1 |iim or even smaller
particles are required to get good synergy of
the properties of the component polymers.
A typical example is shown in Fig. 8-1,
which shows that, for amorphous materials
with a tendency to fracture by crazing, the
optimal rubber particle size for toughening
is uniquely related to the entanglement den-
sity (Wu, 1990).
The mean particle size in polymer blends
is the result of a balance between mechani-
cal and interfacial forces: the lower the
interfacial tension, the smaller the particles
(Chen and White, 1993; Plochocki, 1983).
Moreover, if good dispersion is obtained
after compounding, then it must remain
stable upon further processing and shaping
of the material. The instability of the mor-
phology is due to particle coalescence,
which is favored by high interfacial tension,
B mer blends will be presented and some com-
<D
CO
_CD
O
0.5 -
CO
Q_
Q_
O
0.0 0.1 0.2
Entanglement density of matrix ve(mmol crrr3)
Figure 8-1. Optimum rubber particle diameter d ver-
sus the entanglement density ve of a brittle matrix,
based on the notched Izod impact strength (Wu, 1990).
433
mobility of the interface, and the absence of
repulsive interactions between interfaces of
approaching particles (Favis and Willis,
1990). Good adhesion between the phases
is also often required for the establishment
of good properties (Bucknall, 1977;
Epstein, 1979).
Hence a fine and stable morphology and
good interfacial adhesion can be reached by
effective control of the interfacial proper-
ties through adequate interfacial modifica-
tion. These processes of interfacial modifi-
cation resulting in lower interfacial tension,
inhibited coalescence, and improved adhe-
sion are generally called 'compatibilization
processes' (Utracki, 1982) or 'technologi-
cal compatibilization' (Coran and Patel,
1983). Interfacial modification can be
brought about by the addition of block
(BCP) or graft (GCP) copolymer at the inter-
face (Fayt et al., 1987). However, the syn-
thesis of pre-made block copolymer is often
difficult and/or expensive. Therefore, in
many cases, the block or graft copolymer is
produced in situ by blending reactive mate-
rials.
In this chapter, after a brief review on the
current understanding of the polymer-poly-
mer interface, the principles of interfacial
modification by the introduction of BCP
will be explained. Then the interfacial
aspects of the reactive processing of poly-
ments for the future will be made.
8.2 Polymer-Polymer Interfaces:
Theoretical Background
8.2.1 Interfacial Thickness
and Interfacial Tension
The interface is a space in which the com-
position is not uniform but has a gradient.
The thermodynamics of the inhomogeneous
434 8 Reactive Processing of Polymer Blends: Polymer-Polymer Interface Aspects

system were established by Cahn and Milli-
ard (1958). They formulated the free ener-
gy density (/) as a function of both the com-
position (c) and the composition gradient
(grad c)
/ = j[/o+*-(gradc)2+...]dV
v
where K is the gradient energy coefficient,
V is the volume, and / 0 is the local free
energy for a homogeneous mixture; e.g., for
a polymer solution, f0 is given by the
Flory-Huggins equation. For immiscible
binary systems, the function fo(c) generally
has the shape shown in Fig. 8-2.
Between the coexisting compositions ca
and cp, the phase-separated system is ener-
getically favored and an interface separates
the phases a and /3. On going from a to /3
phase, i.e., crossing the interface, energeti-
cally disfavored compositions are encoun-
tered: hatched region in Fig. 8-2. One way
to minimize this would be the formation of
an infinitely thin interface with an infinite-
ly sharp gradient. However, a very thin
interface is energetically disfavored by the
c the conformational entropy. The conforma-
io
gradient terms of Eq. (8-1). So a balance
between the gradient term and the / 0 term
(A/in Fig. 8-2) is optimized by the interfa-
cial profile.
From the resulting concentration profile,
shown in the inset of Fig. 8-2, the interfa-
(8-1) cial thickness, /, is generally defined by
(8-2)
(dc/dx) max
and the interfacial tension, a, by
(8-3)
where Nv is the number of molecules, S is
the total interfacial area, and/ ref is the ener-
gy of a reference state, which is a hypothet-
ically homogeneous system of A and B
molecules having the same chemical poten-
tials, \ia and fip, as in the bulk phases a and
A
In comparison with systems of small
molecules, macromolecular systems have a
very small entropy of mixing but important
effects due to the conformational entropy of
polymer chains. The number of possible
conformations is reduced near the interface
and this reduction results in a decrease of

\ ^
CO tional entropy should be taken into account
o
Q. as an additional gradient term, which is
E
_ / _r^ > / much larger than the enthalpic gradient term
CO
c -100 -50 0 50 100 / discussed earlier. As a matter of fact, a nar-
CD Distance from interface
row interface minimizes the disfavorable
> enthalpy of contact between the two phas-
CD
C
0
CD
es, but also strongly contrains the possible
Q)
LL conformations of macromolecules that are
entropically disfavored. Then the interfacial
thickness results from the best compromise
0 Ca Cp 1 between the enthalpic contribution favoring
Mole fraction of component B a narrow interface and the mostly entropic
Figure 8-2. Free energy density of a homogeneous
gradient contributions resulting in a broad-
polymer mixture f0 versus the mole fraction of com- er interface.
ponent B. Inset: Composition versus distance from the For an incompressible and symmetric
interface (Cahn and Hilliard, 1958). system, under the hypothesis of high molec-
 8.2 Polymer-Polymer Interfaces: Theoretical Background 435

ular weight, the concentration profile c(x),
interfacial thickness /0, and interfacial ten-
sion cr0 were given analytically by (Helfand
and Tagami, 1972)
c(x) =
with
2b
/n =
where x is the distance perpendicular to the
interface and x = 0 is the midpoint of the
interface, T is the absolute temperature, kB
Boltzmann's constant, % the Flory-Huggins
interaction parameter, b the Kuhn segment
length of a polymer chain, and p 0 the num-
ber density of the polymer segments.
Figure 8-3 shows a typical interfacial
profile in polymer blends, as it is measured
1 1 r i i i
Error/">
- function /
/ come from a better estimation of the %
Hyperbolic
CD
by neutron reflectivity (NR)1 (Anastasiadis
et al., 1990). The hyperbolic tangent profile
given by Eq. (8-4) perfectly fits the experi-
mental results. The error function used by
Fernandez et al. (1988) gives practically the
(8-4) same interfacial thickness. It must be
stressed that in NR experiments, within a
given roughness of the surfaces, the interfa-
cial thickness is defined with only a few
tenths of a nanometer error. The interfacial
thickness (/) in most polymer systems falls
(8-5) between 2 and 20 nm.
The theory was extended to take account
of the effects of polydispersity and finite
(8-6) molecular weight (Anastasiadis et al., 1988;
Broseta et al., 1990)
(8-7)
(8-8)
where cot = x^h ^i being the number of sta-
tistical segments of polymer /. Combining
Eqs. (8-5) to (8-8), we observe that thicker
interfaces and lower interfacial tensions are
expected for systems with smaller % and
lower molecular weight.
However, the results of Eq. (8-8) are still
different from those obtained by NR experi-
ments. Better agreement could possibly

o tangent parameter. As a matter of fact, this parame-

X ter depends on the choice of the Kuhn seg-
^5 ment length b (Helfand and Sapse, 1975;
Helfand, 1975 a). Moreover, the value of x
depends on the model (Kressler, 1994). It
-100 -50 0 50 100 also been shown that the compressibility
Distance (A)
1
Figure 8-3. Comparison of a hyperbolic tangent Neutron reflectivity (NR) is based on the analysis
function where the effective width of the interface is of the reflection of neutrons by a plane sample. This
50 A with the error function profile derived from a technique has one of the best resolutions for the char-
roughness parameter of 20 A. The sample was consti- acterization of the interfacial profile. However, for NR
tuted of a thick PMMA film on an Si substrate over- a deuterated polymer is practically required (Russell,
lapped by a thin film of d-PS (deuterated PS) (Anas- 1990). The main source of discrepancy probably aris-
tasiadis et al., 1990). es from capillary waves on the interface (Jonas, 1997).
436 8 Reactive Processing of Polymer Blends: Polymer-Polymer Interface Aspects
may have a significant effect on the ^param-
eter determined by small angle neutron scat-
tering (SANS) (Kumar, 1994).
8.2.2 Interfacial Segregation
In the reactive blend systems, the chain
ends are often reactive (e.g., amino end
groups of polyamide), and a third compo-
nent with low molecular weight is some-
times added as a reagent (e.g., a coupling
agent).
In the bulk, individual polymer chains
have a gaussian distribution around their
center of gravity. The size of this distribu-
tion is typically described by the radius of
gyration. However, at an interface there is a
spatial perturbation of the chain conforma-
tion (Reiter et al., 1990). The conformation-
al restriction of a long chain at or near the
interface is entropically disfavored, but for
0.08 r
Distance / /0
Figure 8-4. Profile of the excess of the lower mass
compound at the interface between polymer A and
polymer B, which have a bimodal molecular weight
distribution: ^A^=5 and 7 for the low and high molec-
ular weight compounds. The curves come from self-
consistent field calculations including both the entrop-
ic term from the chain conformation limitation at the
interface and the gradient term introduced in Eq.
(8-1). The fraction of the lower molecular weight com-
pound is varied: (dotted) 50%, (full) 33%, and
(dashed) 25% (Broseta et al., 1990).
shorter chains this is not so important.
Therefore polymer systems exhibit an inter-
facial excess of small molecules (Helfand
and Tagami, 1972), chain ends (Helfand and
Tagami, 1972), or lower molecular weight
molecules (Broseta et al., 1990; Helfand
and Sapse, 1975; Helfand, 1975 a; Kressler,
1994; Kumar, 1994; Reiter et al., 1990;
Birosel, 1991).
The situation is shown in Fig. 8-4 where
a low molecular weight compound prefer-
ably locates at the interface, i.e., the concen-
tration is higher at the interface than in both
bulk phases. A similar situation is expected
for chain ends of both polymers, i.e., com-
pared to a mid-chain segment, end segments
have a higher probability of locating at the
interface. This situation can easily be under-
stood by counting the number of chain con-
formations, which remains higher when a
chain end is at the interface than when a mid-
chain segment is at the interface. Hence the
segregation phenomena imply that the
polymer-polymer interface should be a very
interesting place for the reaction in phase-
separated systems.
8 1.0
xf
sz "8 A = 20 nm /
S 0.6
CD nJ3- 200 nm
CD
xo-
< 0.2
0 5 10
Interfacial thickness172/nm1/2
Figure 8-5. Adhesive strength a divided by the adhe-
sive strength of the homogeneous blend o^ versus the
square root of the interfacial thickness of a miscible
PMMA/SAN system (Cho et al., 1994).
 8.3 Interfacial Activity of Block and Graft Copolymers 437

8.2.3 Interfacial Properties

As the interface between two polymers is
often much smaller than the radius of gyra-
tion of the bulk polymers, the entanglement
density is strongly reduced at the interface.
Therefore the mechanical strength of an
interface is directly related to its thickness
(Choetal., 1994).
This relation between the thickness and 0.01 X
strength of the interface is shown in Fig.
8-5 for a weld of miscible polymers where the
interface thickness, which was measured by
103
03
- 0.005 Q.
ellipsometry2, increases with time with a par- O
allel increase of the interfacial strength (Kim
and Wood, 1983; Wu et al., 1986; Brochard- 1
Wyart and de Gennes, 1990; Yukioka et al.,
1992). Similar results were obtained for _ 10 20 30 40 50 60
i
immiscible polymers, as shown in Fig. 8-6 AN content of the SAN (wt. %)
where the interfacial strength in terms of the Figure 8-6. Interfacial thickness /, interaction
parameter %, and fracture energy Gc of a PMMA/SAN
fracture toughness of the interface increases
system versus the AN content in the SAN (Yukioka
linearly with the interfacial thickness or etal., 1992).
equivalently %XI1 [see Eq. (8-5)].

interfacial tension and poor interfacial

8.3 Interfacial Activity of Block
and Graft Copolymers
It was shown that the incompatibility of
most polymer pairs induces relatively high
2
Ellipsometry is based on the analysis of the inten-
sity and polarity of reflected light on a plane sample
(Azzam and Bashara, 1977). It is a remarkable tech-
nique since it only requires the difference in the indi-
ces of refraction, which exists between most polymer
pairs. However, its resolution is not as high as that
obtained by NR (Walsh et al., 1990). It is effective for
systems with an interfacial thickness above 2 - 4 nm
(Yukioka and Inoue, 1993). The validity of the tech-
nique has been confirmed by TEM analysis (Kressler
et al., 1993). Ellipsometry was also applied success-
fully to analyze the diffusion process (Yukioka et al.,
1992). The accuracy of ellipsometry can be improved
by analysis of the retardation angle as a function of
the incident angle (Kim et al., 1989). This improve-
ment was called "scanning angle reflectometry"
(Leermakers and Gast, 1991).
strength. The improvement of these interfa-
cial properties through the addition of block
(BCP) or graft copolymer (GCP) will be
explained.
8.3.1 Thermodynamics of Interfaces
with Block Copolymers
The A - B BCP notation will be used to
signify a diblock copolymer consisting of
polymers A and B. Our main interest is the
interface modification of an A/B sysem with
A - B BCP.
First of all it must be stressed that the
A - B BCP preferentially locates at the A/B
interface with the A and B blocks on the A
and B side, respectively. Experimental evi-
dence of this tendency was given with a film
of poly(2-vinyl pyridine) (PVP) covered
with a thin film of PS containing about 10%
438 8 Reactive Processing of Polymer Blends: Polymer-Polymer Interface Aspects

of dissolved d-PS-PVP BCP. The location (a) 0.20

of the d-PS block in the film and at the inter-
face before and after annealing at 170 C
was analyzed by forward recoil spectrosco-
py (FRES)3, as shown in Fig. 8-7.
In Fig. 8-7 a, it is shown that, before
annealing, the BCP is homogeneously dis-
tributed in the PS film. However, after
annealing at 170 C, (Fig. 8-7 b) a high con-
centration of BCP is found at the interface,
while the concentration of BCP in the PS film
is reduced to about 2% (Shull et al., 1990). o oo
-2000 0 2000
Depth4000
(A) 6000 8000
At equilibrium, the respective concentra-
tions of BCP in the bulk and at the interface
are given by the condition of constancy of
the chemical potential throughout the
system. However, it must be stressed that
the chemical potential of the BCP does not
increase indefinitely. Above some critical
value, small micelles will spontaneously
develop to form a BCP-rich phase. As the
micelles start to form, any increase of the
BCP concentration in the system will only
result in an increasing micelle concentration
with a negligible increase of the chemical 0.00
potential of the BCP. This limiting concen- -2000 2000 4000 6000 8000
tration of BCP above which the micelles Depth (A)
form is the critical micelle concentration Figure 8-7. Block copolymer distribution versus dis-
(cmc). Depending on the system, several tance; 0 A: air/PS interface, 5000 A: PS/PVP inter-
equations are given to predict the cmc (Shull face; (a) prior to annealing and (b) after 8-h anneal-
ing at 178 C (Shull et al., 1990).
etal., 1990; Leibler, 1988).
Since above the cmc the interface is not
modified further, the interface saturated in pure BCP system. For example, for a pure
BCP Is often modeled by the interface in a symmetric BCP a lamellar structure is
formed spontaneously during annealing.
3
FRES requires the use of deuterated and protonat- The spacing of the lamellae D only depends
ed polymer. The technique analyzes the energy of the on the molecular weight of the blocks. In the
elastic recoil of the particles. The incident particles
are He ions. This technique was used successfully to case of PS-PMMA BCP, it was described
show the preferential location of the BCP at the inter- by the following experimental relation
face 20 nm below the surface and at the surface of a (Anastasiadis et al., 1990)
flat sample (Shull et al., 1990). It was also powerful
for the analysis of the surface enrichment in d-PS/PS = 4.1 N 0-65 (8-9)
(Sokolov et al., 1989; Jones et al., 1989). The resolu-
tion is typically 80 nm, but it can be improved with where N is the degree of polymerization or
the time-of-flight technique down to 35 nm (Stamm, the number of monomer units in the chain
1991). and D is given in angstroms.
 8.3 Interfacial Activity of Block and Graft Copolymers
As a result of the space-filling require-
ment, there is some stretching of the BCP
block perpendicular to the interface. The
stretching of individual chains in a lamella
was experimentally confirmed by neutron
scattering (NS) (Matsushita et al., 1990).
End-attached chains on a surface are all
stretched perpendicular to the surface and
are therefore called a polymer brush (Hal-
perin et al., 1992).
As illustrated in Fig. 8-8, the chains in a
brush occupy some area (Sc) defining the
surface coverage and extend to some aver-
age thickness L taken to be the thickness of
the brush. In Eq. (8-9), D was the sum of
two brush thicknesses.
At saturation, the area per BCP corre-
sponding to Eq. (8-9) is given by
S0 = 48.6N 0 - 39 (8-10)
where So is in A2. The surface coverage Zo
is generally defined as the reciprocal of So.
In the strong segregation limit (%N >20),
the effect of A - B BCP on the A/B interfa-
cial thickness is predicted to be quite small
(Noolandi and Hong, 1984). In contrast, in
the weak segregation limit (%N <20), a
Figure 8-8. Schematic representation of a BCP mole-
cule at an interface. Sc is the surface area occupied by
one BCP molecule and SQ is the surface area occupied
by the same BCP in the case of a saturated interface
(Nakayama, 1994).
439
Table 8-1. Thickness of the interface after annealing
as a function of the thickness of the film of a
PS-PMMA BCP at the PS/PMMA interface.
Thickness of Interfacial thickness
PS-d-PMMA
(nm) (nm)
0 5 0.2
8 6.60.3
8.5 6.60.3
19.1 7.40.4
23.9 8.40.5
34.1 26.52
37.2 29.92.5
oo 5 0.2
lower constraint is imposed for the BCP than
for the homopolymer, so the interfacial
thickness becomes more affected by the
presence of BCP (Helfand, 1975 b).
Table 8-1 shows the interfacial thickness
for the PS/PMMA interface with varying
BCP content. The measurement were per-
formed by NR. It is observed that the thick-
ness of the interface increased slightly with
increasing BCP content. Above some criti-
cal concentration, the interfacial thickness
jumps to higher values. This jump is due to
the formation of the first diblock lamella
parallel to the interface. However, in the
neat BCP system constituted of successive
regular PS and PMMA lamellae, the inter-
facial thickness is identical to that of the
PS/PMMA interface (Russell et al., 1991).
Nevertheless, it must be stressed that, when
dealing with such measurements, the inter-
facial roughness or interfacial disorder may
be interpreted as an increased interfacial
thickness (Char et al., 1993).
Although the addition of BCP results in
very little change in the interfacial thick-
ness, the interfacial bonding between the A
and B homopolymer phases is greatly affect-
ed. As a matter of fact, when the BCP is
added the total number of contacts between
the homopolymers strongly decreases. The
BCP pushes the homopolymers away from
440 8 Reactive Processing of Polymer Blends: Polymer-Polymer Interface Aspects
-30 -20 -10 0 10
Distance Ib
Figure 8-9. Interfacial profile of A homopolymer
(full line), A block (dashed line), B homopolymer (full
line), and B block (dashed and dotted line) of an
A/B/A-B/solvent system with polymers A and B of
infinite molecular weight and BCP with A and B
blocks of 500 and 1000 segments, respectively.
Weight of BCP/weight of polymer A = 5%. Here the
calculation is made for a PS/PB/PS-PB BCP/styrene
system (Noolandi and Hong, 1982).
the interface, this is more important for
BCPs of high molecular weight. Figure 8-9
shows the concentration profiles of A homo-
polymer, A block, B block, and B homo-
polymer near the interface (Noolandi and
Hong, 1982). This system consists of sol-
vent, polymers A and B of infinite molecu-
lar weight, and BCP with A and B blocks of
500 and 1000 segments, respectively.
The dotted lines in Fig. 8-9 show the total
concentration of A and B species. This is not
very different from the profile of the A/B
interface. However, the A and B segments
of the homopolymers are pushed away from
the interface. This is more serious on the B
side since the B block has a higher molecu-
lar weight. It is also important to note that
the interpenetrations of A and B block with
A and B homopolymer, respectively, are
achieved at higher levels than the interpen-
etration of the A and B segment in the
unmodified A/B interface. This aspect will
be discussed later in connection with the
interfacial strength.
8.3.2 Reduction of the Interfacial
Tension with Block Copolymers
An interesting benefit of the addition of
BCP is the dramatic reduction of the inter-
facial tension. Figure 8-10 shows the inter-
facial tension measured by the sessile drop
method in a poly(ethylene oxide) (PEO37)/
poly(dimethylsiloxane) (PDMS32) as a
function of the PDMS32-PEO37-PDMS32
30 tri-BCP concentration. The subscripts hold
for the molecular weights in kg/mol (Wag-
ner and Wolf, 1993).
It is observed that with the addition of
small concentrations of BCP the interfacial
tension is dramatically reduced and then lev-
els off. Similar conclusions were obtained
earlier from the dependence on the BCP con-
tent of the particle size after processing. It
was found that 2% BCP gives a dramatic
reduction of the particle size, while higher
concentrations do not strongly improve it
further (Fayt et al., 1986). However, the rela-
tion between the particle size and the inter-
facial tension should be discussed more care-
fully, as will be shown later.
The reduction of the interfacial tension by
the added BCP is theoretically interpreted
in terms of several contributions, as sum-
^ 12
0.5 1.0 1.5 2.0 2.5
Weight fraction of BCP (wt.%)
Figure 8-10. Interfacial tension of a PEO37/PDMS32
interface versus the PDMS 32 -PEO 37 -PDMS 32 tri-
BCP concentration. The subscripts (37 or 32) indicate
the molecular weights in kg/mol (Wagner and Wolf,
1993).
 8.3 Interfacial Activity of Block and Graft Copolymers
Table 8-2. Contributions to the interfacial tension for
a 200-200 BCP with BCP chemical potential =
4/cB7, homopolymer degree of polymerization =
1000, and #=0.1.
Term Energetic
contribution
CAB 0.111 bpokB T
Localization of joints cr, 0.052 b p0 kB T
Homopolymer/
corresponding block <7AA + <7BB 0.0\4bp0kB T
Chain stretching -0A26bp0kB T
Total 0.051 b pokB T
marized in Table 8-2 (Shull and Kramer,
1990).
The main term giving rise to the interfa-
cial tension is the enthalpy of contact
between unlike segments at the interface
(crAB). Then the restriction of the location of
the joint at the interface gives rise to an
entropic term (<7j). The contributions of the
interfaces between the homopolymers and
the corresponding brushes (<JAA and (JBB)
are quite small and are often neglected by
assuming that o"0= crAB + <7AA + crBB, where
<70 is the interfacial tension between the
homopolymers (Leibler, 1991). The term
giving the reduction of the interfacial ten-
sion is due to the stretching of the blocks of
the BCP. It comes from the fact that if the
interfacial area is increased the blocks relax
in a state of lower stretching. Such theories
predict that very low, even zero, interfacial
tensions could be obtained. Moreover, for
plane interfaces it is also shown that the
optimal copolymer is a symmetric block
copolymer (Leibler, 1988, 1991). This is
also concluded from experimental work
(Teyssie et al., 1988).
The plane interface is a quite idealized sit-
uation, since in most practical systems small
particles of one polymer are dispersed in a
matrix. As the particles become very small,
curvature effects cannot be neglected (Lei-
bler, 1988). Hence the optimal block copol-
441
ymer should have a shorter chain on the dis-
persed side of the block. However, this is
modulated by the degree of interpenetration
of the blocks by their corresponding homo-
polymers. This interpenetration or swelling
of the brush of BCP depends on the molec-
ular weight of the homopolymers compared
to that of the blocks: With a homopolymer
of higher molecular weight than the blocks,
swelling was not observed (Roe, 1986;
Cheng et al., 1989; Hashimoto et al., 1990;
Shull and Winey, 1992; Cho et al., 1990),
while it was well established in the other
case (Hashimoto et al., 1990; Tanaka et al.,
1991; Winey et al., 1991; Babaet al., 1994;
Koisumi et al., 1990).
Swelling of the BCP by the homopolymer
induces important modifications to Eqs.
(8-9) and (8-10). When homopolymer of
low molecular weight is added, Sc increas-
es while D is not changed. In the opposite
situation, D increases but Sc is unchanged
(Hashimoto et al., 1990). In PS/PMMA
blends, it was found that a symmetric
PS-PMMA BCP tends to form micelles
preferentially in the phase of lower molec-
ular weight (Marechal et al., 1994).
Swelling of the BCP by a lower molecu-
lar weight homopolymer has an entropic
driving force. However, enthalpy driven
swelling also occurs when the A brush is
surrounded by a polymer C which is mis-
cible with A (with negative %). For exam-
ple, the swelling of a d-PS block by PPO
homopolymer was clearly observed by
FRES (Brown et al., 1990), as well as indi-
rectly by dynamic mechanical analysis
(DMA) (Auschra et al., 1993).
8.3.3 Mechanical Properties of
Interfaces Modified by Block Copolymers
(BCPs) and Graft Copolymers (GCPs)
In addition to the reduction of the inter-
facial tension, the BCP added at an interface
442 8 Reactive Processing of Polymer Blends: Polymer-Polymer Interface Aspects

improves the adhesion and promotes repul- r- , r- pT [ i i .

sive interactions when two interfaces close- : / ' A / A

A
/ / / / *
7 f//
-
ly approach each other. This improvement
of the adhesion was mainly studied by the
analysis of crack propagation at the inter- 100
84K :
face between dissimilar materials. It was :
shown that the adhesion at the interface may :
I /// A 282K ;
A 355K
be improved by up to a hundred times that
of the neat interface.
/^ 900K
10 ~ i , i ~
Figure 8-11 shows the variation of the i ,

20
i i i

40
i

60
i

fracture energy of the interface as a function
of the BCP film thickness added at the inter-
face for various molecular weights of BCP
(Char et al., 1993). The toughness of the
interface increases exponentially with the
amount of block copolymer added. In gen-
eral, it is shown that the main controlling
parameters are the molecular weight of the
BCP, the amount of BCP added, the degree
of symmetry of the BCP, and the structure
of the interface after annealing.
Depending on these parameters, several
fracture mechanisms may be observed. For
low molecular weight BCP, the blocks are
too short to promote entanglements with the
matrix polymer and the resulting fracture
mechanism is pullout of the less entangled
block. For very high molecular weight BCP,
the saturation coverage of the interface
becomes low. Then, although the blocks are
well entangled, fracture occurs through
breaking of the BCP near the joint segment
(Creton et al., 1992). This is exemplified in
Fig. 8-12 with a plot of the maximum
obtainable toughness as a function of
the molecular weight of a symmetric
PS-PMMA BCP at a PPO/PMMA interface
(Char et al., 1993). The highest toughness is
obtained with a BCP with molecular weight
low enough to give high coverage, but also
large enough to promote entanglements
with the matrix.
When fracture propagates through plastic
deformation of the interfacial region, the
interfacial toughness is directly related to
80 100
BCP film thickness (nm)
Figure 8-11. Interfacial toughness Gc versus the
thickness of the film of PS-PMMA BCP added at the
PS/PMMA interface. The tests were performed after
annealing bilayer specimens for 2 h at 150 C (Char
etal., 1993).
500
_E 0
100 200 300 400 500 600
BCP molecular weight x 103
Figure 8-12. Highest obtainable interfacial tough-
ness versus the BCP molecular weight in
PPO/PMMA/PS-PMMA BCP systems (Char et al.,
1993).
the entanglement density. For interfaces at
equilibrium, with well-ordered and regular-
ly distributed BCP, theories based on mean-
field calculations were developed to calcu-
late the entanglement density and the corre-
lated interfacial toughness (Creton et al.,
1992). It was shown that the toughness of
the interface depends on the square of the
surface coverage (Zc), which perfectly fits
the results shown in Fig. 8-11. Moreover,
 8.3 Interfacial Activity of Block and Graft Copolymers
the pullout mechanism of fracture could be
predicted by calculation of the effective
entanglement density of the BCP with the
homopolymers (Creton et al., 1992).
However, for systems with a homopoly-
mer of low molecular weight, if homopoly-
mer chain has an effective entanglement
with the brush, it must also have another
entanglement with the homopolymer in
order to realize bridging of the brush and the
homopolymer. The effective entanglement
concept of the previous model must be rec-
tified by the bridging probability (Washiya-
ma, 1995). The correlation between experi-
ment and theory was found to be very good.
Figure 8-13 illustrates this correlation for a
PS/PVP interface modified by a PS-PVP
BCP as a function of the PS homopolymer
molecular weight. The ordinate axis is the
toughness of the interface reported to that
of the system with high PS molecular
weight. Including the bridging probability,
a much better fit of the experimental results
is obtained.
CO
CO
CD
c why we will consider this case in the next
O)
o paragraph, even though it can hardly be
.H
B A polymer bearing adsorbing groups may
CD
s6
CD
"0.01
500 1000 10000
Degree of polymerization of the PS
Figure 8-13. Ratio of the interfacial toughness to that
measured with a PS of degree of polymerization 6440
versus the degree of polymerization of the PS in
PS/PVP/PS-PVP BCP systems. Full squares: experi-
mental results, triangles: theory including the effec-
tive entanglement density concept, and circles: theo-
ry including both the effective entanglement density
and the bridging probability (Washiyama, 1995).
443
It is surprising that the disorder of a BCP
layer at an interface was also found to be
beneficial to the interfacial toughness. This
is also explained by the higher entanglement
density throughout the disordered interface
(Brown et al., 1993). Upon annealing, order
is obtained and the fracture toughness
decreases. This may be particularly dramat-
ic for BCP layer thicknesses greater than the
thickness of BCP at interfacial saturation.
In this case, lamellar microdomains of BCP
may form parallel to the interface. The inter-
lamellar region was found to be quite weak,
and this weakness is enhanced still further
if low molecular weight components are
concentrated in this region (Washiyama
etal., 1993).
Beside improvement of the interfacial
adhesion, the BCP at an interface promotes
repulsive interactions when two interfaces
are closely approached. Indeed, compress-
ing a brush would cause a change in the scal-
ing in Eq. (8-9), which in principle would
cost energy. In polymer melts, this results in
a reduction of the coalescence of dispersed
particles. Such repulsive forces could not be
measured in polymer melts, but they could
be measured in dilute solutions. That is
applied to the case of BCP brushes in poly-
mer melts.
form a brush on a substrate and, with the
apparatus designed by Israelachvili (Horn
and Israelachvili, 1981, 1988; Israelachvili
et al., 1984), the force as a function of the
distance (from 0 to 300 nm) between two
brushes could be measured directly (Taun-
ton et al., 1988; Hadziioannou et al., 1986).
For PVP-PS BCP adsorbed on mica from
toluene solution, the force measured as a
function of the distance between two mica
plates is plotted in Fig. 8-14. The first the-
ories behind this behavior assumed a step
444 8 Reactive Processing of Polymer Blends: Polymer-Polymer Interface Aspects
200 400 600 800 1000 1200 1400
Separation between surfaces (A)
Figure 8-14. Force of a brush versus the separation
between the plates. Dark and open points: experimen-
tal results. Dotted curve: theory assuming step distri-
bution profile of the brush. Dashed curve: self-
consistent field theory. Solid curve: self-consistent
field theory considering the polydispersity of the
brush (Milner, 1988).
function for the concentration profile of the
brush (Alexander, 1977). The predictions of
the theories are given by the dotted curve in
Fig. 8-14. However, it was recently shown
that the concentration profile of a moderate-
ly concentrated brush has a parabolic shape
(Milner, 1990). With this parabolic profile,
the dashed curve in Fig. 8-14 gives a better
fit to the results (Milner, 1988; Milner et al.,
1988).
The polydispersity is an important factor
affecting the interaction of closely approa-
ched brushes. For similar molecular weight
polymers, a larger polydispersity gives
longer range interactions. Taking account of
the polydispersity, the experimental points
could be correctly fitted as shown by the
solid line in Fig. 8-14.
The steric interactions act between dis-
persed particles in polymer blends and
therefore reduce the coalescence rate. The
other reason for the reduction of the coales-
cence rate is the "immobility" of the inter-
face induced by the presence of BCP (Favis
and Willis, 1990; Elmendorp, 1986; Elmen-
dorp and Van Der Vegt, 1986).
It was shown in this section that modifi-
cation of the interface by the BCP is great-
ly dependent on the brushes formed on both
sides of the interface: the stretching of the
blocks is responsible for the reduction of the
interfacial tension. The entanglements
between the blocks and the corresponding
homopolymer are responsible for the
improved adhesion, and steric interactions
between brushes help inhibit the coales-
cence. Such "brush effects" cannot be
obtained with interfacial modification by a
homopolymer component even if the inter-
facial tension may be reduced in this case
(Noolandi, 1994).
8.4 Interfaces in Reactive Blends
8.4.1 In Situ Formation of Block and
Graft Copolymers by Reactive Blending
As stated before, interfacial modification
by block or graft copolymer is quite power-
ful for the control of the particle size, the
morphology stability, and the interfacial
adhesion. Such a block or graft copolymer
can be produced in situ by reaction between
specific chemical groups of the components
of the blend.
Table 8-3 gives a list of several reactions
that may be applied for the interfacial mod-
ification in polymer blends (Liu and Baker,
1992). For the notation used, P A is any poly-
mer bearing the reactive group and P B is the
one with the coreactive group.
Among the reactive blends, blends
involving polyamide as one of the compo-
nents have been studied, extensively, start-
ing with the works of Ide and Hasegawa
(1974), and provide greately improved
toughening (Epstein, 1979). For polyamide
6 systems, many reactions are conceivable,
as shown in Table 8-4.
 8.4 Interfaces in Reactive Blends 445

Table 8-3. List of the most important reactions used for interface modification by in situ formed BCP a .

Reaction type Reactive group Coreactive Reaction equation

group

Addition/substitution
Amidation carboxyliac acid amine PACOOH + P B NHR- A C O - N R - P B + H2O

CO
Imidation MA PA-C7 V +PB-NH2- hH2O
N-PR
C
/x
CO
Esterification carboxylic acid hydroxyl PACOOH + PBOH > A C - O - P R + H2O
and MA O

Concerted addition maleate double bond

and MA
O R O
II I II
Urea formation carbodiimide carboxylic acid PAN=C=NR + P B COOHP A NHC-N-C-P B
Urethane formation isocyanate hydroxyl P A - N = C = O + PB OH-PA NH CO-OP B
Substitution amine hydroxyl/halide PA NH2 + PBX(X = OH.Br) - PANHPB + HX

Interchange reaction
Aminolysis ester amine PACOOR + P B N H 2 ^ - P A CONHP B + ROH
Ester interchange ester ester P A -COOP A + P B COO P A COOP B
Transesterification ester hydroxyl phenol PACOOP + P B OH *- P A COO^P B + ROH
Amide-ester exchange amide ester P A -CONHP A + P B C O O P B
P A CONHP R + RCOOPA

Ring-opening reaction
O
Epoxide ring epoxide hydroxyl PAO+PR-- - P A CH(OH)CH2OPB

amine B N H 2 - PACH(OH)CH2NHPB
O
carboxylic acid PBCOOH -+ P A -CH(OH)CH 2 -O-C-P B

Oxazoline ring oxazoline carboxylic acid PA<( J + P B COOH * PACNHCH2CH2OCPB

O

phenol PAC-NHCH2CH2-O-P

o
II
Lactam ring lactam P A - N - C O + P B N H 2 - ^ P A NHC-(CH 2 hNHP B
v
(CH 2 ) 3

Ionic bonding
Pyridine/amine acid PANH3 + P B SO 3 H^ PANHR3SO3PB
Ionomer ionomer (PASO3)2Z^+ (PBSO3)2Zn ^ P A s6 3 Zns6 3 P B

a
PA indicates polymer A and P B indicates polymer B.
446 8 Reactive Processing of Polymer Blends: Polymer-Polymer Interface Aspects

Table 8-4. List and examples of reactions used for in situ interfacial modification in reactive blends containing
polyamide 6.

Polyamide Other polymer Reactive group Concentration References

PA6 PP-g-MA anhydride 1.15% Ide and Hasegwa (1974)

3% Park etal. (1990)
0.5% Holsti-Miettinen et al. (1992)
ExxelorPO2011 Rosch and Mulhaupt (1993)
PA-6 PP/E co butyl- fumaric acid 0.4% Holsti-Miettinen et al. (1992)
acrylate-g-
fumaric acid
PA6 PP/ionomer methacrylic acid, 20% Favis and Willis (1990)
isobutyl aery late
70% neutralized
with Zn
PA6 PE-g-MA anhydride 3% Serpeetal. (1990)
PA6 PE-co-YA vinyl acetate 20-30% D'Orazio et al. (1986)
or to 40% Addonizio et al. (1991)
PA-6 PE-co-BA butyl acrylate 17.6% Ravaletal. (1991)
PA-6 PE-co-MAA methacrylic acid 6.8-18% Macknight et al. (1985)
PA-6 PE-co-EA ethyl acrylate 8 or 25% Kung and Williams (1988)
PA6 PE/C1PE chlorinated PE 36-40% Deaninetal. (1990)
PA-6 PE-g-AA acrylic acid 3.5-6% Deaninetal. (1990)
PA-6 PE functionalized carbonyl 0.07,0.11, Curtoetal. (1990)
by photooxidation 0.28 mol/1
PA-6 ionomer (Du Pont Surlyn Borggreve et al. (1988)
9950 with Zn cation)
PA-6 EPDM-g-MA anhydride 0.1,0.2,0.4, Borggreve et al. (1988)
and 0.8%
PA-6 EPR-g-MA anhydride 3% D'Orazio etal. (1988)
0.6, 2.4, or 4.5% Greco etal. (1987)
0.7% Ban etal. (1988)
PA-6 PS-co-MA anhydride 11-25% Chang and Hwu (1991)
2.6 or 13% Takeda and Paul (1992)
2% Angola etal. (1988)
15 and 30% Angola etal. (1988)
8% Kim and Park (1991)
KratonG 1901 X Rosch and Mulhaupt (1993)
208 mmol/kg
PA-6 PS-&-MA anhydride chain end 85 or 60% Park etal. (1992)
of the chains
PA6 PS-co-MAA methacrylic acid 10% Ide and Hasegawa (1974)
PA-6 PS-oxazoline oxazoline 1% Takeda and Paul (1992)
PA6 PS-glycidyl glycidyl 3% Chang and Hwu (1991)
methacrylate methacrylate
PA6 sulfonated PS sulfonic acid 2.2, 5.4, or Molnar and Eisenberg (1991)
or sulfonic acid 9.7 mol%
neutralized with Li
PA-6 ABS/SMA anhydride 30% Triaccaetal. (1991)

Table 8-4. (continued)
Polyamide Other polymer Reactive group
PA-6 ABS-g-MA anhydride
PA-6 ABS-g-oxazoline oxazoline
PA-6 SEBS-g-MA anhydride
PA6 PET amide ester
interchange reaction
catalyzed by
p-toluene sulphonic
acid
PA6 PA 66 amidation organic
phosphites
In the reactive systems in Tables 8-3 and
8-4, the concentration of the reactive group
may be varied. Moreover, in some cases, a
catalyst may be added in order to improve
the reaction kinetics.
Comparing the efficiency of interfacial
modification of various reactive groups with
polyamide, it was found, for example, that
the sulfonic acid group is better than the car-
boxylic acid group (Molnar and Eisenberg,
1991), and the anhydride group is more effi-
cient than the carboxylic acid group
(Epstein, 1979), showing that high reactiv-
ity of the reactive group with the polyamide
is important for efficient interfacial modifi-
cation. To balance the lack of reactivity of
carboxylic groups with polyamide, their con-
centration was increased up to 10% (Deanin
et al., 1990) or 20% (Favis and Willis, 1990).
Even with a high concentration of acetate
groups, some instability of the morphology
was still observed in PA/PE-co-vinyl acetate
blends (Addonizio et al., 1991).
However, the processing temperatures of
the polymers are generally between 180 and
300 C. Therefore, beside the well-known
room temperature chemistry, other "unex-
pected" reactions may occur. For example,
for the amine-anhydride reaction, which is
8.4 Interfaces in Reactive Blends 447
Concentration References
1% Aoki and Watanabe (1992)
1% Triaccaetal. (1991)
2% Holsti-Miettinen et al. (1992)
1.84% Oshinskietal. (1992)
Pillon and Utracki (1984)
1% Aharonietal. (1984)
Largman and Aharoni (1984)
widely used in polyamide blends, different
assumptions were made for the occurrence
of a parallel amide-anhydride reaction
(Borggreve and Gaymans, 1988), which
were nevertheless found to be negligible
under normal polyamide processing condi-
tions (Marechal et al., 1995). Moreover, in
general there are very few published data on
the reaction kinetics at high temperatures in
a molten polymer medium (Guegan et al.,
1994). In spite of the lack of such informa-
tion, the most important and well-established
phenomena in reactive polymer blends will
be described in the following sections.
At first, it is quite obvious that the product
of the reaction between two immiscible poly-
mers is a block or a grafted copolymer. It may
have a quite complicated structure, since
after reaction some insoluble fraction may be
found even in a good solvent of the two com-
ponents of the blend (Guegan et al., 1993;
Baker and Saleem, 1987). However, at least
it is possible to discuss the location of the
block or graft copolymer after the reaction.
In the case of a PA 6/maleic anhydride
grafted PP blend, the unreacted polyamide
could be removed by solvent extraction; the
remaining particles were then dispersed in
epoxy resin, microtomed, and stained with
448 8 Reactive Processing of Polymer Blends: Polymer-Polymer Interface Aspects
0.1 put
Figure 8-15. TEM observation of PP particles sur-
rounded by the reacted PA of a PA 6/maleic anhydride
grafted PP blend. PP particles accompanied by the
grafted PA were separated, dispersed in epoxy resin,
microtomed, and stained with iodine. The grafted
PA 6 appears dark around the PP particles (Yokoya-
maetal., 1994).
iodine before TEM observation. Iodine
stains PA preferentially, so that the grafted
PA 6 appears dark around the PP particles,
as shown in Fig. 8-15 (Nishio et al., 1991).
This clearly shows that the reaction produc-
es graft copolymer which tends to remain at
the interface.
The situation may however, be slightly
different in a system where the interfacial
area is not mechanically extended. For
example, it was shown that by static anneal-
ing of a bilayer system made of amorphous
PA (Grilamide TR 55 LX) and poly(styrene-
co-maleic anhydride), the interfacial thick-
ness measured by ellipsometry increases as
the reaction proceeds (Yokoyama et al.,
1994; Okamoto and Inoue, 1993). However,
it was also shown by TEM that micelles with
an SMA core are diffusing into the PA phase
(Higashida and Inoue, 1994). This shows
that when the interface cannot be extended,
the BCP may escape from the interface.
However, the mechanism is still not clear.
In the following sections, special atten-
tion will be paid to the main results concern-
ing the control of the morphology develop-
ment in reactive polymer blends, the param-
eters controlling the reaction kinetics at an
interface, the relative advantages of the in
situ versus the pre-made block or graft
copolymers, and the effect of interfacial
modification on the mechanical properties
of reactive blends.
8.4.2 Effects of Chemical Modification
on Morphology Development
Because of the importance of the mor-
phology in relation to the mechanical prop-
erties of polymer blends (Fig. 8-1), the pre-
diction and control of the final particle size
is of primary importance. From the early
work of Taylor describing the stability of a
Newtonian droplet of diameter d suspended
in another Newtonian liquid undergoing a
steady shear flow shear rate y, the dimen-
sionless Weber number or capillary number
(We = rim ydld), which is the ratio of the
shear forces (T]m y) to the interfacial forces
of the droplet {aid), is generally the starting
point for all predictions of the particle size
in polymer blends. When the Weber num-
ber of a particle is above the critical Weber
number, the particle will break, otherwise it
cannot (Taylor, 1932, 1934). For polymer
blends with a fixed volume fraction of dis-
persed phase, Wu (1987) pointed out that the
critical Weber number was a function of the
viscosity ratio (p = T]d/7]m)
-f(p) (8-11)
The function f(p) was defined by plotting
the Weber number as a function of the vis-
cosity ratio (/?), as shown in Fig. 8-16. There
is a minimum at p = 1.
In Fig. 8-16 both reactive and nonreactive
blends are found. To calculate the Weber
number for the reactive blend, an interfacial
tension of 0.25 mN/m at 280 C was used,

100
PET/EP rubbers
Nylon Z-1/EP rubbers
Nylon Z-2/EP rubbers
A Nylon Z-1/EPX rubbers
10
1 I
0.1 1 10
Viscosity ratio p
as measured by the pendent drop method
(Wu, 1982). For the corresponding nonre-
active PA/EPR blends the interfacial tension
was much higher at 9.7 mN/m. All effects
of the reaction on the interface were
assumed to affect the interfacial tension.
Therefore, when the particle size is known,
Eq. (8-12) is sometimes employed to calcu-
late the relative interfacial tension with a
reference value for the nonreactive blend
(Tang and Huang, 1994).
In subsequent work by Serpe and co-
workers (Serpe et al., 1990), it was found
that upon variation of the dispersed phase
volume fraction, the particle size is changed.
An additional empirical factor was intro-
duced into Eq. (8-12) to consider this effect.
Moreover, in the formulation of the Weber
number used by Wu, the term representing
the mechanical force only included the vis-
cosity of the matrix phase (7]m). This proce-
dure is valid in relatively dilute systems,
while in concentrated ones, the viscosity of
the blend (rjb) should be more representative
of the actual mechanical forces. As a matter
of fact, in a concentrated system with good
dispersion of the phases, the viscosity
becomes higher than that of the matrix (Plo-
chaki, 1983; Sherman, 1968; Utracki and
8.4 Interfaces in Reactive Blends 449
Figure 8-16. Dimensionless
master curve of yrjm dla ver-
sus p after melt of different
polyamide and PET/rubber
blends. EPX means reactive
rubber (Wu, 1987).
100
Kamal, 1982). The improved formulation
given by Serpe and co-workers is
a
d= -ftp) (8-12)
The effect of the coalescence was pre-
sumably introduced in the composition
dependent factor [l4(<Pd # m ) 0 " 8 ]. How-
ever, the coalescence process is also depen-
dent on the interfacial modification (Elmen-
dorp, 1986). It would therefore be very
interesting to distinguish between the
respective effects of the reduction of the
interfacial tension and the inhibition of the
coalescence on the particle size. For this dis-
cussion, Fig. 8-17 shows the mean particle
size measured by light scattering4 as a func-
4
Compared with electron microscopy, light scatter-
ing (LS) is a remarkably rapid method for the charac-
terization of the morphology of submicrometer to sev-
eral micrometers size. For two-phase blends, the
Debye-Bueche analysis often holds to obtain the cor-
relation length () (Debye and Bueche, 1949). From
this parameter, the mean particle size (d) and the spe-
cific interfacial area (Ssp) are easily calculated, i.e.,
d=l.5 /(l -<2>)andSsp = 4 0(1 - <)/ as soon as the
volume fraction of the dispersed phase is known. LS
is also quite powerful for the analysis of the size reduc-
tion during mixing and of the coalescence kinetics of
blended materials (Okamoto and Inoue, 1993).
450 8 Reactive Processing of Polymer Blends: Polymer-Polymer Interface Aspects
Nonreactive
1.5 - o Reactive
Coalescence
^-Taylor limit
0 10 20 30 40 50
Fraction of dispersed phase (wt.%)
Figure 8-17. Diameter measured by light scattering
versus the weight fraction of the PMMA dispersed
phase in PS/PMMA blends mixed at 180C in the
minimax molder. Full points: nonreactive blends.
Open points: reactive blends. With cr=1.5mN/m,
p = 3l, ??m = 420 Pa s, and 7= 21 s"1, the Taylor pre-
diction in the low concentration limit is 0.15 jLtm
(Nakayama, 1994).
tion of the weight fraction of the dispersed
phase for PS/PMMA and PS-COOH/
PMMA-epoxy blends (Sundaraj, 1994;
Nakayama, 1994). [These blends were
mixed in a small scale Maxwell mixer (Max-
well, 1972) at HOrpmand 180C].
For the nonreactive blend, the particle
size significantly depends on the volume
fraction of the dispersed phase. This behav-
ior was well integrated by Eq. (8-12). How-
ever, for the reactive blend, the dependence
of the particle size on the dispersed phase
volume fraction was much smaller. More-
over, when comparing the limiting particle
size for a small volume fraction of the dis-
persed phase, there is only a very small dif-
ference between the reactive and the nonre-
active blends. In this range of concentra-
tions, the coalescence process becomes very
slow and may reasonably be neglected.
Therefore the particle size may be compared
to the prediction of the Taylor law giving the
biggest size of a particle that cannot break
up. The result of this calculation, with inde-
pendently measured interfacial tension, is
presented as an horizontal line called the
Taylor limit in Fig. 8-17. Both the reactive
blend and the nonreactive blend have a par-
ticle size above the Taylor limit. The differ-
ence could either be explained by a visco-
elastic effect of polymer melts (Milliken and
Leal, 1991; Bousfield etal., 1986; Van
Oene, 1972) or by difficulties in accurate
estimations of the actual shear stresses.
Nevertheless, near the Taylor limit the
difference existing between the particle size
of the reactive and the nonreactive blends is
only due to the interfacial tension reduction.
For higher volume fractions, the difference
in the particle size observed is far more
important. Therefore the smaller particle
size observed in reactive polymer blends
seems to mainly result from inhibition of the
coalescence process.
The reduction of the coalescence rate in
reactive blends is well exemplified in
Fig. 8-18 in the case of PS-COOH/
PMMA-epoxy (70/30) blends, where the
coalescence rate at 180C as measured by
light scattering (LS) is plotted as a function
of the relative interfacial coverage (SQ/SC) in
a block copolymer (Nakayama, 1994). In
Fig. 8-18, the abscissa is the surface per
BCP at saturation of the interface (50),
which was calculated from Eq. (8-10),
divided by Sc.
It is observed that the coalescence rate in
a static condition decreases rapidly with the
interfacial coverage, and that above a criti-
cal value the coalescence is completely
inhibited. It is also remarkable that this crit-
ical value of Sc is much larger than the sat-
uration value. Again the results emphasize
the important reduction of the coalescence
rate brought by the in situ formed BCP.
Since it was shown in this part that inter-
facial modification by in situ formed block
or graft copolymer is a quite efficient way
to control the morphology and improve the
morphology stability, the next question is

0.3
o R1
A R2
O R3
+ R4
0.2 A R5
R6
CO
CD R7
o
V NR
0.1
CO
o a>
O CD
0 0.4 0.8 1.2
Relative interfacial coverage S0/Sc
Figure 8-18. Coalescence rate upon static annealing
at 180C of different PS/PMMA blends versus the
interfacial coverage of the BCP relative to the satu-
rated interface S0/Sc (Nakayama, 1994).
how fast is the interfacial modification in
reactive blends.
8.4.3 Kinetics of the Interfacial Reaction
In comparison with the reaction rate in an
inhomogeneous system, effects of the mix-
ing rate, the dispersability of the materials,
the chemical reaction rate, the polymer chain
diffusion rate, and the presence of a catalyst
can be expected in the interfacial reactions.
A kinetic analysis on interfacial modifi-
cation was carried out for OH-terminated
-caprolactone (PCL)/a,co-carboxy termi-
nated poly(butadiene) or poly(butadiene-
co-acrylonytrile) (CTBR or CTBN) blends
with a coupling agent: y-aminopropyl tri-
ethoxysilane (APS (Okamoto and Inoue,
1993). Figure 8-19 shows the dependence of
the fraction of rubber converted to BCP on
8.4 Interfaces in Reactive Blends 451
CJ
(wt.%)
0) 2.0
_Q
-Q CTBR >/
faction of cc)nverted i
en
/ / CTBN
b
/
0.5
/
n/ I I I
0 1 2 3
APS content of the blend (wt.%)
Figure 8-19. Weight percent of liquid rubber con-
verted to BCP versus the APS content for PCL/CTBR
or CTBN/APS blends mixed for 5 min at 120 C (Oko-
moto and Inoue, 1993).
the coupling agent content. The BCP con-
tent was measured by GPC5 in THF. Obvi-
ously, the APS improved the reaction kinet-
ics and resulted in a higher conversion level.
As expected from the interfacial modifi-
cation by BCP, the particle size was reduced
in proportion to the content of BCP. This is
exemplified in Fig. 8-20 where the specific
interfacial area, relative to that of the corre-
sponding blend without APS, is plotted as a
function of the APS content. By comparing
Fig. 8-19 and 8-20, it is seen that APS
improves the reaction level and consequent-
ly the morphology becomes finer.
5
Gel permeation chromatography (GPC) is a unique
technique for the characterization of the reaction level
in polymer blends for system with a common solvent.
The product of the reaction, BCP or GCP, is general-
ly of higher molecular weight than the initial compo-
nent polymers. Hence it can be distinguished from the
unreacted polymer (Okamoto and Inoue, 1993). Quan-
titative analysis may be obtained using a good choice
of detector.
452 8 Reactive Processing of Polymer Blends: Polymer-Polymer Interface Aspects
1.2
- (a)
^ -
I -8
CTBN
0.4 - CTBR
CO
0 i i 1 i i
5.0 - (b)
CTBR
CO
3.0 -
- /^ CTBN
1.0
1 i
0 1.0 2.0
APS content of the blend (wt.%)
Figure 8-20. (a) Rate of increase of the specific inter-
facial area Ssp during processing, and (b) normalized
rate: Ssp divided by the rate of increase of the specif-
ic interfacial area without APS (Ssp0) versus the APS
content for PCL/CTBR or CTBN/APS blends mixed
at 120C (Okomoto and Inoue, 1993).
Similar results were obtained for a ternary
system, for example, a PA 6/maleic anhy-
dride grafted PP/PP system, where an
increased concentration of the reactive
groups is beneficial for obtaining a higher
concentration of BCP (Rosch and Mul-
haupt, 1993). This was shown by keeping a
constant dispersed phase volume fraction in
a ternary blend and varying the ratio of reac-
tive to nonreactive component. If the parti-
cle size is plotted as a function of the frac-
tion of reactive component, it has similar
shape to that shown for the interfacial ten-
sion as a function of the content of BCP in
Fig. 8-10; the particle size decreases rapid-
ly for small concentrations of reactive com-
ponent, but on increasing the concentration
of the reactive component further, the par-
ticle size decreases more and more slowly
down to that of the fully reactive system.
The mixing rate is also important for the
development of the reaction at the interface.
Such an effect was found in polyamide
50
"O CD Complete
C "O conversion
40
I O 10 rpm
-Or~ 30 rpm
30 O 75 rpm
20
CO
t
E 10
(2 minutes of mixing)
CD
0
0 10 20 30 40 50 60
Anhydride introduced in the blends with
the EP-g-MA in ^imol g~1 of polyamide
Figure 8-21. Conversion level versus EP-g-MA
i
weight fraction in PA 6/EP-g-MA blends mixed for
3.0
2 min at 240 C at 10, 30, and 75 rpm in a Brabender
batch mixer (Marechal, 1993).
6/reactive rubber blends (Marechal, 1993;
Marechal et al., 1992). In Fig. 8-21 the reac-
tion level, calculated from amine chain end
titration results6, is plotted as a function of
the anhydride group concentration intro-
duced in the blend with the reactive rubber.
The blends were mixed for 2 min at 240 C
at various shear rates.
It is observed that the reaction level is
higher for the blends mixed at high shear.
High shear promotes fast dispersion and dis-
tribution of the materials and therefore gives
a larger specific interfacial area (5sp).
Hence, since the reaction occurs at the inter-
face, the larger Ssp gives a faster reaction.
It must be stressed that upon further pro-
cessing the blends in Fig. 8-21, the reaction
Titration is quite helpful for the characterization of
the reaction level. Of course, it must be ensured that
the reaction between the blend components does not
progress significantly in the titration solution. For
example, amine chain end titration of the polyamide
is an accurate method for the analysis of the reaction
level in polyamide blends (Waltz and Taylor, 1947;
Kruissinket al., 1958; Hermans et al., 1958; Giori and
Hayes, 1970). However, below 10 jimol of amine per
gram of PA the accuracy of the technique becomes
poor (Waltz and Taylor, 1947).
 8.4 Interfaces in Reactive Blends 453

levels of the blends mixed at 30 and 75 rpm 1 1 i i

do not improve. For the blends mixed at CO

10 rpm, although improving during pro- 0.8 60 I
cessing, the reaction level never gets as high
CD
as under high shear mixing. This could be 0.6 50 r
due to a reduction of the reaction rate as the 03

interface coverage with the BCP approach- 0.4

es saturation (see Figs. 8-25 and 8-26).
Therefore, with constant total deformation
(shear multiplied by mixing time), a high
shear is favorable to the reaction rate.
In relation to the effect of the specific
interfacial area, it was also shown that the
initial state of dispersion of the materials
before mixing is important for the final con-
version level. It was shown in PS-COOH/
PMMA-epoxy blends that the reaction level
is higher when powdered materials are
mixed than when pellets of the same poly-
mers are mixed (see Fig. 8-26 and Table
8-5 in next section) (Nakayama, 1994).
A high specific interfacial area and a thick
interface should be favorable to the reaction
rate. Indeed, a thick interface can either be
obtained by adjusting the % value between
the two polymers (Paul, 1993, 1994;
Majumdar et al., 1994) or by the addition of
small molecules at the interface (Lambla,
1991; Seadan, 1992). In both cases, the reac-
tion level was found to be improved. For
example, the % value of polyamide x, x with
SEBS-g-MA is a function of x. For small x,
the amide groups are numerous and there is
a very narrow interface. For larger x, the
polarity of the PA is lower and this gives a
broader interface. Figure 8-22 shows the
reaction level calculated from amine chain
end titration results and an estimate of the
interfacial thickness of these PA-JC, x/SEBS-
g-MA blends as a function of the amide/
methyl ratio of the polyamide. The blends
were processed in a single screw extruder at
240 C. It is observed that a thin interface
(high amide concentration) is disfavorable
to the reaction level.
5,9/
40
CD
CL
\
\*6,10
D
CD
0.2 - 30 "cc
12,12
6,12
1 I LLJ
I I 20
11 13
NHCO/CH 2 Of the PA
Figure 8-22. Reaction level and estimate of the inter-
facial thickness versus the amide/methyl ratio of the
polyamide of PA-x,x/-SEBS-g-MA blends processed
in a single screw extruder at 240 C (Paul, 1994).
For further discussion on the reaction
kinetics at an interface, a comparison with
the adsorption of polymer chains from a
dilute solution on a substrate can be made.
In both cases, the reactive/adsorbing group
has to reach the interface before undergoing
reaction/adsorption.
The kinetics of adsorption from a dilute
solution were found to be limited by diffu-
sion of the chains from the solution to the
interface. As the coverage of the interface
increases, the adsorbing chains have to cross
a layer of grafted chains forming a wet brush
at the interface. As shown in Fig. 8-23, the
adsorbing chain has to overcome a steric
repulsive barrier (Ligoure and Leibler,
1990).
As the adsorption progresses, the brush of
adsorbed chains becomes denser and dens-
er, and it is more and more difficult for poly-
mer chains to reach the interface. Conse-
quently, the adsorption kinetics decrease
with coverage of the interface (Hugenard
et al., 1991). Figure 8-24 shows an example
of the evolution of the adsorption kinetics
with the surface coverage in the case of the
454 8 Reactive Processing of Polymer Blends: Polymer-Polymer Interface Aspects

, Brush

S
0
(D

o Figure 8-23. Schematic pro-

Q_ file of the potential energy act-
ing on a chain penetrating a
grafted layer of macromole-
cules. ji is the maximum of the
potential barrier for a given
coverage and A is the energy
gain by adsorption (Ligoure
andLeibler, 1990).

10" As diffusion is strongly dependent on the

10~ 6
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Surface coverage (mol/cm2)
Figure 8-24. Kinetic coefficient of adsorption versus
surface coverage for a PVP-PS BCP adsorbing on sil-
ica from a toluene solution (Hugenard et al., 1991).
adsorption of a PVP-PS BCP on silica from
toluene solution. As the interface becomes
saturated in block copolymer, a dry brush
tends to form and, at this point, any progres-
sion of the reaction/adsorption becomes
quite improbable. This is exemplified in the
right part of Fig. 8-24 with a more rapid drop
of the adsorption kinetics.
molecular weight, it should be interesting to
analyze the importance of the molecular
weight of the reacting molecules. For exam-
ple, in polyamide 6/reactive rubber blends,
the molecular weight of the free polyamide
as well as that of the grafted polyamide
could be measured. Figure 8-25 shows these
molecular weights as a function of the reac-
1.4 tion time for various rubber concentrations
(Marechal, 1993; Marechal et al., 1993 a).
The rubber particles with the grafted poly-
amide can be separated by centrifugation.
Then the molecular weight of the nonreact-
ed polyamide was measured by viscometry
and that of the grafted by dividing the weight
of grafted PA by the reaction level. The
decrease of the molecular weight during
mixing was explained by hydrolysis of the
polyamide after amine chain end reaction
with the anhydride of the rubber (Marechal
et al., 1995; Marechal, 1993). However, the
most striking effect is that the molecular

[75 rpmj
O PA/20%EPMA
O PA/30%EPMA
D PA/40%EPMA
8 12
Mixing time (min)
weight of the grafted polyamide is about
half that of the unreacted polyamide. This
difference could only be explained by a fast-
er reaction at the interface of the chain ends
of the polyamide chain of low molecular
weight.
This was called molecular weight segre-
gation induced by interfacial reaction. In the
case of a fast reaction and of a reaction
involving end groups like in PA 6/EPR-g-
MA blends, it may originate mainly from
chain elasticity effects at the interface. It
may also partly be caused by the diffusion
kinetics and segregation of low molecular
weight species at the interface (see
Sec. 8.2.2). The effects of these various phe-
nomena should be modulated by varying the
mixing conditions, reaction rate, concentra-
tion of reactive groups, location of the reac-
tive groups on the chain, and fraction of
reactive chains (Marechal, 1993; Marechal
etal., 1993 a).
8.4.4 Pre-Made Versus In Situ Formed
Block Copolymers
From a technological point of view it
should be very interesting to compare the
effects of pre-made BCP and in situ formed
BCP on the interfacial modification. This
8.4 Interfaces in Reactive Blends 455
Figure 8-25. Number average molec-
ular weight of the nonreacted poly-
amide (open symbols) and the reacted
polyamide (full symbols) versus the
mixing time for PA 6/EP-g-MA blends
mixed at 75 rpm and 240 C in a Bra-
bender batch mixer (Marechal, 1993).
16 20
comparison was made for PS(40K)/
PMMA(40K)/symmetric BCP(80K) non-
reactive and PS-COOH(40 K)/PMMA-
epoxy(40K) reactive blends. All compo-
nent polymers had narrow molecular weight
distributions. For both, since the equilibri-
um of the interface should be the same, the
kinetics of interfacial modification by pre-
made or in situ formed BCP can be com-
pared. Figure 8-26 shows the particle size
measured by LS as a function of the mixing
time for nonreactive blends, one with BCP
(Bp 1) and one without (NR 1), and two reac-
tive blends mixed from initial pellets (R 1)
or powder (R4). For these blends, the con-
tent of BCP was determined by GPC.
Table 8-5 summarizes the results of particle
size and BCP content (Nakayama, 1994).
It is remarkable comparing Pb 1 and R 1
that the particle size is smaller in the reac-
tive blend although the content of BCP is
lower. This is explained by the fact that in
the case of Pb 1, not all the BCP is at the
interface. In Fig. 8-27 part of the pre-made
BCP is found in the form of micelles in the
PS phase. In this TEM micrograph, the PS
phase was stained with RuO4. Such micelles
could not be observed for the R1 and R4
blends. Therefore the specific interest of the
in situ formed block copolymer comes from
456 8 Reactive Processing of Polymer Blends: Polymer-Polymer Interface Aspects

c5
CO

CC
CD

200 nm
Figure 8-27. TEM picture of Pb 1 blend (see Fig.
8-26) mixed for 15 min. The PS is stained with RuO4
and appears darker (Nakayama, 1994).
10 15 20 25
Mixing time (min)
Figure 8-26. Mean particle diameter measured by this ternary system, the EPR-g-MA was first
light scattering versus mixing time for different mixed with the PA, then after complete reac-
PS/PMMA blends mixed at 180C in the mini-max- tion, the EPR was added. The interfacial
molder from Custom Scientific Instrument. NR1:
nonreactive; Pb 1 with 5% pre-made BCP; R 1 and R4 modification of the EPR particles was found
reactive system mixed from pellets and powder, to be very slow, and large EPR particles
respectively (Nakayama, 1994). were surrounded by small EPR-g-MA par-
ticles (Marechal, 1993; Marechal, et al.,
Table 8-5. Particle size and BCP content in PS/ 1992).
PMMA pre-made BCP and PS/PMMA in situ formed
BCP blends.
8.4.5 Search for Optimal Reactive
Blend name Particle size measured BCP Molecules
by light scattering content
(Jim) (wt.%) The efficiency of reactive components for
NR 1.1 0 interfacial modification by melt reactivity
Pbl 1 5 was investigated on polyamide 6/anhydride
Rl 0.75 1.6 terminated PS (one chain end functionalized
R4 0.5 1.7
for 60% or 85% of the chains)/PS ternary
blends (Park et al., 1992). High anhydride
concentration (or low molecular weight of
the fact that the reaction rate to provide BCP the reactive species) gave higher efficiency
at the interface can be faster than the rate of for a fixed fraction of reactive PS, but had
diffusion of a pre-made BCP to the inter- lower efficiency per reactive group intro-
face. duced. This could again show that a high
The slow diffusion of a BCP in micelles concentration of reactive groups is favor-
or a very finely dispersed phase to a poorly able, but a high molecular weight of the
modified interface is generally conceivable. blocks is also interesting.
In connection with this, of particular inter- However, extensive reaction of PA with
est is a bimodal particle size distribution SMA of high MA concentration (11 or 25%)
generated in PA 6/EP-g-MA/EPR blends. In can lead to embrittlement of the polymer

(Chang and Hwu, 1991), showing that an
excess of reaction can be, in this kind of
blend, detrimental to the mechanical prop-
erties. This comes from degradation of the
poly amide if a large amount of amine
chain ends are consumed (Marechal et al.,
1995). This detrimental effect of an excess
of reaction is also found for PA/PC blends.
Through an excess of exchange reactions,
the polymers lose both their identity and
their properties. It was shown in this case
that interesting blends could be obtained by
a reduction of the reaction rate between the
PA and the PC if rapid consumption of the
amine chain ends of the PA by an anhydride
occurred (Smith, 1958).
8.4.6 Morphology, Interfaces,
and Properties
The relationship between the morpholo-
gy and the properties is well exemplified by
Fig. 8-1. It seems also that the kind of rela-
tionship between the optimal morphology
for toughening and the entanglement den-
sity can be extended to the materials that
mainly deform by shear yielding without
crazing. For these materials, the critical
interparticle distance required for toughness
is proportional to the entanglement density
(Wu, 1990). The morphology was consid-
ered to be the unique parameter defining the
toughness.
On the other hand, it is generally recog-
nized that the interfacial adhesion is bene-
ficial to the mechanical properties (Noolan-
di and Hong, 1982; Triacca, 1991; Saleem
and Baker, 1990). In most cases, an
improvement of the properties was observed
in relation to the occurrence of the reaction
at the interface (Yokoyama et al., 1994; Liu
and Baker, 1994). Sometimes, the proper-
ties of a reactive blend are found to be bet-
ter than those of a nonreactive one, and
therefore it is concluded that a reaction has
8.4 Interfaces in Reactive Blends 457
occurred (Legros et al., 1994). However, in
these studies, the reaction could modify not
only the interfacial adhesion, but also the
particle size. It would therefore be very
interesting to compare reactive and nonre-
active blends having the same morphology
in order to point out the pure effect of the
interfacial adhesion.
ForPP/PP-oxazoline/poly(acrylonitrile-
butadiene-acrylic acid) (NBR) blends the
particle size was varied either by changing
the processing temperature or by changing
the PP-oxazoline content. It was found that
the fracture energy in notched Charpy tests
for reactive and nonreactive blends are sig-
nificantly different. Figure 8-28 a shows
this fracture energy as a function of the aver-
age particle size (Liu and Baker, 1994). For
a particle size of about 0.8 |Lim, the tough-
ness of the reactive blend is about three
times higher than the toughness of the non-
reactive one. This difference is therefore
only due to the improved interfacial adhe-
sion brought about by the reaction.
Poly(ethyleneterephthalate)/EPR-epoxy
blends showed similar results. In Fig.
8-28 b, the Izod impact strength is plotted as
a function of the particle size determined by
light scattering. At a given particle size,
reactive blends had higher toughness than
nonreactive blends (Yokoyama et al.,
1994).
Using the finite element method to ana-
lyze the deformation mechanism of rubber-
toughened PA, it is shown that fracture
occurs much faster if the dispersed rubber
particles having good adhesion with the
matrix are replaced by voids (Fukui et al.,
1991). This suggests that, with poor adhe-
sion, dispersed particles are not very differ-
ent from voids at sustaining the mechanical
stresses, hence a certain level of interfacial
adhesion is required for toughening.
In Fig. 8-28, it also appears that some
adhesion of the phases promoted by the in
458 8 Reactive Processing of Polymer Blends: Polymer-Polymer Interface Aspects

15 improved characterization of the structure

and molecular weight of the BCP or GCP

I12
CD Reactive blends
produced at the interface. Actually, in
Sec. 8.4.6 on the analysis of the effect of the
interfacial modification on the mechanical
properties, nothing was described about
either the molecular weight or the surface
coverage, but these parameters were recog-
05
nized as essential for the interfacial tough-
ness, as shown in Figs. 8-11 and 8-12.
Some experiments of this sort were per-
Nonreactive formed in the case of polyamide 6/reactive
blends rubber blends. In these blends, with a con-
0.3 0.5 1 stant rubber volume fraction, it was found
(a) Mean particle diameter that the brittle-tough transition temperature
(BTTT) increases with the particle size of
T 5 the rubber (Borggreve et al., 1987, 1988;
PET/f-EPR
o 7 mix =260C Borggreve, 1988). However, for these
o 270C blends, the molecular weight of the block
280C copolymer could not be controlled and
^3h \ PET/EPR decreases with increasing particle size
c 0 7~mix =: 280C (Marechal et al., 1993 b). Blends with var-
CO
ying particle size and constant grafted poly-
^ ^ PET/f-EPR
T> amide molecular weight could be prepared
Q. 1 by control of the molecular weight segrega-
E PET/EPR -CQj-O OO
g , i , i
tion (see Sec. 8.4.3) (Marechal et al.,
2 4 1993 a). For these blends with constant
(b) Mean particle diameter (urn) molecular weight at the interface, the BTTT
Figure 8-28. Impact strength versus (a) the particle was found to be nearly independent of the
size measured by image analysis on SEM pictures for particle size (between 0.15 and 0.4 (im).
PP/NBR blends and (b) particle size measured by light Figure 8-29 shows the BTTT for PA 6/EPR-
scattering for PET/EPR blends [28 a: Saleem and g-MA (80/20) blends with constant grafted
Baker (1990) and 28b: Yokoyama et al. (1994)]. polyamide molecular weight (full symbols)
and with decreasing grafted polyamide
situ formed BCP is important in achieving molecular weight (open symbols) as a func-
more easily a transition from brittle to tough tion of the particle size. From this figure it
behavior. can be concluded that the grafted polyamide
molecular weight controls the BTTT. The
constancy of the BTTT with particle size
8.5 Concluding Remarks seems provocative in view of most results
obtained previously (Margolina, 1988,
Future development in the reactive pro- 1990; Wu and Margolina, 1990). In the case
cessing of polymer blends will more and of polyamide/reactive rubber blends, as a
more require an analysis of the reaction sufficient level of reaction is reached, adhe-
level between the two polymers, and also an sion between the PA and the rubber is not
 8.5 Concluding Remarks 459

10

Increasing particle size> lower reaction level

decreasing grafted PA molecular weight

Figure 8-29. Brittle-tough

transition temperature ver-
sus mean particle diameter
l|
5= .0)
Gain with control
of the BCP
for polyamide 6/reactive
rubber (80/20) blends. Full
-20- symbols: PA 6/EP-g-MA/
DQ
phthalic anhydride blends;
Increasing particle sizeslower reaction level open symbols: PA6/EPDM-
but constant grafted PA molecular weight g-MA blends (Marechal,
-30
0.10 0.15 0.20 0.25 0.30 0.35 0.40 1993).
Mean rubber particle diameter (jim)

the critical parameter, but the entanglement

density in the grafted polyamide around
the rubber is, since the grafted polyamide is
not a negligible fraction of the polyamide of
the blend. Nevertheless, Fig. 8-29 under-
lines the importance of the control of both
the amount and the molecular weight of
BCP or GCP formed during reactive pro-
cessing.
It was shown in Sec. 8.4.1 that the BCP
locates at the interface, but in some cases,
the BCP formed at the interface during reac-
tive blending can escape the interface in 500 nm
the form of micelles. This is, for exam- Figure 8-30. TEM picture of a PS-COOH/PMMA-
ple, the case in a reactive blend of epoxy 30K/20K (70/30) blend mixed at 180C for
PS-COOH (30 K) / PMMA-epoxy (20 K), 15 min (Nakayama, 1994).
where the amount of BCP formed by reac-
tion exceeds the saturation coverage. The
fine morphology of this blend is revealed by Nevertheless, interesting interfacial mod-
TEM in Fig. 8-30. It is shown that large ification could be obtained with low molec-
PMMA particles are surrounded by small ular weight PS-PMMA BCP if the PS and
clouds of micelles. The mechanism of for- PMMA are replaced by PPO and SAN,
mation of these micelles is still not estab- which are miscible with the PS and PMMA
lished, but it is strongly related to the molec- blocks, respectively (Auschra, 1993). Such
ular weight of the BCP. In this case, micelles a system, generally referred to as A/C-D/B,
could escape the interface while in a system with A/C and B/D miscible, seems to have
involving a BCP of higher molecular quite interesting possibilities (Vilgis and
weight, this process of micelle formation Noolandi, 1990; Jo et al., 1991;Braunet al.,
did not occur (Nakayama, 1994). 1994). However, interfacial modification of
460 8 Reactive Processing of Polymer Blends: Polymer-Polymer Interface Aspects
the PPO/PMMA blend with PS-PMMA
BCP in melt blending appeared quite disap-
pointing, all the BCP ending up forming
micelles in the PMMA phase (Khandpur
et al., 1994).
It was also found that A-r and B-r" poly-
mers do not need to react if a third compo-
nent (r') can make the link by reacting with
both A-r and B-r" polymers, as in the case
of PCL/APS/CTBR presented in Figs. 8-19
and 8-20. Such A-r/r7r"-B blends may also
be quite interesting from an industrial point
of view. For example, it was found that the
interface in polyamide/rubber blends could
be modified by the addition of maleic anhy-
dride and peroxide. This anhydride has the
ability to react both with the PA through the
anhydride function and with the rubber
through the insaturation if a peroxide is
present. This way of reactive blending is
quite cheap since polyamide, rubber, anhy-
dride, and peroxide can be blended as
received in a single extrusion step (Lambla,
1991; Seadan, 1992; Willis et al., 1990).
In the next step of the science of reactive
blends, it is expected that knowledge of the
chemical reaction rate in molten polymers
will be improved, that the amount and
molecular weight of the graft copolymer
will be characterized further, and then also
that the range of possible reactions and reac-
tive polymers will be extended.
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 8.6 References 463

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9 Structure Development in Reactive Systems
John L. Stanford, Anthony J. Ryan, and Michael J. A. Elwell*

Polymer Science and Technology Group, Materials Science Centre,

University of Manchester and UMIST, Manchester, U.K.

* Present address: Dow Benelux N. V., P.O. Box 48, 4530 AA Terneuzen, The Netherlands

List of Symbols and Abbreviations 466

9.1 Introduction 469
9.1.1 Reactive Polymer Processes 469
9.1.2 Concepts of Structuring 471
9.1.2.1 Time-Temperature-Transformation Diagrams 471
9.1.2.2 Phase Diagrams 473
9.2 Single-Phase Materials 475
9.2.1 Gelation and Network Formation: Classical Theory 476
9.2.2 Evolution of Structure and Properties During Polymer Network Formation . 478
9.2.3 Application of Network Theory to Reactive Processing:
Model Reaction Injection Molding (RIM) Systems 481
9.3 Multiphase Materials 483
9.3.1 Phase Diagrams and Reactive Processing: Basic Principles 483
9.3.1.1 Blends, Mixtures, and Solutions of Homopolymers 484
9.3.1.2 Block Copolymers 488
9.3.2 Linear Segmented Block Copolymers 490
9.3.2.1 Copolyurethanes 490
9.3.2.2 Copolyamides 496
9.3.3 Lightly Crosslinked Copolymers 497
9.3.3.1 Copolyurethanes and Copolyureas 497
9.3.3.2 Flexible Copolyurethane Foams 498
9.3.4 Highly Crosslinked Copolymers and Resins 502
9.3.4.1 Rigid Copolyurethane Foams 502
9.3.4.2 Isocyanurate-Based Resins 503
9.3.4.3 Rubber-Modified Epoxy Resins 505
9.3.5 Interpenetrating Networks 508
9.4 Summary 509
9.5 References 510

Materials Science and Technology

Copyright WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
466 9 Structure Development in Reactive Systems

List of Symbols and Abbreviations

A, B, C composition
d interdomain spacing
Deff interdiffusion coefficient characterizing phase separation
/ functionality, block copolymer composition
/an'/bn'/aw/bw number-average, weight-average functionalities of A and B
reactants
G free energy
G', G " elastic shear modulus, loss shear modulus
G static shear modulus for a perfect network at complete conversion
G static shear modulus for a perfect network at conversion a
AG m Gibbs free energy of mixing
A//m enthalpy of mixing
AHU heat of fusion per mole of repeat unit
I(q,t) scattering intensity
k crystallization rate constant
K ratio of rate constants
/ number of units of RA 2
m, n degree of polymerization
MQ ideal number-average molar mass between elastically active
junction points
Mc molar mass between network junction points
Mn, M w number-average, weight-average molar mass
n number of units of RB^, critical rheological exponent at gelation,
Avrami exponent
N polymerization index, degree of polymerization, chain length
n
a0> ^bo initial numbers of A and B groups
nc number of elastic chains in a perfect network
n,/-mer chain comprising n units of RB^ and / units of R A 2 reactants
7Va, Afb number of moles of A- and B-functionalized reactants
^A2> NBf initial numbers of R A 2 and RByr units
7Vn, Afw number-average, weight-average sequence length
N0l, Nn> r number of RA 2 monomers, n^'-mers
AfHcrit critical hard-segment block length
p conversion
/7a, ph extents of reaction of A- and B -functional groups
PNCO> P(NCO)c,th,exP extent of reaction of isocyanate groups, critical, theoretical,
experimental
q scattering vector
q* scattering peak intensity
Q' relative scattering invariant
r stoichiometric ratio
R gas constant
Rg radius of gyration
 List of Symbols and Abbreviations 467

R (q) scattering amplification factor

RA 2 , RB^ bifunctional, multifunctional reactants
ASm entropy of mixing
t reaction time
tg gel time
T absolute temperature
7, r p temperature
Tc cure temperature
Tg glass-rubber transition temperature
r | , T soft-segment, hard-segment glass transition temperature
r g 0 gel 7 g , r goo reactant(s), gel, complete conversion glass transition temperature
7^, Tm pure polymer, polymer-solvent melting point
Tx crystallization temperature
r0, rmold reactant(s), mold temperature
u u u
$, g, sfi ugf un
i t fractions of sol and gel
un i unit fraction of n,/-mer
unV unit fraction of n,/-mer in the sol
Vu dry undeformed volume of network
Vu, Vx molar volume of repeat unit, monomer
w weight fraction of each component
jcn, xw number-average, weight-average degree of polymerization
fractions of RA2 and RB^ reactants

a product of extents of reaction of A and B groups

a* lowest root of P=a(l-a)f~2
acth predicted gel point
tan<5 loss tangent
0 relative proportion of ordered material (Avrami)
p density of network
0 volume fraction
X Flory-Huggins interaction parameter

AIBN azobisisobutyronitrile
ATBN, CTBN, ETBN amino-, carboxyl-, epoxide-terminated butadiene-acrylonitrile
random copolymer
ATR adiabatic temperature rise
BDO 1,4-butanediol
CFC chlorofluorocarbon
CM compression molding
DBTDL dibutyltin dilaurate
DETDA diethyltoluene diamine
DGEBA diglycidylether of bisphenol-A
DMTA dynamic mechanical-thermal analysis
DP degree of polymerization
DSC differential scanning calorimetry
468 9 Structure Development in Reactive Systems

DVB divinylbenzene
EDO 1,2-ethane diol
FTIR Fourier transform infrared (spectroscopy)
IPN interpenetrating polymer network
LS light scattering
LT light transmission
MDI 4,4'-diphenylmethane diisocyanate
MMA methylmethacrylate
MST microphase-separation transition
NCO isocyanate
NG nucleation and growth
NMR nuclear magnetic resonance
ODT order-disorder transition
OH hydroxyl
PBMA poly(butylmethacrylate)
PDO 1,5-pentane diol
PMMA poly(methylmethacrylate)
POE polyoxyethylene
POP polyoxypropylene
PU copolyurethane
PUr copolyurea
PUrl copoly(urea-isocyanurate)
PUUr copoly(urethane-urea)
RIM reaction injection molding
RTM resin transfer molding
S styrene
SALS small-angle light scattering
SANS small-angle neutron scattering
SAXS small-angle X-ray scattering
SD spinodal decomposition
SEM scanning electron microscopy
TBA torsional braid analysis
TDI toluene diisocyanate
TEM transmission electron microscopy
TTT time-temperature-transformation
WAXD wide-angle X-ray diffraction

9.1 Introduction
The reactive processing of polymers and
composites involves simultaneous develop-
ment of the polymer structure and materials
shaping to produce polymer artifacts with
final properties suitable for particular appli-
cations. In engineering terms, reactive pro-
cessing is concerned primarily with the
design and control of the equipment and the
rheological processes required for particu-
lar polymer-forming systems. Equally
important, in scientific terms, is an under-
standing of the molecular processes
involved in the transformation from (reac-
tive) liquid state to solid polymer material,
which occurs during reactive processing.
The transformation processes, which define
polymer structure development, require in
situ measurements and analyses to provide
the fundamental understanding upon which
appropriate process models can be devel-
oped for the control and improvement of
reactive processing and materials proper-
ties.
This chapter deals specifically with poly-
mer structure development in reactive
systems in terms of polymerization, cross-
linking, and gelation; phase separation and
vitrification processes, and the basic theo-
ries underpinning these processes in single-
phase and multiphase (linear and nonlinear)
systems are presented. Often such process-
es occur competitively, either simultaneous-
ly or consecutively, in terms of the kinetics
of the chemical reactions and the thermody-
namics that define structure development.
As a consequence, reactively processed
materials are characterized by complex
morphologies, which largely determine
their final physical properties, and post-
mortem studies on structure-property rela-
tions for such materials are extensive. How-
ever, the emphasis in this chapter is placed
upon in situ studies of reacting systems,
9.1 Introduction 469
involving the use and results obtained from
time-resolved analytical techniques. Exam-
ples are presented from studies reported on
systems that produce a wide range of poly-
mer types, classified, in general terms, as
linear thermoplastics and crosslinked ther-
mosets (single-phase materials), and block
copolymers, toughened resins, and inter-
penetrating networks (multiphase materi-
als).
9.1.1 Reactive Polymer Processes
By way of introduction, a brief overview
of some of the more common reactive poly-
mer processes is presented first. More
detailed descriptions are given elsewhere
(Charrier, 1990; Elias, 1993). The methods
used in reactive processing come under the
general headings of casting, coating, and
molding, and involve the use of viscous (as
opposed to viscoelastic) materials, which
include liquid monomers, pre-polymers,
polymer solutions, dispersions, and (low
molar mass) polymer powders. The reactive
processing of such materials may be char-
acterized, therefore, by the flow (usually
under gravity and requiring little pressure)
of liquids either within a mold cavity or on
a substrate surface.
The simplest reactive polymer process is
perhaps monomer casting, and examples
include monomers such as methylmeth-
acrylate, styrene, 8-caprolactam, and N-
vinyl carbazole. This process requires inex-
pensive molds and is used for the small vol-
ume production of shaped articles. The
polymerizations are exothermic and require
good temperature control and long reaction
times. Structure development in this process
is via molar mass development and may, in
some cases, involve polymer crystalliza-
tion.
Coating is a surface-modification meth-
od that may be divided into planar and con-
470 9 Structure Development in Reactive Systems

tour techniques. The former include spread,

roller, and spray coating of flat substrates, JL
and the latter involve the coating of objects Preform
having complex shapes using liquid-
dipping and fluidized-bed equipment.
Reactive molding processes include com-
Hydraulic
pression (CM), resin transfer (RTM), and plunger
reaction injection molding (RIM), and these
are shown schematically in Fig. 9-1. Com-
pression molding (Fig. 9-1 a) is used almost
exclusively for temperature-activated ther-
mosetting polymers, usually requiring tem-
peratures in the range 140 - 200 C and mold
(b)
pressures in the range 35-700 bar
(3.5-70MPa). Structure development in-
volves crosslinking processes that occur in
~1 min as, for example, in the production of
phenolic moldings, and vulcanization pro-
cesses taking >60 min for the manufacture Pneumatic
line
of very thick rubber components. (i) fibre mat placed (ii) mould is closed (iii) mat impregnation
in mould by injected resin
Resin transfer molding (Fig. 9-1 b) is a
process intemerdiate between compression
and injection molding, and is used primari-
ly for the manufacture of composite mate-
rials products based on unsaturated polyes-
ter and epoxy resins as matrices. The low-
viscosity thermosetting resin, containing a
catalyst, is pumped under moderate pressure
[~5 bar (0.5 MPa)] into a mold cavity con- (iv) heat-activated
crosslinking
(v) mould opening
and demoulding
(vi) demoulded and
postcured article
taining the pre-placed reinforcing fiber
mats. Gel- or in-mold coating prior to mat
placement is frequently employed. Mold (c)
filling and fiber impregnation are facilitat-
ed by evacuation of the cavity.
Reactant A Reactant B
Polymerization is temperature-activated
(140-200C) and structure development
occurs by crosslinking and gelation in cycle
times of up to 20 min. Additionally, phase
separation processes are involved when displacement displacement
cylinder cylinder
reactive liquid rubber or thermoplastics are

Figure 9-1. Schematic representations of various

reactive polymer molding processes: (a) compression
molding; (b) resin transfer molding; and (c) reaction
injection molding.

included in the resin formulations to
improve the toughness of the otherwise brit-
tle polyester and epoxy resins.
Reaction injection molding (Fig. 9-1 c) is
a relatively new process, and for the rapid
and automated production of large, thin
(~3 mm), and complex-shaped parts. Capi-
tal investment and operational costs are
much less than those for conventional injec-
tion molding. In RIM two or more low-
viscosity reactant liquids (monomers and/or
pre-polymers) are accurately metered,
according to chemical stoichiometry, and
impingement mixed at high pressure
[200-300 bar (20-30 MPa)] in a hydraul-
ically operated mixhead. The reactant
mixture then flows under low pressure [<10
bar (1 MPa)] into a mold cavity. Reactant
throughputs can be up to 100 kg s"1;
mold-fill times of ~ 1 s and cycle times of
<60 s are typical. Mix-activated copoly-
(ether-urethane) and copoly(ether-urea)
systems are most commonly used in RIM.
Nylon copolymer (based on e-caprolactam),
epoxy, acrylic, and olefinic (polydicyclo-
pentadiene) systems have also been devel-
oped commercially. Compared to the other
reactive process methods, structure devel-
opment in the RIM copolymer-forming
systems is much more complex, involving
polymerization (often with crosslinking and
gelation) processes and competitive phase-
separation and vitrification processes.
9.1.2 Concepts of Structuring
In the production of a useful polymer arti-
fact, via reactive polymer processing, the
transformation of a liquid polymer or pre-
polymer mixture is carried out using a
device such as a die or a mold cavity. If the
liquid is not to lose its shape it must be solid-
ified either in the cavity (during molding)
or shortly after exit from the die (during
extrusion or pultrusion). This chapter deals
9.1 Introduction 471
with reactive molding; the initial stage of
the shape stabilization process involves
polymerization, during which solidification
occurs (often in competition with polymer-
ization) by any of the primary mechanisms
of endlinking and crosslinking (involving
gelation), vitrification, crystallization, and
phase separation, either individually or in
combination. Both reactively processed
single-phase (amorphous) and multiphase
materials are considered. In the former,
molar mass development and crosslinking,
due to chemical reactions, sometimes
accompanied by vitrification, are the impor-
tant mechanisms for solidification during
processing. The fundamental relationships,
based on polymerization statistics, between
molar mass development, chemical gela-
tion, and network formation will be
addressed. In multiphase systems, the solid-
ification processes, namely, reaction-in-
duced crystallization in the case of semi-
crystalline polymers, and macrophase and
microphase separation in the case of poly-
mer blends, block copolymers, and their
mixtures, are also considered. Generally,
during the reactive processing of blends,
IPNs, and block copolymers, chemical reac-
tion causes a chemical quench from a one-
phase region to a two-phase region of the
phase diagram. The morphology developed
in the material produced is dominated by the
route taken through phase space, and this
aspect of structure development will also be
dealt with in detail.
9.1.2.1 Time-Temperature-
Transformation Diagrams
Structure development in single-phase
materials, compared with that in multiphase
materials, is relatively easy to model and
interpret using polymer statistics. In nonlin-
ear systems, gelation and network theories
are used to predict the evolution of struc-
472 9 Structure Development in Reactive Systems
ture, principally in terms of the number of
network chains or the density of junction
points (or crosslinks) formed, which,
together with chemical structures and the
average molar mass (Mc) between junction
points, determine the network properties.
For example, viscosity, modulus, and glass
transition temperature (Tg) all increase dur-
ing processing. In particular, for highly
crosslinked (thermoset) systems with low
Mc, the increase in the Tg as polymerization
progresses can be such that vitrification
occurs as the Tg becomes equal to the pro-
cessing or cure temperature.
In the context of the reactive processing
of thermosets, considerable progress has
now been made in the description and under-
standing of both the relationship between
the cure and the properties of the materials,
and the significance of the Tg of a system
undergoing cure. This (and other) relation-
ships have been characterized in general
terms through cure-property diagrams,
such as the time-temperature-transforma-
tion (TTT) isothermal cure diagram (Enns
and Gillham, 1983). An abbreviated version
of the TTT diagram is shown in Fig. 9-2, and
is based on contours of the time-to-gelation
and the time-to-vitrification for systems
cured at different isothermal reaction or cure
SOL -GEL &,
SM>(I^
RUBBER \ J? GEL
X RUBBER
3 el
T
g
\1
LIQUID
SOL -GEL G L A S S ^ ^ ^ o g
Tnr,
SOL GLASS
Log (time)
temperatures (Tc). Such data were obtained
using torsional braid analysis (TBA) on var-
ious thermosetting systems, including
epoxy, polycyanurate, and polyimide resins.
The glass transition temperatures for the
initial reactants and the partially cured reac-
tant mixture at the gel point are designated,
respectively, as Tg0 and gel T g on the ordinate
in Fig. 9-2. Also shown is Tgoo, the glass
transition temperature of the fully cured
thermoset material. Curing the system to
complete conversion produces a change in
the r g from Tg0 to Tgoo. The characteristic
features of the TTT diagram are the gelation
and full cure contours, and the S-shaped
vitirification contour marked on Fig. 9-2,
which also shows the various states of mat-
ter in which the thermosetting material can
exist during cure. The gelled glass region is
divided into two parts by the full cure con-
tour (Tg = Tgoo), i.e., the sol-gel glass and the
fully cured gel glass. The char region results
from thermal degradation, which also caus-
es devitrification and a decrease in Tg at high
values of Tc.
Overall, the evolution of structure and
properties is controlled and determined ulti-
mately by the two dominant processes,
namely, gelation and vitrification. Chemi-
cal gelation occurs at a specific conversion
CHAR
^ R
Figure 9-2. Schematic time-temperature-
transformation (TTT) isothermal cure dia-
gram for a thermosetting system. (Adapted
from Enns and Gillham 1983.)

of the reactant functional groups (see
Sec. 9.2) corresponding to the incipient for-
mation of "infinite" molecular species (the
gel). Vitrification occurs either on cooling
from the liquid or rubbery state through Tg
to the glassy state, or by increasing Tg
(through reaction) up to or above Tc. Con-
version can be related to any time and tem-
perature cure path by modeling the TTT dia-
gram in terms of kinetic- and diffusion-
controlled reactions. The relationship
between the Tg and conversion can also be
established.
The TTT diagram approach provides con-
venient summaries of the relationships
between conditions of cure and the states of
the resulting materials. It is possible, there-
fore, to design cure paths in order to opti-
mize processing and materials properties,
and to provide a more complete understand-
ing of structure development during reac-
tive processing.
9.1.2.2 Phase Diagrams
The concept of the phase diagram (famil-
iar to physical chemists or materials scien-
tists) is the key to understanding and con-
trolling the reactive processing of polymers,
and the phase diagram is the starting point
for this section. Relatively simple phenom-
ena, such as vitrification and crystallization,
are considered before attempts are made to
relate the morphologies of multiphase poly-
mers to the mechanism(s) of phase separa-
tion.
In basic terms, a binary phase diagram
comprises two axes; one for composition
and the other for temperature. The existence
or co-existence of various phases, such as
separated liquids, crystalline phases, vitri-
fied glasses, and various mixed phases, is
denoted by their phase boundaries.
The simplest phase diagram in polymer
terms is that of a mixture of a single-phase
9.1 Introduction 473
amorphous polymer and a good solvent. The
only boundary is that of the glass transition
temperature (not actually a phase transi-
tion), which is dependent on the composi-
tion of the mixture according to the Fox
(1956) equation
(9-1)
T
where w is the weight fraction of each com-
ponent and the subscripts p and s refer to the
polymer and solvent, respectively. Figure
9-3 illustrates the phase diagram for
poly(methylmethacrylate) (PMMA) and its
monomer, methylmethacrylate (MMA),
which is a good solvent for PMMA. The
value of Tg for the mixture varies continu-
ously with composition between 243 K
(-30 C) for the monomer solvent and 400 K
(127 C) for the polymer.
The process typically used to form PMMA
into sheet, tubes, and rods involves slow
polymerization rates and slow cooling rates
to give stress-free articles with isotropic
properties, particularly the refractive index,
so that the PMMA products are crystal clear.
Batch and continuous processes are utilized
and, essentially, both involve taking an iso-
thermal path through the phase diagram until
the vitrification curve is intersected.
150
PMMA: Tg = 127 C~
9ioo:
0.8
Figure 9-3. Simple phase diagram of the polymer-
monomer system, PMMA-MMA. The solid curve is
calculated from the Fox equation and represents the
boundary between liquid and glassy phases.
474 9 Structure Development in Reactive Systems
Cast PMMA is produced using simple
molds that comprise a cavity (formed by
glass plates) and a diaphragm (in the form
of a rubber gasket). Typically, a mold is
charged with a mixture of 20% by weight of
PMMA in MMA containing an appropriate
amount of free-radical initiator, usually
azobisisobutyronitrile (AIBN). (It is pos-
sible to start with pure monomer, but the
shrinkage on polymerization is unaccept-
ably high.) The filled mold is heated slow-
ly to 60 C and maintained at this tempera-
ture until a monomer conversion of-80% is
achieved. (The time taken is dependent upon
the thickness of the casting being prepared.)
At this conversion, the T2 of the mixture is
reached and the propagation reaction
becomes diffusion controlled so that poly-
merization is effectively arrested. The tem-
perature is raised to 105 C and held for a
period until complete conversion of the
monomer is attained. (Note that the ceiling
temperature of PMMA is 105 C.) The mate-
rial is cooled at a rate that keeps the temper-
ature gradient through the thickness of the
molding to <10C cm"1, and when the mid-
plane temperature is <60 C, the PMMA can
be removed from the mold. Because of the
relatively long times involved and the slow
release of the enthalpy of polymerization,
thermal gradients in the mold are minimal.
All regions (on the molecular level) of the
casting experience similar homogeneous
thermal and chemical histories, and the
material is annealed uniformly to equilibri-
um so that structure development in this
polymerization system results in the forma-
tion of materials with isotropic properties.
In terms of the shape stabilization process
during the formation of multiphase poly-
mers, phase diagrams such as that shown
in Fig. 9-3 are equally important as they
can be used to define the composition of
a vitrified phase in a phase-separating
system.
Another example of a simple phase dia-
gram in polymer terms is that for a mixture
of a crystallizable polymer and a good sol-
vent, which may also be its monomer. This
situation is analogous to a liquid-gas
system. Two phase boundaries now define
the two phases in equilibrium, namely, the
solidus and liquidus regions, and the equa-
tion (Mandelkern et al. 1952) defining the
melting point of the polymer-rich composi-
tion (ignoring the effects of molar mass and
crystal size) is
<9 2)
-
where (f)x is the volume fraction of diluent,
T^ is the melting point of the pure polymer,
Tm is the melting point of the mixture, R is
the gas constant, Vu and Vx are the molar
volumes of the repeat unit and of the
monomer, AHU is the heat of fusion per mole
of repeat unit, and %x is the Flory interac-
tion parameter. Thus when a solution of
composition C, comprising a crystallizable
polymer melt in its liquid monomer, is
cooled from a temperature Tp to a crystal-
lization temperature Tx, a crystalline solid
phase of composition A is formed, which is
immediately surrounded by a liquid phase
of composition B, which cannot crystallize
at Tx. This behavior is illustrated in Fig.
9-4 in which the upper line defines the melt-
ing point of the polymer-rich phase. The
solution of a polymer in a good solvent has
two equilibrium phases (one rich in crystal-
line polymer and the other rich in solvent)
at any combination of composition and
temperature. Generally, the composition of
the polymer-rich crystalline phase tends
towards that of the pure polymer.
The process generally used to produce
cast nylon-6 involves isothermal polymer-
ization, and this process has been used for a
number of years in the production of small
and complex parts. (The process was com-

TO i
9.2 Single-Phase Materials
1
m
***'*^liquidus
\
solidus
A B
0 1
pure Composition pure
polymer
Figure 9-4. Binary phase diagram showing the sol-
idus and liquidus curves for a crystallizable polymer polymerizations are also important in reac-
(with melting temperature 7^) in equilibrium with a
solvent of melting point 7,. Cooling a homogeneous
polymer-solvent mixture of composition C from Tp
(>7^) to Tx (<T^) results in a two-phase solid-liquid monomers, and addition reactions between
mixture comprising solid-rich (A) and liquid-rich (B) a small proportion of double bonds in pre-
components.
mercialized in the 1980s under the trade
name NYRIM by Monsanto and DSM.) vinyl adipate, and styrene with divinylben-
Monitoring crystallization during nylon-6
formation (a relatively simple two-phase
system) exemplifies some of the problems
associated with the study of structure devel-
opment during rapid reactive processing.
Only recently have these problems been
overcome, as reported by Ishida and Scott
(1986) in a study on the fast isothermal
polymerization of -caprolactam, which
required the use of specially constructed
RIM equipment interfaced to an FTIR spec-
trometer. Details of this study are given la-
ter (see Sec. 9.3.2.2), but it is useful to
consider this study in general terms. The
isothermal polymerization takes a hori-
zontal route through the phase diagram sim-
ilar to that shown in Fig. 9-4. However, by
using time-resolved FTIR spectroscopy, it
is possible to measure the crystallization
kinetics continuously along the route, and
to interpret the mechanism(s) responsible
for the development of the crystalline struc-
ture.
9.2 Single-Phase Materials 475
In the context of reactive processing,
many of the polymer-forming systems of
interest involve step polymerizations, par-
ticularly non-linear systems that exhibit the
phenomenon of chemical gelation. Poly-
merization in such systems usually proceeds
via endlinking reactions of functional
groups on polyfunctional (f>2) monomers
and/or low molar mass pre-polymers.
Crosslinking reactions based on chain
tive processing and include systems involv-
ing mixtures of divinyl and monovinyl
formed unsaturated polymer chains of rela-
tively high molar mass. Examples of the for-
mer include methylmethacrylate with ethy-
lene dimethacrylate, vinyl acetate with di-
zene, which has been used in structure
development studies on semi-IPNs (inter-
penetrating polymer networks) and is dis-
cussed in detail in Sec. 9.3.5. Examples that
involve unsaturated polymers include the
vulcanization of rubbers and the curing with
vinyl monomer of unsaturated polyester
pre-polymers.
In all cases, the development of structure
and properties essentially begins at the gel
point, accelerates in the post-gel region, and
is optimized (often by so-called postcuring)
as the network material is formed at com-
plete reaction. The evolution of the struc-
ture in nonlinear step polymerizations,
including predictions of the gel point and
the network properties, can be modeled
using polymerization statistics; this was
initially developed by Flory (1953 a) and
Stockmayer (1943, 1952). To a first approx-
imation, the early theories give good
descriptions of network development but
they treat the ideal case since they neglect
476 9 Structure Development in Reactive Systems
known experimental phenomena, such as
side reactions, intramolecular reaction,
incomplete reaction, nonrandom reactions
(as in crosslinking), topological entangle-
ments, and chain interactions (even those
developed at a very localized or simplistic
level). Thus many theories and models, for
example, cascade theory, rate theory, Monte
Carlo simulation, and percolation models,
some of which account for the various
experimental phenomena, have been devel-
oped in an attempt to give more complete
descriptions of structure development dur-
ing network formation. Discussion of these
theories is beyond the scope of this chapter
and the reader is referred to an excellent
review of this subject published recently by
Stepto(1992).
The importance of the gel point in
reactive processing terms is obvious, par-
ticularly when considered in a broader tech-
nological context, as depicted by the so-
called cure-property diagrams, i.e., the
time-temperature transformation (TTT)
diagram (Enns and Gillham, 1983), de-
scribed earlier. The two major events occur-
ring during network formation (gelation and
vitrification), together with the network
chemical structure, determine all the prop-
erties of thermosetting materials. Gelation
marks the point of incipient network forma-
tion, when infinite molecular species form
and the reacting system develops infinite
viscosity and significant elasticity, as the
number of junction points or crosslinks
increases (see Fig. 9-6, Sec. 9.2.2). This
liquid-to-solid transformation must be pre-
dictable and controllable for successful
reactive processing in which the shaping of
the polymer networks (involving material
flow during molding or extrusion) must be
achieved prior to gelation.
9.2.1 Gelation and Network Formation:
Classical Theory
The prediction of gel points and the mod-
eling of network formation are essential.
However, despite recent advances, none of
the theories and models of nonlinear poly-
merization referred to in the previous sec-
tion describes, either accurately or com-
pletely, the development of the structure and
properties in network-forming systems. In a
chapter dealing with reactive processing,
however, the use of classical Flory-
Stockmayer statistics may be considered
adequate in order to demonstrate how struc-
ture development during single-phase net-
work formation can be modeled.
For a network-forming system compris-
ing polyfunctional reactants, RA^a and RB^,
in which only A-functional groups can react
with B-functional groups, the condition for
gelation (Stockmayer, 1952, 1953) is given
as
-1) = 1 (9-3)
where oc=pSipb, and/?a and/?b are the extents
of reaction of the A and B groups. This equa-
tion is based on mixtures of N.di and NbJ moles
of A- and B-functionalized reactants with
any funcionality,/a/ and/ bj , where /, j= 1, 2,
3 , . . . The average functionalities/^ and/ bw
in Eq. (9-3) are given by the summations
f =-L _
and / b w = J
(9-4)
1
Jaw v
At the gel point, infinite molecular spe-
cies are formed and the degree of polymer-
ization (DP) distribution diverges. From the
beginning of the polymerization up to the
gel point, the expressions for xn and JCW, the
number-average and weight-average DP,
are given by Eqs. (9-5) and (9-6)
xn = (f +rf )-rp f f (9-5)
an bn a an bn

^ \\7
In Eqs. (9-5) and (9-6),/ an and/ bn are the
number-average functionalities given as
=
/an v^
and (9-7)
r (=na0/nb0=pb/ps) is the stoichiometric
ratio of the functional groups, and na0 and
nb0 are the initial numbers of A and B
groups. Equations (9-5) to (9-7) clearly
show that at the gel point xn is finite, where-
as xw becomes infinite. All finite species
formed before and after the gel point con-
stitute the sol fraction; infinite species
formed at the gel point and up to complete
network formation constitute the gel frac-
tion. However, the infinite species cannot be
enumerated as individual molecules, and
post-gelation distributions are better
defined in terms of reactant units that have
combined to form finite and infinite species.
Thus the unit fraction (approximately
equivalent to the mass fraction) of gel (wg)
is the sum of units combined in infinite spe-
cies. The value of ug increases from zero at
the gel point to unity at complete network
formation, assuming r- 1. The unit fraction
of sol (us) is evaluated directly by summing
the units in finite species using the DP dis-
tribution. The case of a simple RA^ self-
polymerization, for which the unit fraction
ux of x-mer is
s = 5 X = ( l - K g ) (9-8)
has already been dealt with in detail (Step-
to, 1992). It should be noted that at the gel
point and onwards for any network-forming
9.2 Single-Phase Materials 477
(9-6)
system containing polyfunctional reactants,
the distribution of finite species reverts so
that, with reference to the generalized gel
point equation [Eq. (9-3)] conjugate values
of a(a and a*) exist at which the distribu-
tions, pre-gel and post-gel, are identical.
In the context of reactive processing, for-
mulations based on RA2 + RB^ polymeriza-
tions are more commonly encountered. In
such systems, an x-mer is more precisely
defined as an nj-mer comprising n units of
RB^and / units of RA2. The nj-mer possess
(fn-2n + 2) chain ends of which (/ - n + 1)
are A groups and (fn-n-l+1) are B groups.
In addition, Eq. (9-8) needs to be modified
to take account of RA2 monomer, that is, by
including the unit fraction u0 x for the spe-
cies,ft,/= 0, 1. Thus Eq. (9-8) becomes
oo fn-n+\
n=\ l=n-\
The double summation in Eq. (9-9) is
made (Stepto, 1992) by transforming the
limit / to V [= (/ - n + 1)] with n= 1, 2, . . .,
oo, The unit fractions of RA2 monomer and
n,l'~ mer are, respectively
and unV = 1) ^ (9-10)
NA2+NBf
where N0l and Nnr are the numbers of RA2
monomers and ft,/'-mers, and NA2 and NBf
are the initial numbers of RA2 and RB^units.
After substitution and summation (Rolfes,
1992), the expression for us becomes
u =X (I- )2+X ( 1 - a
) <**
478 9 Structure Development in Reactive Systems

where XA2 and XBf are the monomer unit RA2 + RBf network formation. This is done
fractions, i.e., in terms of the distributions of species {unj>)
in the sol fraction, the unit fractions (us and
fr wg) of sol and gel, and the DP distributions
fr+2 (xn and JCW), given by Eqs. (9-9) to (9-15),
and XBf = (9-12) which apply in both the pre-gel and the post-
fr+2 gel regions.
As an example, the distributions evaluat-
In Eq. (9-11), a and a* are conjugate val-
ed for a stoichiometric RA2 + RB 3 network-
ues, where a* is evaluated as the lowest root
forming system are shown in Fig. 9-5. In
of the equation p=a(l - a)f~2. Thus a*
this case, Eqs. (9-9) to (9-15) are plotted as
<l/[(/aw " l)C/bw ~ 1)] a n d ^* ^ 0 as com- functions of the conversion p (= a 1/2 ); the
plete network formation is reached (a>l). reversion is unsymmetrical about p at the
Note that prior to the gel point, a* = a and
gel point (/?= 1/V2), although the distribu-
MS=1.
tions, pre- and post-gel, map onto each other
The unit fraction (unl>) of any species in accordance with the conjugate values
within the sol is then given as determined for a and a*. During network
formation, the larger species possess pro-
<v^Uf- (9-13) portionally greater numbers of unreacted A
and B groups and therefore react with high-
Generalized DP distributions for xn and
er probability than smaller species, so that
xw are obtained (Stanford and Stepto, 1996)
in the post-gel region increasing numbers of
using the expressions
units become attached to gel species. The
finite species therefore diminish in number
x
n oo fn-2n+2 (9-14)
and comprise increasing proportions of
X I Nn,l> smaller molecules. Figure 9-5 shows clear-
n=\ /'=0
ly that as p 1, the sol fraction decreases
(9-15) rapidly and eventually contains only RA2
and RB3 reactants (u'ox + u'l0), and the gel
fraction [= (1 - us)] becomes the network at
n=\ l'=Q complete reaction.
To obtain a perfect network with ideal
Equations (9-14) and (9-15) are numeri- physical properties, all reactions (sol-sol,
cally equivalent in the pre-gel region to Eqs. sol-gel, and gel-gel) are assumed to yield
(9-5) and (9-6) for xn and xw given previous- elastically active network chains between
junction points at complete network forma-
tion. Gel-gel reaction (which must occur to
give the final network) is by necessity intra-
9.2.2 Evolution of Structure
molecular, but some of this reaction leads to
and Properties During Polymer
elastically inactive chains. Application of
Network Formation
Flory-Stockmayer statistics (Stepto, 1990)
The Flory-Stockmayer statistics pre- allows the relative amounts of sol-sol,
sented in the previous section can now be sol-gel, and gel-gel reactions to be evalu-
used to describe, to a first approximation, ated in RA2 + RByrpolymerizations. For stoi-
the development of the structure during chiometric systems at a= 1, the proportion

0.8 -
Unit fraction
(u)
0.6 -
0.4 -
0.2 -
0 0.1 0.2 0.3 0.4
Extent of reaction (p)
of gel-gel reaction was calculated as 1/6. In
real networks, it has been shown experimen-
tally that -10% of bonds formed via sol-sol
and gel-gel reactions in the post-gel region
produce inelastic loops. Such loops, togeth-
er with those formed by pre-gel intramolec-
ular reactions, produce imperfect networks
with physical properties inferior to those
expected for corresponding perfect net-
works. These observations lead to the con-
clusion that the occurrence of structural
defects is inevitable in single-phase network
materials produced experimentally.
Structure development during the for-
mation of such networks may be moni-
tored using a variety of time-resolved tech-
niques. For example, simultaneous time-
resolved FTIR spectroscopy and rheometry
have been used (Griffiths et al., 1996) to
study model RA2 + RB3 polyurethane-
forming systems, in which RA2 is 4,4'-
diphenylmethane diisocyanate (MDI) and
RB3 is polyoxypropylene (POP) triol
9.2 Single-Phase Materials 479
Figure 9-5. The evolution of
molecular structure in a stoichio-
metric RA2 + R'B 3 network-
forming system, in terms of the
distribution curves for the sol spe-
cies. Reversion of the distributions
occurs at the gel point (p= 1/V2),
as indicated by the vertical dashed
line. The solid curves for
monomer, dimer, and tetramer are
given, respectively, as the unit
fractions (uQl + u\0), (u'ul), and
(u\3 + ^2,2)' calculated according
to Eq. (9-13). Pre-gel, the sol frac-
tion us= 1 and decreases post-gel
according to Eq. (9-11), as shown
dimers
by the curve marked us. Distribu-
--tetramers tions for the degree of polymeriza-
tion (DP) are shown as the dashed
0.5 0.6 0.7 0.8 0.9 1
(Mn^700 g mol l). Polymerizations were
carried out at 60 C in bulk using a catalyst
(triethylene diamine) with different stoichi-
ometric ratios r {- [NCO1/[OH]) in the range
2/3 < r < 3/2. Both of the time-resolved tech-
niques allowed structure development in
terms of polymerization kinetics and rheo-
logical data to be monitored continuously
through the gel point and up to complete net-
work formation. The rheological data were
obtained in steady shear (giving the viscos-
ity and normal stress difference versus time
data), and in oscillatory shear (giving the
storage and loss moduli, G' and G"\ and the
loss tangent, tan 8 versus time data). In the
latter case, multifrequency data in the range
20-100rad s"1, were obtained in single-
sweep, oscillatory shear runs utilizing com-
posite dynamic wave forms analyzed via a
Fourier transform algorithm. The gel point
(in terms of the time to gelation) was eval-
uated from (i) the divergence in plots of vis-
cosity and normal stress difference versus
480 9 Structure Development in Reactive Systems
time, (ii) cross-over points in G' and G" ver-
sus time plots, and (iii) tan S congruency
(frequency independent) points. The results
showed clearly that the only truly accurate
and absolute method for determining the gel
point, as a materials parameter independent
of reaction and test conditions, was based
on data obtained from tan S congruency
measurements.
Power-law dependencies of the moduli
(G' and G") and the loss tangent (tan S) in
terms of the critical exponent, n, were deter-
mined using dynamic scaling theory. The
values of n obtained were interpreted in
terms of gel point theories based on branch-
ing (for which n-112) and percolation (for
which ft = 2/3), to examine critically the
principle of universality of (model)
network-forming systems. The results
clearly showed that gelation for the model
PU (copolyurethane)-forming system was
nonuniversal, since ideal branching behav-
ior was observed only for systems formed
in bulk, either with stoichiometric equiv-
alence of NCO and OH functional groups or
with an excess of the bifunctional (RA2)
unit. With increasing excess of the branch-
ing unit (RB3), the value of n increased from
a minimum (branching) value of 0.5 towards
an apparent (percolation) limiting value of
0.67. The trends observed were interpreted
in terms of hydrodynamic screening and
interactions.
Such simultaneous time-resolved data are
extremely important for providing a funda-
mental insight into structure development
during reactive processing. For example,
accurate reaction kinetics data (FTIR) and
unambiguous gel times (rheometry) allow
chemo-rheological plots (representing
structure development during network for-
mation) to be constructed by transposing the
time axes of functional group conversion
and rheological property (viscosity, G', and
G") plots. Figure (9-6) shows such a plot for
the bulk PU-forming system defined earli-
er. In this case,ft= 0.5 and the G7G" cross-
over point and the divergence of the viscos-
ity clearly define the gel point in terms of
the critical extent of reaction, (/?Nco)c> f
isocyanate functional groups. The predict-
ed gel point for this system is a*h = 0.5 [see
Eq. (9-3)], giving (/^co^th^ 0 - 7 0 7 * a n d i s
shown as the dashed vertical line in Fig.
9-6. The experimental gel point (indicated
by the solid vertical line) gives a value of
(/?NCO)c,exp = 0-740. As reported (Stanford
and Stepto, 1982; Stanford et al., 1984)
for other polyurethane network-forming
systems, experimental gel points always
exceed the ideal values predicted by the
classical Flory-Stockmayer theory, and the
excess reaction required for gelation is
attributed to the loss of functional groups
via intramolecular reaction.
Figure 9-6 indicates that the storage shear
modulus increases rapidly in the gel point
region: at the gel point, G' -0.04 MPa and
reaches a limiting value of ~ 1.0 MPa at
complete network formation (/?NCO-1-0)-
The static shear modulus, G, of a perfect
network is related to the number of elastic
chains, nc, as given by the statistical rub-
ber elasticity theory
G=-^K-RT = !^-RT (9-16)
where p and Vu are, respectively, the den-
sity and the dry (undeformed) volume of the
network at absolute temperature T, and MQ
is the number-average molar mass between
elastically active junction points. Equation
(9-16) can be generalized (Stanford and
Stepto, 1996) using Flory-Stockmayer sta-
tistics to predict the ideal shear modulus,
G, as a function of the conversion a in the
post-gel region.
Thus
0 _ /b
(9-17)
 9.2 Single-Phase Materials 481

8.00 106

Viscosity
6.00-
Storage modulus, G1
r 105
Loss modulus, G"

b
4.00-

2.00-

Figure 9-6. Structure development in

r10 3 terms of viscosity and modulus increases
0.00-
with conversion for an experimental RA2
(pNC0)c.exp = " 7 4 0 + R'B 3 network-forming system. Polyure-
thane network formed from the stoichio-
(PNC0)c.th = " 7 0 7 metric polymerization of MDI and POP
10 2 triol (Mn=700 g mol"1) at 60 C in bulk.
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Extent of reaction, c

where A ^ is the initial number of branched example, G^= 1.53 MPa, and increases to a
units of functionality / b , and wg^is the unit limiting value of 3.48 MPa at complete
fraction of the gel species, given as reaction. The lower shear modulus values,
obtained experimentally in the post-gel
ugf =(l-usf) = l- {\-af region in Fig. 9-6, therefore provide direct
a (l-a*Y evidence that, as complete network forma-
(9-18) tion is approached, increasing proportions
Thus the general expression describing of elastically inactive network chains are
the development of the elastic shear mod- formed which, as described earlier, result
ulus G, from the gel point to complete net- from intramolecular reactions. Such real-
work formation, becomes time experimental data and their theoreti-
cal interpreation demonstrate clearly, there-
r0
a
_ /b ^Bj
RT fore, how structure development in poly-
~ 2 Vn mer network-forming systems can be quan-
(9-19) tified.
In the case of an RA2 + RB 3 system,/b = 3
and a* = (l - a), and Eq. (9-19) reduces to
9.2.3 Application of Network Theory
3 3 to Reactive Processing: Model Reaction
~a -(l-a) '
RT (9-20) Injection Molding (RIM) Systems
Using Eq. (9-20) for the polyurethane The development of structure during RIM
network-forming system shown in Fig. 9-6, copolymerizations has been modeled (Stan-
the calculated value for the shear modulus ford et al. 1995) in terms of the growth of
at a= 0.55 (equivalent top NCO = 0.74) is, for the weight-average copolymer molar mass
482 9 Structure Development in Reactive Systems
(Mw) and hard segment sequence length
(Nw) as functions of the conversion (p). The
modeling uses recursive method calcula-
tions (Lopez-Serrano et al., 1980) based on
classical Flory-Stockmayer polymerization
statistics. The recursive method is a simple
method for calculating the average molar
masses of polymers without first determin-
ing their distributions, and has been applied
to linear (Pannone and Macosko, 1988) and
nonlinear (Wang et al., 1990; Stanford
et al., 1995) RIM copolymerizations. This
method utilizes the recursive nature of a
step-copolymerization modeled as a first-
order Markov chain process (Lopez-
Serrano et al., 1980). Thus to determine the
weight-average molar mass in a typical
three-component RIM system, a unit of each
reactant is selected at random and the
expected weight of the molecule of which it
is a part is calculated; Mw is then obtained
by averaging the weights of the three select-
ed polymer molecules.
To demonstrate the recursive method,
calculations have been made on a nonline-
ar, three-component system, RA2 + R'B 2 +
R"Cj, as a model for copoly(urethane-urea)
(PUUr) and copolyurea (PUr) RIM systems
(Stanford et al., 1995). Formulations used
in these RIM copolymers are based, typical-
ly, on MDI and diethyltoluene diamine
(DETDA) as the hard segment, and either
hydroxy- or amino-functionalized polyeth-
er pre-polymers, withMn~2000 g mol"1 per
functional group and/= 2, 3, or 4 as the soft
segment. The data on various formulations,
for copolymers comprising 50% by weight
of polyurea hard segment, were coupled
with a set of kinetics differential equations
to introduce time dependence and unequal
reactivity between the reactants. Assump-
tions used in the modeling require that
homogeneous reaction conditions exist
and that all groups react independent of
each other. Additionally, the ratio, K,
of the rate constants for the two basic
reactions, isocyanate-polyether and iso-
cyanate-DETDA, is assumed to be indepen-
dent of temperature and conversion. As for
linear systems (Pannone and Macosko,
1988), overall second order kinetics were
assumed, and the values of K used for the
nonlinear systems corresponded approxi-
mately to the degree of unequal reactivity
expected in the formation of RIM copolym-
ers, that is, 0.1<#<1.0 for PUUr and
100<^<1000 for PUr. The kinetics equa-
tions were solved numerically to determine
the conversion of each reactant as a func-
tion of time which, when coupled with the
recursive method calculations, allowed the
calculation of Mw and A^w as functions of the
isocyanate conversion (p).
Representative plots of Mw (normalized
to Mw0, the molar mass of the initial reac-
tant mixture) and Nw versus p are shown in
Fig. 9-7 for trifunctional (/=3) RIM
systems (Stanford et al., 1995). When the
reactivity of the soft segment pre-polymer
is high (K= 1000 or 100), the pre-polymer
is consumed during the early stages of the
reaction (that is, 0</?<0.1), resulting in a
sharp increase in Mw as the prepolymer
undergoes oligomerization and is capped
with MDI. At lower values of K, this sharp
increase in Mw is not observed, and only a
gradual increase in MJM^0 with p occurs
and the rate of molar mass development
increases with the value of K. For the non-
linear RIM systems with/= 3, the ideal con-
version of isocyanate at gelation, calculat-
ed according to Eq. (9-3), is 0.96. The
dependence of Nw onp for various values of
K (see Fig. 9-7 b) shows the limiting value
of 7VW to be 20.8, which is dictated by the
initial ratio of the three components. When
the relative reactivity of the soft segment
pre-polymer is very low (K=0.l), this lim-
iting value is reached at p = 0.96, whereas
for higher values of K it is achieved only in

10
0.2 0.4 0.6 0.8
Extent of reaction, p
0.2 0.4 0.6 0.8
Extent of reaction, p
Figure 9-7. Distribution curves for model RIM
systems. Variations with the extent of reaction, p, of
(a) the relative molar mass, Mw/Mv,0, and (b) the
hard segment sequence length, Nw, for a nonlinear
polymerizing system comprising three reactants
RA2 + R'B 2 + R"C3, for which the B- and C-functional
groups are not mutually reactive but have different
intrinsic reactivities toward A-functional groups. K
is the ratio of the rate constants for the reactions
RA2 + R'B2 and RA2 + R"C3.
the limit of complete reaction. The model
therefore proposes that PUUr copolymers
develop longer hard segment sequence
lengths compared to equivalent PUr copol-
ymers, and PUUr should therefore exhibit
superior properties such as stiffness and
glass transition temperature, Tf. However,
experimental data obtained using dynamic
mechanical-thermal analysis (DMTA)
(Stanford et al., 1990; Ryan et al., 1988,
1991 a, b, 1993) show the reverse with PUr
9.3 Multiphase Materials 483
materials having higher values of T^ than
the equivalent PUUr. The differences
between experiment and theory are readily
explained by additional critical phenomena,
such as phase separation and vitrification,
which inevitably occur in experimental RIM
systems. Phase separation creates heteroge-
neous polymerization conditions which
slow the rates of reaction, and the onset of
vitrification effectively quenches copoly-
merization at relatively low conversions;
chemical gelation is often prevented in these
nonlinear RIM systems. Despite these dif-
ferences, the use of polymerization statis-
tics to predict molar mass development pro-
vides a useful basis for modeling RIM
systems.
9.3 Multiphase Materials
9.3.1 Phase Diagrams and Reactive
Processing: Basic Principles
In Sec. 9.1.2.2, two examples were given
to illustrate the use of simple phase dia-
grams to describe reactive polymer process-
ing. The first (Fig. 9-3), describing the vari-
ation with composition of a liquid-to-glass
transition, is not really a phase diagram. The
second (Fig. 9-4) was a liquid-solid (crys-
tal) separation, and it is important to distin-
guish it from the liquid-liquid phase separ-
ation process. Liquid-liquid phase separa-
tion can occur with any polymer in solution
(or with a blend), whereas crystal-liquid
phase separation is restricted to those poly-
mers that can crystallize. The differences
between the two processes, as defined by the
terminology liquid-liquid and liquid-solid,
refers precisely to the separation process,
not the separated phases. As shown later,
liquid-liquid phase separation can eventu-
ally result in rubbery, glassy, or crystalline
precipitates.
484 9 Structure Development in Reactive Systems
9.3.1.1 Blends, Mixtures,
and Solutions of Homopolymers
Consider initially liquid-liquid phase
behavior. As the thermodynamic behavior
of most polymer mixtures is dominated
by the free energy of mixing, classical
solution theory (Flory, 1953 b) is the most
convenient starting point for describing
liquid-liquid phase diagrams. All polymer
solution theories are based on the determi-
nation of the enthalpic and entropic contri-
butions to mixing, and for mixing to occur,
the conditional expression
AG m = AHm TASm<0 (9-21)
m
applies, where AG is the Gibbs free ener-
gy, AHm is the enthalpy, and A5m is the
entropy associated with the mixing process
at the absolute temperature T. This solution
theory is based on a lattice model, and poly-
mer segments and solvent molecules are
assumed to have the same volume, such that
for a polymer-solvent mixture, the entropy
change is defined by the combinatorial
expression
A5m= - R [nx \n(fa) + n2 In (02)] (9-22)
where n and (j) are, respectively, the numbers
and volume fractions of components 1 and
2, and R is the gas constant. The enthalpic
term contains a temperature-dependent
interaction term, y1? so that
nx 02 (9-23)
These two expressions may be combined
to give the Flory-Huggins equation
AGm = - RT[nx\n(fa)
(9-24)
which may then be used to calculate phase
boundaries for polymer mixtures if the tem-
perature dependence of the interaction
parameter, X\-> *s known.
Equation (9-24) is dominated by the con-
tact dissimilarity term %xn x (1 - fa), since the
combinatorial terms, being products of
molar mass and volume fraction, are con-
stant. For example, simple mixtures, such as
pairs of isomeric polyolefin polymers or
polystyrene-polyisoprene, which are dom-
inated by van der Waals interactions, have
interaction parameters of the form
Z = A+| (9-25)
where A is the constant entropic contribu-
tion and B/T is the temperature-dependent
enthalpic contribution. More complex mix-
tures, such as polystyrene-poly(vinylmeth-
ylether), have interaction parameters that
are dominated by volumetric parameters
and are of the form
X = A + ^ + CT (9-26)
where CT is a second enthalpic term given
by a complex function of the coefficients of
thermal expansion of the two polymers
(Olabisi et al., 1979).
The Flory-Huggins theory and the
temperature-dependence of x c a n then be
used to predict the equilibrium behavior of
two liquid polymers (in the form of a homo-
geneous melt) or a polymer and a solvent. (It
may be noted that this theory describes the
behavior of polymer mixtures better
than the behavior of the polymer-solvent
systems for which it was derived.) A good
derivation of the theoretical aspects of poly-
mer blends and a review of the phenomenol-
ogy is given by Hashimoto in Volume 12 of
this Series (Chap. 6, p. 251). The thermody-
namics and phase diagrams of polymers have
a number of important implications for poly-
mer processing which are often overlooked.
Thus a phase separation mechanism can dic-
tate the morphology of a material formed
from a polymer blend or produced by reac-
tive processing. Different morphologies
result depending on how and at what rate a
material passes through the phase diagram.

88
critical point
ex *-
Composition, <>
| phase diagram and an effective "tempera-
Figure 9-8. Free energy of mixing versus composi-
tion curves (top) defining the generalized phase dia-
gram (bottom) for a liquid-liquid system.
A generalized phase diagram for a poly-
mer mixture is shown in the top part of
Fig. 9-8. The binodal is obtained from the
points of cotangency in the free energy ver-
sus composition curve (shown in the top
part of Fig. 9.8), where the temperature
increases from Tx to T5. The spinodal
depicts the condition of thermodynamic
stability and is where the free energy versus
composition curve changes from concave to
convex (that is, when 82G/S(j)2 = 0). The crit-
ical point is where the binodal and spinodal
converge (that is, when <53G/<503 = O). Con-
ventionally, the abscissa is labeled as com-
position and the ordinate as temperature. As
already stated, the product of the molar mass
9.3 Multiphase Materials 485
HI one-phase region
Composition,
Figure 9-9. A generalized phase diagram, in terms of
1/(^AO versus the composition for a polymerizing
mixture, showing the coexistence and spinodal curves.
The vertical lines I, II, and III represent quenching
routes from the miscible region into the stable (single-
phase), the metastable, and the unstable (two-phase)
regions of the phase diagram. The equilibrium con-
centrations of the two phases formed are $ and $>
(coexistence) and (f)\ and (pi (spinodal).
and the interaction parameter dominates the
ture" may be defined as 1/(%N), where % is
the the Flory-Huggins interaction parame-
ter and N is the polymerization index. Thus
polymerization, which changes % and
increases N, is parametrically equivalent to
quenching a polymer mixture, and the gen-
eralized phase diagram may be redefined as
shown in Fig. 9-9. The use of the phase dia-
gram in this form may be exemplified by
considering three quenching or polymeriza-
tion routes, marked as I, II, and III on Fig.
9-9. These routes represent changes in the
position of a polymerizing mixture: (I) from
the one-phase region of the phase diagram
to another position in the one-phase region;
(II) to a position in the metastable region;
or (III) to a position below the spinodal
curve. No phase separation occurs via route
I. Polymerization via route II may result in
phase separation by nucleation and growth
and, in the case of polymerization via route
486 9 Structure Development in Reactive Systems
One-dimensional evolution of concentration profiles
Two-dimensional representation of
the resultant phase structure
Ill, phase separation will occur by spinodal
decomposition.
The nucleation and growth process is
shown schematically in Fig. 9-10 and
occurs when a mixture in the metastable
region is stable to infinitesimal (thermal)
concentration fluctuations but is unstable to
sufficiently large concentration fluctuations
where nuclei are formed. [A more detailed
review of the thermodynamics of nucleation
has been reported by Pelton in Volume 5 of
this Series (Chap. 1).] Once the energy bar-
rier has been overcome by the formation of
nuclei, randomly in space and time, the
nuclei then grow. Note that the concentra-
tion of nucleated species is depleted around
the nucleus and the molecules or chain seg-
ments that feed the new phase follow the
ordinary transport phenomena with a posi-
tive diffusion coefficient ("downhill" diffu-
sion). The early stages of the phase separa-
Figure 9-10. Schematic represen-
tation of the nucleation and growth
process showing the evolution of
(sharp) concentration profiles for
the two continuous-discontinuous
phases being formed.
tion process are characterized by the exis-
tence of a continuous-dispersed phase mor-
phology. Only if the nuclei grow to such an
extent that they reach the percolation limit
and coalesce, will they achieve continuity
and, unless phase separation is arrested
either by vitrification or by crystallization,
two layers will eventually form.
The spinodal decomposition process is
shown schematically in Fig. 9-11. In the
unstable region of the phase diagram
(beneath the spinodal curve) the mixture is
unstable to infinitesimal concentration fluc-
tuations and there is no thermodynamic bar-
rier to phase growth, so that phase separa-
tion occurs by a continuous and spontane-
ous process. Since the mixture is initially
uniform in composition, this spontaneous
process must occur by a diffusional flux
against the concentration gradient. Diffu-
sion of a species from a region of low con-

Jf\
J
1\ f \
One-dimensional evolution of concentration profiles
Two-dimensional representation of
the resultant phase structure
centration to a region of high concentration
is unusual and is termed "uphill" diffusion,
and when this process occurs, negative dif-
fusion coefficients can be measured. The
spinodal decomposition process is charac-
terized by a bicontinuity of the phases in the
early stages, although this feature may be
lost through Ostwald ripening as the system
seeks to minimize its free energy by mini-
mizing its interfacial area. As for nucleation
and growth, unless phase separation is
arrested, either by vitrification or by crys-
tallization, two layers will eventually form.
This minimization of the interfacial area
causes Ostwald ripening in a system under-
going spinodal decomposition and the
coalescence of particles in systems under-
going nucleation and growth: both mecha-
nisms, given time, eventually form two
layers. The morphologies are generally
fixed by the classic solidification mecha-
9.3 Multiphase Materials 487
Ostwald
ripening
Figure 9-11. Schematic represen-
tation of the spinodal decomposi-
tion process showing the evolution
of (sinusoidal) concentration pro-
files for the two co-continuous
phases being formed.
nisms of vitrification, crystallization, and
crosslinking, and it is nearly impossible to
discern from the final morphology which
phase separation mechanism was operative
if the early stage structure is lost. Neverthe-
less, it is possible in some cases to observe
relics of a phase separation mechanism, and
some examples are presented in later sec-
tions.
A novel technique, used to produce poly-
mer membranes for filtration purposes,
involves the thermally induced phase sep-
aration of a polymer solution (Hikmet et al.,
1988; Aubert, 1988). In this technique, a
polymer solution is cooled rapidly causing
phase separation to occur, and the demixing
solution travels down the tie-lines on the
coexistence curve until the polymer-rich
phase intersects the glass transition versus
composition curve (at the Berghmans
point). When this temperature-dependent
488 9 Structure Development in Reactive Systems
homogeneous solution
Berghmans
Point
1 Block copolymers are fundamentally dif-
pure Composition, pure
solvent polymer ferent from polymer mixtures in that they
Figure 9-12. A generalized phase diagram in terms
of T versus the composition for a nonpolymerizing
polymer-solvent mixture, showing how the phase sep-
aration process interacts with vitrification. Vitrifica- illustrates the phase diagram and equilibri-
tion arrests phase separation and leaves nonequilibri-
um structures with compositions (// and </>" which are
relics of the spinodal decomposition process.
composition is reached, the polymer-rich
phase vitrifies and the phase separation pro-
cess effectively stops. The solvent may then
be removed by freeze-drying to leave a low-
density polymer foam with a fine structure,
which is a relic of spinodal decomposition.
The phase diagram in Fig. 9-12 is a sche-
matic representation of the process and the
characteristic length of the structure formed
may be controlled by arresting the spinodal
decomposition process by vitrification at
different stages, as illustrated. The limita-
tions of the process are obvious in that the
solidification process requires heat transfer
and the structure formed is temperature- and
time-dependent. Asymmetric membranes
are formed if there is a thick section of solu-
tion relative to the rate of heat transfer: the
solution closest to the cooled surface under-
goes a rapid, deep quench, whereas the
material furthest from the surface undergoes
a slow, shallow quench. The reactive analog
to this processing route is the situation
where one polymer is immiscible with a sec-
ond polymer but soluble in its monomer.
The quench is performed by allowing the
monomer of the second polymer to polymer-
ize, and this process is used as a method of
processing intractable polymers, as dis-
cussed by Lemstra and Meijer (Chap. 10 of
this Volume).
9.3,1.2 Block Copolymers
comprise only one type of molecule contain-
ing sequences of unlike monomer units
covalently bonded together. Figure 9-13
um morphologies of model di-block copol-
ymers. When a homogeneous melt of block
copolymers is cooled, unlike interactions
will become unfavourable and unlike
monomer units will try to segregate, so that
an apparent upper-critical solution point is
observed. Phase separation per se is impos-
sible and a local ordering process will occur.
For block copolymers in the bulk state, free-
energy minimization results in the forma-
tion of ordered structures which are depen-
dent on the composition. The surface curva-
ture and domain size are effectively set by
the ratio of the radii of gyration of the poly-
mer chains forming the two blocks. The
transition, analogous to freezing, is from a
disordered state (liquid or melt) to an
ordered state (crystal), although the poly-
mer chains are amorphous locally and the
microstructure has long-range order. The
phase diagram shown (Fig. 9-13) was deter-
mined experimentally via a combination of
small-angle X-ray scattering (SAXS),
small-angle neutron scattering (SANS),
transmission electron microscopy (TEM),
and rheology (Khandpur et al., 1995), com-
pared with that predicted theoretically
(Leibler, 1980). The phase diagram is pre-
sented in terms of the product %N (which is
 9.3 Multiphase Materials 489

Im3m HEX :
40

30

20

10
Disordered

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

L
PI

Im3m HEX Ia3d HPL LAM

Cylinders Perforated
Spheres Bicontinuous Layers Lamellae

Figure 9-13. An experimental phase diagram for the polystyrene-polyisoprene di-block copolymer system in
terms of %N versus/ PI , the volume fraction of polyisoprene. Open and closed symbols represent the order-order
and order-disorder transitions, respectively, determined from rheological transition temperatures. The ordered
phases formed (Im3m, HEX, Ia3d, HPL, and LAM), determined from a combination of scattering and micros-
copy data, are illustrated at the bottom of the figure. The solid curves have been drawn to delineate the differ-
ent phases observed and may not define precise phase boundaries. The dashed curve (bottom) is the mean field
prediction (Liebler, 1980) of the ODT (order-disorder transition). (Adapted from Khandpur et al., 1995.)

inversely proportional to the temperature) which have alternating polystyrene-poly-

and the block copolymer composition,/.
There are effectively two routes for the
synthesis of block copolymers. Anionic
polymerization is used to make very well
characterized di-block and tri-block copol-
ymers by sequential monomer addition to a
living polymerization. Typical examples
are the polyolefin block copolymers
butadiene blocks (di-blocks and tri-blocks
are the most common, although multi-
blocks are available). Anionic polymeriza-
tion tends to form polymers with narrow
molar mass distributions of both the blocks
per chain and the block length. Step poly-
condensation is used to make multiblock
copolymers, and industrially, these are
490 9 Structure Development in Reactive Systems
made via one-step bulk reactions where a
low Tg oligomer is introduced into a poly-
merization forming a high Tm polymer. A
typical example is the use of a poly ether diol
in the reaction between 1,4-butane diol and
an aromatic isocyanate to form a segment-
ed block copoly(ether-urethane) which has
rubbery polyether segments and semi-
crystalline polyurethane segments. Typical-
ly, this process is used to make polymer
components via the RIM process. Step
copolycondensations always form multi-
block copolymers with distribution in both
the blocks per chain and the block lengths.
9.3.2 Linear Segmented Block
Copolymers
This section mainly deals with a class of
block copolymers that are formed via reac-
tive polymer processing. For most of the
materials discussed, reaction injection
molding (RIM) is the process (Becker,
1979; Kresta, 1982; Macosko, 1989; Ryan
and Stanford, 1989) that is most commonly
employed to form the block copolymers: the
RIM process is described in Sec. 9.1.1. The
unique combination of physical properties
provided by block copolymers is related
to their microphase-separated morpholo-
gies. The development of a microphase-
separated morphology during polymeriza-
tion is extremely complex. As the different
chemical reactions proceed, the chain
lengths of all the polymeric moieties pro-
duced increase, giving an increase in the
overall degree of polymerization, N. Addi-
tionally, the interaction parameters (#),
characterizing the miscibilities between the
different moieties, also change as a result of
the increase in N. In the specific case of seg-
mented block copolymerization, such
changes in % a n d N (or more strictly the
product %N) drive the system across ther-
modynamic boundaries and result in a tran-
sition from an initial homogeneous (disor-
dered) state to a microphase-separated
(ordered) state. The resultant morphology is
determined by the competition between the
kinetics of polymerization and those of
microphase separation (Ryan, 1990; Ryan et
al., 1990). Additionally, both homopoly-
meric and oligomeric species undergo sim-
ilar phenomena, resulting in macrophase
separation. The copolymer morphology that
eventually evolves may reflect phase separ-
ation and/or vitrification, crosslinking, or
crystallization, and is determined by the
competition between the kinetics of two or
more of these processes.
Understanding the complex competition
between polymerization and microphase
separation requires in situ, time-resolved
analytical techniques. The application of
FTIR spectroscopy and rheometry to obtain
chemical and macroscopic property infor-
mation during polymer formation in single-
phase systems has already been discussed
(Sec. 9.2.2). In multiphase systems, moni-
toring the kinetics of structure formation
requires time-resolved scattering tech-
niques such as SAXS and SALS (small-
angle light scattering), depending on the
length scales of the evolving molecular
structures. The acquisition of absolute and
accurate time-resolved scattering data then
enables the length scales, microphase-
separation transitions and mechanisms,
density changes, and derived diffusion coef-
ficients to be determined for any reactive
polymer-forming system. An example
(Elwell etal., 1994) of the information
obtained in a time-resolved SAXS experi-
ment carried out on a polyurethane foam-
forming system is given in Fig. 9-14.
9.3.2.1 Copolyurethanes
The formation of polyurethanes and poly-
ureas is based principally on the chemistry
 REAL-TIME SAMPLE LOCATION OF MICROPHASE
DENSITY CHANGES SEPARATION TRANSITION

MST
t = 60 2 s

X
20 40 60
time /s

EVALUATION OF MECHANISM OF
INTERDOMAIN SPACING 'd' DIFFUSION COEFFICIENTS MICROPHASE SEPARATION

The maximum in / (q) occurs at q = 0.05 A

corresponding to a d spacing of = 126 A
1 +O.6A 2 S 1
CO
GO
86 s
80s

[R(q)/q2]/AV

CD

0.01 0.03 0.05 0.07 0.09 0.11 0.002 0.004 0.006 0.008 0.01
scattering vector q /A q 2 /A 2

Figure 9-14. The application of time-resolved SAXS to the study of structure development in reactive polymer systems. The three-dimensional SAXS data
from a flexible polyurethane foam-forming system, comprising 38% by weight of polyurea hard segments, provide information on macroscopic density chang-
es, microphase separation, and domain size-scale, with simultaneous cell formation and copolymerization. The I(q) versus time plot shows data obtained at CO
scattering vector values of # = 0.036 (+), 0.050 (O), 0.076 (A).
492 9 Structure Development in Reactive Systems
of the isocyanate functional group involv-
ing, in particular, reactions with hydroxyl
and amino-functional groups. Several ex-
tensive reviews exist on the chemistry of
isocyanates (Saunders and Frisch, 1962;
Wright and Cummings, 1969;Lyman, 1966;
Reegan and Frisch, 1971).
Much of the work carried out on linear
segmented copolyurethanes formed by RIM
has been reviewed by Macosko (1989). For
example, structure-property relations were
determined for copolyurethanes comprising
a polyoxyethylene (POE)-tipped polyoxy-
propylene (POP) diol (Mn-2000 g mol"1) as
the soft segment, and hard segments formed
from 4,4/-diphenylmethane diisocyanate
(MDI) and 1,4-butane diol (BDO). Factors
that determined the final properties of the
copolyurethane included the hard segment
content, the structure, the degree of crystal-
Unity, the copolymer molar mass, and the
degree of microphase separation. The
effects of processing variables on the seg-
mental structure, molar mass, and degree of
phase separation of a linear poly ether-based
copolyurethane elastomer have also been
investigated (Camargo et al., 1982, 1983,
1985). In these studies, copolyurethanes
prepared in the absence of catalysts exhib-
ited macrophase separation and were of low
molar mass. Consequently, the materials
were brittle and possessed a highly hetero-
geneous morphology comprising hard
segment-rich globules with a spherulitic
texture. In contrast, the use of catalysts
drove the copolyurethane-forming system
into the high-temperature, single-phase
region of the phase diagram. The resulting
materials were microphase-separated and of
higher molar mass. Cooling after copoly-
merization produced materials with a fine,
interconnected microstructure. Monitoring
structure development in slow reacting
systems at low temperatures using FTIR
spectroscopy indicated that phase separa-
tion occurred at a characteristic number-
average, hard-segment sequence length
(iVn= 1.2). This observation was in agree-
ment with results obtained from earlier stud-
ies (Camargo et al., 1981) using light trans-
mission and differential scanning calorime-
try. In a later study (Camargo et al., 1985),
the molar mass of the polyether and the
structure of the chain extender were varied.
The polyether molar mass was varied from
2000 to 4000 g mol"1 and the butane-1,4-
diol (BDO) was replaced by ethane-1,2-diol
(EDO). Employing a higher molar mass
polyether at the same hard-segment content
resulted in materials that exhibited a higher
degree of microphase separation. The EDO-
based materials gave hard segments with
higher melting temperatures compared with
the BDO-based materials.
The dynamics of microphase separation
during fast, isothermal bulk copoly-
urethane-forming systems were studied at
different temperatures and concentrations
of dibutyltin dilaurate (DBTDL) catalyst
(Yang and Macosko, 1989). The copolyure-
thanes comprised 50% by weight hard
segment (MDI and BDO), and the soft
segment was a POE-tipped POP diol
(Mn^2000 g mol"1). FTIR spectroscopy and
dynamic rheometry were used to investigate
structure development during the bulk
copolymerizations. Reaction kinetics, ana-
lyzed by calculating the isocyanate conver-
sion from the decay in the isocyanate
absorption band, showed the copolymeriza-
tion to follow second order kinetics in the
initial stages, but to become diffusion con-
trolled at higher conversion. The phase sep-
aration dynamics were monitored using the
carbonyl absorption bands to determine the
extent of inter-urethane hydrogen bonding.
The point at which the concentration of free
carbonyl passed through a maximum and
that of the hydrogen-bonded carbonyl
showed a rapid increase was designated as

the onset of phase separation. The data indi-
cated that phase separation occurred early
in the reaction (<50% conversion of isocya-
nate). At low temperatures (<100C), the
onset of phase separation occurred at an
average sequence length of 1.0 to 1.3, in
good agreement with the results from earli-
er studies by Camargo et al. (1982, 1985).
The trend with temperature (at constant cat-
alyst concentration) for the onset of phase
separation, as detected by the growth in the
dynamic mechanical modulus, was consis-
tent with the FTIR data. However, the two
techniques probe different types of structu-
ral development, so that the estimates of the
time for characteristic phase separation
were not in agreement.
Similar studies by Blake et al. (1987)
using adiabatic rheometry to investigate a
linear, phase-separating RIM system,
showed the sharp rise in viscosity to be coin-
cident with physical gelation resulting from
vitrification of the hard segment-rich phase.
As the hard-segment content, catalyst con-
centration, and initial reactant temperature
were increased, the gel time decreased and
the conversion at gelation increased. Iso-
thermal rheometry on similar, but highly
catalyzed, copolyurethane-forming systems
was carried out (Perry et al., 1985) using
laboratory scale RIM equipment interfaced
to a specially designed rheometer. Systems
at four different hard-segment contents were
studied at various temperatures and catalyst
concentrations. The results showed that the
increase in viscosity during the reaction
occurred more rapidly than predicted sole-
ly from molar mass increases. Viscosity
increases were shown to be due to phase
separation of the hard-segment blocks,
which subsequently associate via hydrogen
bonds to form domains rich in hard segment
which act as physical (labile) crosslinks.
As the glass transition temperature of
the hard segment-rich phase approaches
9.3 Multiphase Materials 493
and exceeds the copolymerization temper-
ature (Tg>Treaction), vitrification occurs,
"freezing-in" the incipient morphology.
Synchrotron small angle X-ray scattering
(SAXS) has been used (Ryan et al., 1991 b)
to study microphase separation during the
bulk polymerization of a copolyurethane
comprising 48% by weight hard segment
(MDI and BDO) and a POE-POP diol soft
segment. A constant concentration (0.02%
by weight) of DBTDL catalyst was used.
Small-scale microRIM equipment was used
to meter, mix, and inject stoichiometric
amounts of the reactants into a thermostatted
cell, positioned in an optical bench in the
SAXS beam line. The results showed that the
rate of microphase separation was faster the
higher the polymerization temperature, but
that the degree of microphase separation in
the finally formed material was lower.
Although the scattered intensity at a fixed
angle was observed to increase with the
square of time and the length scale charac-
terizing the morphology of the material to
increase with temperature, it was not possible
to distinguish with certainty whether the ulti-
mate morphology was due to crystallization
of the hard segment or microphase separa-
tion of the noncrystalline regions. Despite
further analysis (Elwell et al., 1996 b) of the
FTIR and SAXS data (Yang and Macosko,
1989; Ryan et al., 1991b) in terms of the
Avrami equation, it is still not possible to
resolve which of these processes is dominant.
The reanalyzed data are shown in Fig. 9-15
and, for both the FTIR and the SAXS data,
the structural growth exponent n~2. The
plots indicate that growth occurs either by
microphase separation involving nucleation
and growth (Fig. 9-15 a) or by crystallization
involving either homogeneous nucleation of
discs or heterogeneous nucleation of rods
(Fig. 9-15b). The use of wide angle X-ray
diffraction (WAXD) to resolve this question
has proved inconclusive.
494 9 Structure Development in Reactive Systems

least squares fit with slope = 2.03

least squares fit with slope = 2.05 and correlation coefficient = 0.98
and correlation coefficient = 0.99

-0.5 -

2.5 -0.5
Int

Figure 9-15. Analyses in terms of the Avrami equation "] of the structure development occurring
1
during the formation of linear copolyurethanes from a polyether diol (Mn~2000 g mol" ), 1,4-butane diol, and
MDI. The hard segment content equals 48% by weight and the reaction temperature was 60 C. (a) Avrami plot
with 6 as the fractional degree of hydrogen bonding, normalized by NCO conversion. Data derived from time-
resolved FTIR obtained during polymerizations catalyzed with -0.01% by weight of DBTDL. (b) Avrami plot
with 6 as the relative invariant, Q/Q^, derived from time-resolved SAXS data obtained during polymerizations
catalyzed with -0.02% by weight of DBTDL.

Other attempts to model phase separation
in linear segmented copolyurethanes have
been made by Speckhard et al. (1986 a, b)
using Monte Carlo simulations. The effects
of molecular parameters such as the extent
of reaction, the structure and relative reac-
tivity of monomer on the copolyurethane
composition, the hard-segment length dis-
tribution, and the molar mass distribution
were studied. Additionally, the effects of
premature phase separation on the compo-
sition, molar mass, and hard segment
sequence length were predicted using a par-
titioning model which separates the reac-
tants into two separate phases prior to reac-
tion. Although the initial reaction condi-
tions used in the model are not a true repre-
sentation of reaction-induced phase separa-
tion, typical in many multiphase polyure-
thanes, the model does give some insight
into the numerical values of critical param-
eters, their distributions, and their influence
on the structuring processes.
More recent advances (Bras et al., 1995)
in the understanding of structure develop-
ment during the bulk copolymerization of
linear segmented copolyurethanes have
involved the use of simultaneous time-
resolved SAXS/FTIR. The system studied
comprised 30% by weight of hard segment
(formed from MDI and pentane-l,5-diol)
and a soft segment based on a monofunc-
tional POE-POP (monol pre-polymer,
M n ^2000 g mol"1). The kinetics of micro-
phase separation were derived from SAXS
data, while FTIR provided reaction kinetics
and hydrogen bonding dynamics data. The
importance of this work is twofold. First, it
demonstrates (for the first time) the use of
the simultaneous SAXS/FTIR technique
 9.3 Multiphase Materials 495

d118A (b) ' \

KI-LJ rY~K a s *
D^

'. K ' D

hydrogen-
bonded ^
135 urethane
" (1700 cm"1) a
a
ff H ^

I free urethane
| (1730 cm-1) ;

0 20 40 60 80 100 120 140

time /rnin.

(C) (d)
0.80

15 25 35 45 55 65 75 85 0 20 40 60 80 100 120 140

time An in. time /min.

Figure 9-16. Simultaneous SAXS-FTIR data showing microphase separation and hydrogen bonding occurring
during the formation of a model linear copolyurethane from a polyether monol (Mn~2000 g moP1), 1,5-pentane
diol, and MDI. The hard-segment content was 30% by weight and the reaction temperature was 20 C. (a) SAXS
presented as I(q,t)q2 versus time; (b) relative FTIR absorbances of hydrogen-bonded urethane (D) and free
urethane (O) versus time; (c) relative SAXS invariant and relative FTIR absorbance of hydrogen-bonded urethane
(normalized to isocyanate conversion,/?NCO) versus time; (d) FTIR reaction kinetics data expressed as isocyanate
conversion versus time.

and, second, it shows clearly that in a phase-
separating copolyurethane system, the onset
of microphase separation precedes that of
hydrogen bonding. The latter is illustrated
in Fig. 9-16c, which shows the growth in
the SAXS invariant (scattering power) and
the concentration of hydrogen-bonded ure-
thane carbonyl moieties as functions of the
reaction time. The order in which these phe-
nomena occur has been a source of contro-
versy for many years. Hydrogen bonding
will not in itself drive a phase transition. The
mixture phase separates first, creating
regions containing high local concentra-
tions of urethane structures, thereby
increasing the rate of hydrogen bonding.
The important conclusion drawn from this
study is that in the characterization of mul-
tiphase copolyurethane-forming systems,
the use of a single technique should not be
relied upon for the detection of the onset of
a phase transition. The fact that there is no
496 9 Structure Development in Reactive Systems

indication of hydrogen-bonded urethane es involving the developing polyamide

and/or urea carbonyl moieties does not sim-
ply imply that the reacting system is still in
a single phase.
9.3.2.2 Copolyamides
Structure development during the
anionic ring-opening polymerization of
8-caprolactam to form nylon-6 has been
investigated by Ishida and Scott (1986).
Competition between the kinetics of the
polymerization and crystallization process-
es, occurring during the reactive processing
of nylon-6, was determined spectroscopical-
ly using computer-controlled micro-RIM
equipment interfaced to an FTIR spectropho-
tometer. The technique enabled detailed data
on the competitive kinetics processes to be
obtained independently and, in addition, pro-
vided information on subtle structural chang-
chains. Information regarding the transient
crystallization behavior prior to completion
of the polymerization reaction was obtained.
Figure 9-17 a shows the change in the peak
position of the amide N-H stretch band dur-
ing the reaction. The shift indicates an
increase with time of the strength and/or the
extent of hydrogen bonding of the amide
hydrogen. The break in the curve at ^50 s
indicates the point at which the monomer
was completely consumed. Figure 9-17 b
shows the variation of the normalized area
under the absorption peak at 1201 cm"1 asso-
ciated with the a-crystal form of nylon-6
which develops during the reaction.
The curve in Fig. 9-17b essentially
describes the crystallization kinetics during
the reaction. Initially, the concentration of
monomer is high; this plasticizes the poly-
mer formed and, as polymerization pro-

0.2-

3300
300 300

Figure 9-17. Crystallization kinetics derived from real-time FTIR data obtained during the polymerization (via
RIM) of 8-caprolactam to form nylon-6. The polymerization was carried out at 160 C using hexamethylene di-
isocyanate as the initiator and sodium hydride as the catalyst, (a) Shift in peak position of the amide N-H stretch
band with polymerization time, (b) The increase with time of the amide N-H stretch band at 1201 cm"1 (nor-
malized to the band at 2930 cm"1) associated with the a-crystal form of nylon-6.

gresses, the rate of crystallization increases
due to the increased rate of nucleation. The
crystallization process continues until at
-50 s, as again indicated by the break in the
curve, there is insufficient monomer
remaining to plasticize the polymer: at this
point, there is a transition to homopolymer
crystallization kinetics.
9.3.3 Lightly Crosslinked Copolymers
9.3.3.1 Copolyurethanes
and Copolyureas
The majority of the work reported on
lightly crosslinked copolyurethanes and
copolyureas formed via RIM has involved
post-mortem analyses (see, for example,
Stanford et al., 1985, 1995,1996;Macosko,
1989). However, there have been some theo-
retical studies of mold filling and mold cur-
ing during RIM. A series of theoretical mod-
els was used (Manzione and Osinski, 1983;
Tighe and Manzione, 1988) to investigate
the effects of the resin and mold properties
on mold filling and mold curing during reac-
tion injection molding of crosslinked poly-
urethanes. Computer simulations of the
reactant flow and polymerization of these
systems within a mold cavity were present-
ed in the form of a three-dimensional con-
version map. However, the application of
these models required prior knowledge of
the physical and chemical properties of the
resins. The curing and temperature profiles
that develop in the mold cavity were com-
puted and applied to predict the process
cycle time and the possibility of excessive
exotherms within the mold.
There have been no reports on in situ stud-
ies of the structure development in these
copolymer-forming systems mainly due to
the rapid rates of the reactions involved. In
these nonlinear systems, the reactions are so
fast (7gel <2 s are common) that quite often
9.3 Multiphase Materials 497
the time resolution of the analytical equip-
ment is unsuitably slow. However, the model
linear systems discussed in Sec. 9.3.2.1 can
be used to interpret the nature of the struc-
ture development processes. In nonlinear
copoly(urethane-urea) and copolyurea
systems, the macro-diol has been replaced
by, respectively, a nominally trifunctional
hydroxy and amino-functionalized polyeth-
er as the soft-segment phase, and hindered
aromatic diamines are used as chain extend-
ers with MDI to form the hard-segment
phase (Ryanet al., 1988,1990,1991 a; Stan-
ford et al., 1995, 1996). Typically, nonsto-
ichiometric systems containing a small
excess (up to 5 mol%) of isocyanate groups
are used. The isocyanate conversion
required for such systems to form a covalent
chemical network is >90% (see Sec. 9.2.3).
However, as before, there is competition
between the kinetics of polymerization and
those of phase separation, and the critical
hard-segment block length (NUcrit) a t the
onset of microphase separation for the
majority of the systems studied is between
1.0 and 1.3 (Camargo et al., 1981-1985;
Yang and Macosko, 1989). This corresponds
to an extent of reaction, with respect to the
chain extender, of approximately 50-55%
and amounts to an overall isocyanate con-
version of the order of 50-60%.
Thus microphase separation of the hard-
segment sequence lengths in these nonline-
ar systems occurs via spinodal decomposi-
tion (Ryan, 1990) well before a covalent net-
work can be formed. Once the hard segment-
rich phase attains a composition that has a
r g >r m o l d , the material undergoes vitrifica-
tion to produce a nonequilibrium co-
continuous morphology in the as-molded
materials. Annealing these types of RIM
materials at temperatures above T^ leads to
an increase in the degree of purity of the
hard- and soft-segment phases and a sharp-
ening of the interfaces between the phases.
498 9 Structure Development in Reactive Systems
However, complete microphase separation
and a truly covalent chemical network are
difficult to achieve in these fast copolymer-
forming systems (Ryan et al., 1993; Stan-
ford etal., 1995, 1996).
9.3.3.2 Flexible Copolyurethane Foams
The reactive processing of water-blown
flexible polyurethane foam from liquid
monomers and oligomers involves a com-
plex combination of chemical and physical
events (Artavia and Macosko, 1990). From
room temperature and in less than five min-
utes, a liquid mixture of relatively low molar
mass components is transformed into a
material with a supramolecular architecture
in the form of a solid foam. Flexible poly-
urethane foam is formed by the simultane-
ous reactions of a diisocyanate with a poly-
ether polyol and water. The combination of
these two exothermic reactions leads to the
formation of a segmented block copoly-
(urethane-urea), of the -(HmS)w-type, where
Hm represents the polyurea hard segment
with a degree of polymerization m, and S is
the poly(ether-urethane) soft segment; n is
the degree of polymerization of the block
copolymer.
During copolymer formation and as the
viscosity increases, foaming occurs by the
co-generation of carbon dioxide gas evolved
from the water-isocyanate reaction. Mor-
phological development of the copolymer
during foam formation is complex (Artavia,
1991; Elwell, 1993). As the chemical reac-
tions proceed, the chain lengths (N) of all the
products increase and the interaction param-
eters (%) also change, forcing the system
across thermodynamic boundaries and caus-
ing a transition from an initial homogeneous
(disordered) state into a microphase separ-
ated (ordered) state as discussed previously
in Sec. 9.3.2. As copolymerization proceeds,
the core of the rising foam bun becomes self-
insulated by the surrounding polymerizing
mixture creating, in effect, a quasi-adiabetic
temperature environment. It is this particu-
lar aspect of the study on foam production,
especially of the kinetics processes
involved, that early investigators ignored.
Many of the kinetics studies (Merten et al.,
1968; Rossmy etal., 1977, 1979, 1981;
Hauptmann et al., 1980; Bailey and Critch-
field, 1981) were conducted under isother-
mal conditions and this led to erroneous
results and misinterpretation of the kinetics
data. Only when it was realized that analyt-
ical investigations had to be conducted under
forced-adiabatic conditions, was further
progress made in the understanding of
structure development for foam-forming
systems. The use of a forced-adiabatic FTIR
cell placed in the sample compartment of an
FTIR spectrometer was first reported by
Artavia and Macosko (1990) for determin-
ing the reaction kinetics during the forma-
tion of TDI-based polyurethane foams. More
recently, Elwell et al. (1996 c) developed the
technique further by using a different cell
design which enables sampling to be done
outside the spectrometer, they have also
applied this technique to the study of struc-
ture development during the formation of
MDI-based polyurethane foams. Further
details of the experimental arrangement and
analytical procedure are given elsewhere
(Elwell et al., 1993, 1995, 1996a).
Several studies of forced-adiabatic, time-
resolved FTIR spectroscopic measurements
during polyurethane foam formation have
been reported (Artavia and Macosko, 1990;
Priester etal., 1990; Elwell etal., 1993,
1995). The results demonstrated that the for-
mation of both urethane and soluble urea
moieties occurred in the initial stages of the
foaming reaction rather than sequentially, as
suggested in earlier studies conducted under
isothermal conditions. The onset of micro-
phase separation (MST) of polyurea hard-

segment sequence lengths occurs early in
the reaction at 50-60% conversion of the
isocyanate functional groups (Artavia and
Macosko, 1990; Elwell et al., 1993, 1995),
and, as discussed previously, this is well
before a covalent network could be devel-
oped.
Figure 9-18 shows the wide range of
information on in situ structure develop-
ment that is obtained from time-resolved
FTIR measurements conducted during the
formation, under forced-adiabatic condi-
tions, of MDI-based polyurethane foam.
The three-dimensional data clearly illustrate
the decay of isocyanate absorbance and the
growth in the carbonyl absorbance (Elwell
et al., 1995, 1996 a). This study also showed
the correlation between the isocyanate con-
version calculated from adiabatic tempera-
ture rise data and that from FTIR spectros-
copy to be within 3% after approximately
40 s of the reaction. In Fig. 9-18 b, the plots
of the normalized concentrations of soluble
and hydrogen-bonded urea groups versus
time clearly show the onset of microphase
separation (MST), indicated at the isocya-
nate conversion of 0.550.05. The rate of
association of the microphase-separated
urea, hard-segment sequences have been
observed to increase with an increase in the
amount of added water, thereby increasing
the ratio of urea to urethane groups (Elwell,
1993). The rate of association passes
through a maximum in close proximity to
the onset of vitrification of the polyurea hard
segments, as the system passes through the
Berghmans point (Ryan et al., 1993).
FTIR spectroscopy alone, although
capable of providing much information on
the reaction chemistry and on the sequence
of chemical events, both prior to and after
microphase separation, does not give any
indication of the mechanism(s) of phase
separation, the size scale of the developing
morphology, or the degree of microphase
9.3 Multiphase Materials 499
separation. The study of real-time morpho-
logical changes during polyurethane foam
formation requires the acquisition of kinet-
ics data for the structure development
obtained using time-resolved, forced-
adiabatic SAXS measurements. Such in situ
SAXS experiments during foam formation,
employing a forced-adiabatic SAXS sam-
pling cell positioned in the optical bench
assembly of a synchrotron beam line, have
been reported by Elwell et al. (1994). The
importance of such time-resolved SAXS
analyses, in terms of the wide range of struc-
tural information that can be obtained, has
already been demonstrated (see Fig. 9-14 in
Sec. 9.3.2). It is also possible to conduct a
more rigorous analysis on data such as those
in Fig. 9-14 (Connell et al., 1991) to deter-
mine the mechanism of phase separation
and the effective diffusion coefficients of
particular moieties during the phase separ-
ation process.
Despite the widespread applications of
cellular polymers, little has been reported
on the development of rheological proper-
ties during foam formation. The reason for
this lack of information is explained by the
scale of the dramatic changes that occur as
the foam is formed. A 20- to 30-fold change
in volume, a rapid increase in the viscosity
from -10 to ~104 Pa s, and a rapid reaction
exotherm make the acquisition of accurate
and reproducible data, via conventional rhe-
ometry, and the analysis and interpretation
of data for reacting polymer foams extreme-
ly difficult. Much of the work reported on
reacting foam systems was conducted under
isothermal conditions (Bessette and Sund-
strom, 1985; Nabata et al., 1988; Carriere
et al., 1992). The development and use of
an adiabatic rheometer was first reported
by Mora et al. (1991). More recently, the
evolution of rheological properties during
the formation of MDI-based copoly-
(urethane-urea) foams, under adiabatic
 1.00 cn
o
o
0.80"

0.60" CD

CD

reaction
(a) kinetics
0.40"
CD
o
0.20" CD
CD_
O

o.oo-
1
CD
13

33
CD
0 50 100 150 200 250 300 350 400 0)
O
time/s

N-H' N-H CD
H soluble urea
(1715 cm-1) hydrogen-bonded
urea (1654 cm 1 )
o
urethane
(1730 cm-
hydrogen 2
(b) bonding I
dynamics

1580

50 100 150 200 250 300 350 400

time/s

1.00
0.80
Q1
0.60
0.40
0.20
0.00
0.00 0.20 0.40 0.60 0.80
temperature conditions, has been investigat-
ed using a Rheometrics (RMS 800 series)
rheometer (Elwell et al., 1995). In this
study, a specially designed, temperature-
controlled rheometer plate was used in the
rheometer (Elwell, 1993). The technique
was developed further by Neff and Macos-
ko (1995). In general, the studies on foams
formed under adiabatic conditions show
that the rheological development can be
Figure 9-18. Time-resolved FTIR data obtained
under forced-adiabatic reaction conditions during the
formation of flexible polyurethane foam from a poly-
ether trial (Mn~6000 g mol"1), water, and an isomer-
ic MDI mixture, (a) Copolymerization kinetics in
terms of isocyanate conversion, /?NCO versus time,
determined from the decay of the NCO stretch band
(2270 cm"1), (b) Hydrogen-bonding dynamics, in
relation to the microphase-separation transition
(MST), derived from the variations with time of
the ^ C = O absorbances associated with soluble
urea (1715 cm"1) (O) and hydrogen-bonded urea
(1654 cm"1) ().
9.3 Multiphase Materials 501
Figure 9-19. Structure develop-
ment in terms of microphase- and
G'/Pa
macrophase-separation processes
occurring during the formation of
the flexible polyurethane foam
described in Fig. 9-18. Compara-
tive plots versus time of the rela-
tive invariant, Q\ from SAXS (A),
the hydrogen-bonded urea concen-
tration, [ / C = O ] b , from FTIR (o),
and the elastic shear modulus, G',
from rheometry ().
1.00
divided into four main stages: (i) bubble
nucleation, (ii) liquid foam and microphase
separation, (iii) physical gelation resulting
from vitrification of the hard segment-rich
phase, and (iv) chemical gelation to yield
the foamed copolymer. A graphical repre-
sentation of the structure development
occurring during the formation of MDI-
based foam is shown in Fig. 9-19 in terms
of the combined date derived from SAXS,
FTIR, and rheological analyses (Elwell
etal., 1995, 1996a). In Fig. 9-19, micro-
phase separation is shown to occur at an iso-
cyanate conversion of/?NCO~0.5 and is fol-
lowed quickly by hydrogen bonding. The
rheological properties around this conver-
sion are not well developed and are typical
of a liquid foam system: the system rheolo-
gy is only sensitive to hard-segment vitrifi-
cation, which causes an increase of approx-
imately two orders of magnitude in the value
of the elastic shear modulus G'. This rapid
development in the system rheology is
502 9 Structure Development in Reactive Systems
"^ ~
~*
Microphase separation
p N C 0 = 0.5$ 0.05
1/XN
V 1
pure Composition, <|> pure
soft segment M
hard segment
shown by the dramatic change in slope of
the G' versus /? NCO plot at /?NCO~0-8- An
interpretation of the structure evolution of
this foam-forming system, in terms of a gen-
eralized phase diagram, is presented in
Fig. 9-20. The sequential processes occur-
ring during foam formation as the system
passes down through the phase diagram
have been correlated with the conversion
(PNCO) of isocyanate groups, as indicated on
the right-hand side of Fig. 9-20.
9.3.4 Highly Crosslinked Copolymers
and Resins
9.3.4.1 Rigid Copolyurethane Foams
Rigid polyurethane foam is also formed
by the simultaneous reactions of a diisocya-
nate with a polyether polyol and water
except that, compared with flexible foam
systems, polyols with a much lower molar
mass (typically 400-2000 g mol"1) and a
higher (nominal) functionality (4-8) are
emloyed. In rigid foams, the majority of the
cells (>80%) are closed, whereas the reverse
Start of reaction Figure 9-20. Application of the gen-
PNCO = eralized phase diagram for a copoly-
decrease in density merizing system to the interpretation
of structure development during the
formation of copolyurea and poly-
urethane foam. Superimposed on the
Cell opening phase diagram is the Tg versus com-
constant density position (0H) curve. The vertical line
Modulus growth through the critical point represents
PNCO = -' 1 0 0 2 the increasing extent of reaction
(pNco) a s t n e system approaches
equilibrium (Eq) and the horizontal
lines represent the degree of micro-
phase separation achieved as copoly-
merization proceeds, relative to the
maximum amount defined by the
coexistence curve. Vitrification of
the hard segment-rich phase occurs
when TgH = Tfoam, i.e., where the Tg
curve intersects the coexistence
curve (the Berghmans point).
is the case in flexible foams. Very little work
has been carried out on the structure devel-
opment during rigid foam formation. Inves-
tigations (Marciano et al., 1982) of the effect
of the catalyst concentration on the curing
kinetics, carried out using the adiabatic tem-
perature rise technique, showed that second-
order kinetics gave a good fit to the data prior
to the gel point. Isothermal curing of a rigid
foam system was studied by Nabata et al.
(1988) utilizing a dynamic viscoelastic
method, although there was little discussion
of structural development. In studies on rigid
polyisocyanurate foam systems incorporat-
ing different blowing agents (CFC and a
50/50 w/w % CFC/H2O mixture), time-
resolved, forced-adiabatic FTIR spectrosco-
py was used (Priester et al., 1990) to moni-
tor differences in the reaction chemistry, par-
ticularly in the formation of carbodiimide
moieties. A recent, in-depth study (Griin-
bauer et al., 1992) has investigated the
effects on the structure development of
reducing the functionality and increasing the
equivalent molar mass of the polyol in
systems incorporating either water or CFC

blowing agents. Time-resolved, forced-
adiabatic FTIR spectroscopy showed that in
water-blown systems, urea formation occurs
early in the reaction, followed by competi-
tive polyurethane formation. In FTIR spec-
tra, a peak associated with hydrogen-bonded
urea is readily discernible at -1654 cm"1.
Post-mortem analyses on the foams were
conducted using dynamic mechanical-
thermal analysis (DMTA) and SAXS. The
DMTA data showed that the value of Tg was
unaffected by a variation in the polyol func-
tionality, and the damping peak around Tg
was broad in all cases. The SAXS data
showed no maxima in the scattered intensity,
as observed in flexible copoly(urethane-
urea) foams. A more recent SAXS study on
water-blown rigid foam by Griinbauer and
Folmer (1994) suggests that the phase-
separated morphology in rigid foam systems
is of an irregular 'fractal' nature.
9.3.4.2 Isocyanurate-Based Resins
Isocyanurate-based resin-forming sys-
tems involve multiple competitive reactions
which can be tailored to provide controlled
processability during the reactive process-
ing of structural composites (Vespoli and
Alberino, 1985; Ryan et al., 1993, 1995).
For example, copoly(urea-isocyanurate)s
(PUrls) have been formed by reacting (via
RIM) a polyether diamine (Mn^2000 g
moP1) with a large stoichiometric excess of
MDI in the presence of an organic trimer-
ization catalyst (Ryan et al., 1993). Copol-
ymerization occurs by a two-stage process
initially involving the rapid formation of
isocyanate-tipped poly(ether-urea) oligo-
mers and, secondly, involving the trimeriza-
tion of isocyanate-functionalized moieties
to form the final glassy, highly crosslinked
PUrl resin. Thus in the production of struc-
tural composites via RIM, the mold-filling
viscosity, the gel time, PUrl resin formation,
9.3 Multiphase Materials 503
and final properties are readily controlled
by systematically varying the molecular
structure, the stoichiometric ratio of the
monomers and polyether, and using appro-
priate catalysts and temperature levels.
Both in situ and post-mortem studies have
been carried out on the formation and prop-
erties of PUrls, and their use as matrices in
RIM structural composites. In the former
case (Wilkinson et al., 1996), structure
development was monitored using time-
resolved synchrotron SAXS. Micro-RIM
apparatus was used to meter and mix the
two reactants [MDI and polyoxypropy-
lene(POP)diamine], and to inject the reac-
tant mixture into a mold cell positioned in
the optical bench assembly of the synchro-
tron beamline. Typical scattering data for a
copolymerization carried out at 90 C are
shown in Fig. 9-21 a, in which the evolution
of a microphase-separated structure is illus-
trated by the development of a maximum in
the scattering profile at g*~0.065 A"1,
which increases in intensity as copolymer-
ization progresses from -38 to 68 s. The
interdomain spacing (d) of this structure was
calculated from the scattering maxima to
give a value of d~91 A, which agrees well
with post-molding values of d determined
via static SAXS and TEM measurements on
this system (Ryan et al., 1993).
PUrl formation was studied at different
temperatures in the range 70-135C, and
values of Q' (the relative invariant) were
determined from SAXS data as a function
of the reaction time. At each temperature,
Q versus time is characterized by an induc-
tion period (negligible growth), a period of
rapid growth (microphase separation), and
a plateau region (growth arrest). Represen-
tative data are shown in Fig. 9-21 a for a
PUrl formed at 70 C for which the induc-
tion period (0-74 s) and the microphase-
separation region (74-128 s) are clearly
evident. The onset times for microphase
504 9 Structure Development in Reactive Systems

(a) 1 , 1 . . . .

90 c ; 70 C

reaction * V) 0.7-
time t = 128 0.5 s j$P^

rbit rary ui

68 s " oo^

/J
arbitrary units

-
CO
0.5-
50so b
/

varic
cr _
A
=
0.3- //
/
A
AAA
>
38 s /
0)
DC
/ 20 s; oo I ^ N = 74 0.5 S
0.1-
8s
nr i,,,, 1 1 1 1 1 ri 1 1 rT 1 . 1 1 1 1 1 1

0.00 0.05 0.10 0.15 0.20 50 100 150 200

q/A"1 Time / s

(b) 4000

1000 -

0.00 0.05 0.10 0.15 0.20 0.25

q/A" 1
Figure 9-21. Structure development in copoly(urea-isocyanurate)s (PUrls) formed via RIM of a polyether dia-
mine (Mn=2000 g mol"1), liquefied MDI, and a trimerization catalyst. Reactant temperatures = 35 C; mould tem-
perature =90 C. The copolymers comprise -50:50 v/v % polyether rubber: polyisocyanurate glass, (a) Time-
resolved SAXS data with derived plots of the relative intensity I(q)q2 versus q and the relative invariant Q ver-
sus time, (b) TEM and SAXS data (post-mortem) for a PUrl formed at 90 C, showing the effects of annealing
on the microphase-separated structure. The improvement in the phase contrast of the co-continuous morpholo-
gy is shown clearly by comparing the as-molded PUrl (top TEM) and the PUrl annealed at 150C for 1 h (bot-
tom TEM).

separation decrease with increasing temper- temperatures, the scattering peak intensity
ature following an Arrhenius rate depen- increases exponentially with time, indica-
dence, indicating that the MST occurs at the tive of spinodal decomposition, as predict-
same degree of isocyanate conversion, inde- ed by the linearized theory of Cahn and Hil-
pendent of the temperature. At all reaction liard (1958).

As expected for a block copolymer, the
size scale of the growing structure is inde-
pendent of temperature and the molecular
connectivity between the polyether and
polyisocyanurate phases restricts the inter-
domain spacing to values in the range
2<(<?* Rg)<3, as predicted by Leibler (1980).
The radius of gyration Rg of combined hard
block-soft block segments in the PUrl is not
known, although values of Rg have been
determined from SANS data for a polyure-
thane block copolymer formed using a
POP pre-polymer of similar molar mass
(-2000 g mol"1). The radius of gyration
(T^g)pop for POP chains was measured as
13.5 A in the disordered (relaxed) state, and
16 A in the ordered (stretched) state. Using
these values for the PUrl, for which the vol-
ume fraction of POP is </>pOp = 0.43 and Rg
is approximated by [(/?g)pop/0pop]> gives
values of (q* Rg) in the range 2.0-2.4.
These values are typical of a block copol-
ymer. Thus values of d calculated using
(^g)pop= 16 A lie in the range 74<d<l 15 A
and are in reasonable agreement with the
experimental value of 97 A determined from
the SAXS data (Wilkinson et al., 1996).
These studies lead to the somewhat surpris-
ing conclusion that a complex copolymer-
ization, ultimately producing a microphase-
separated glassy polymer network, shows
the dynamics of simple liquid-liquid phase
separation.
Microphase separation is arrested prema-
turely by vitrification of the polyisocyanu-
rate phase, and produces materials with non-
equilibrium, co-continuous morphologies.
Some representative data from post-mortem
studies on the as-molded and post-cured
PUrl materials are shown in Fig. 9-21 b
(Ryan et al., 1993). The TEM micrographs
show that high-temperature annealing
improves the phase contrast of the
microphase-separated structure, as con-
firmed by the increases in both the peak
9.3 Multiphase Materials 505
intensity q* and the relative invariant Q' in
the static SAXS data. These data confirm
the co-continuous morphologies (with
length scales -100 A) of the post-cured
PUrl materials, which may be classed as
rubber-modified resins exhibiting two glass
transition temperatures, one at -40 C
associated with the polyether rubber phase,
and the other at ^180C associated with
the crosslinked polyisocyanurate phase.
The PUrl materials show only a small
modulus-temperature dependence between
-20 and 250 C, with flexural moduli of =2.0
and 0.5 GPa at 20 and 200 C, respectively.
In addition, the PUrl systems were success-
fully used to produce structural hybrid com-
posites (Ryan et al., 1995) comprising up to
40% by weight of pre-placed fiber mats, in
cycle times of under 60 s.
9.3.4.3 Rubber-Modified Epoxy Resins
Structure development resulting from
reaction-induced phase separation in epoxy
resin systems containing functionalized liq-
uid rubbers has been studied by a number of
workers (Chen et al., 1993; Ohnaga et al.,
1994). The liquid rubbers used are amino-,
carboxyl-, and epoxide-functionalized ran-
dom copolymers of butadiene and acrylo-
nitrile, designated, respectively, ATBN,
CTBN, and ETBN, with Mn typically
between 2000 and 4000 g mol"1.
In one study (Ohnaga et al., 1994), net-
work formation of epoxy resin systems,
comprising diglycidylether of bisphenol-A
(DGEBA), a secondary amine curing agent,
and either a CTBN or an ATBN, was mon-
itored using light scattering (LS), torsional
braid analysis, and scanning electron
microscopy (SEM). For systems cured at
100 C, the use of a high-reactivity curing
agent (Versamid) produced an epoxy resin
containing uniformly sized spherical
domains, whereas with a low-reactivity cur-
506 9 Structure Development in Reactive Systems
10 20 30 40 50
Scattering angle, 20/degree
Figure 9-22. Time-resolved light scattering data for
the rubber-modified epoxy resin system comprising
DGEBA, amine-terminated butadiene-acrylonitrile
liquid rubber, and Versamid (100:45 :50 pbw). The
development of a regular, phase-separated structure
begins after ~4 h at a polymerization temperature of
24 C, as shown by the growing peak at 20-28.
ing agent (piperidine), the spherical domain
structure produced comprised a bimodal
size distribution. In contrast, an epoxy
system containing ATBN, cured with piper-
idine at room temperature, yielded a resin
with a co-continuous, two-phase morpho-
logical structure. For the latter system, light
scattering data obtained at increasing reac-
tion times, given in Fig. 9-22, show that
after ~4 h, a scattering peak appears, sug-
gesting the development of a regular phase-
separated structure. The intensity of this
peak increases exponentially with time,
although the peak position does not change
with time. Similar behavior was also
observed for the CTBN system cured with
piperidine at 90 C. Such behavior is indic-
ative of phase separation proceeding via spi-
nodal decomposition. Figure 9-23 shows
representative SEM micrographs of the dif-
ferent types of morphological structure
formed in these rubber-toughened epoxy
resins by varying the curing schedule.
More recently, Chen et al. (1993) have
investigated epoxy resin-forming systems
Figure 9-23. Scanning electron micrographs of the
fully cured epoxy resin defined in Fig. 9-22. (a) The
resin cured at 24 C for 10 h and postcured at 100 C
shows an interconnected globular structure, (b) The
resin cured at 100 C (without prior curing at 24 C)
shows a spherical domain structure.
comprising DGEBA, 4,4'-diamino-3,3'-
dimethyldicyclohexylmethane, and 15% by
weight of ETBN rubbers of different molar
mass. Investigations included the influence
of the pre-cure temperature, the molar mass
of the rubber, the postcure, vitrification, and
gelation on the evolution of the structure.
Reaction-induced phase separation was
monitored in situ using SAXS, light trans-
mission (LT), and light scattering (LS) tech-
niques to provide structural information
over two size scales, that is 20-1000 A
(SAXS) and 0.1 |im (LT). In addition,
post-mortem analyses of final morphologies
were carried out using DSC (differential
scanning calorimetry), DMTA, SEM, and
TEM. Reaction-induced phase separation

200 400 600
Time / minutes
was attributed to entropy changes resulting
from molar mass increases in the system as
the polymerization proceeded. The SAXS
scattering data given in Fig. 9-24 show three
distinct regions which may be described as
follows:
Region I: An initial period (from time zero
to tx), during which the reaction
mixture is homogeneous. At the
onset (time t{) of phase separa-
tion, there is a monotonic
increase in the scattered inten-
sity (SAXS) with time over the
period tx to t2.
Region II: As the structure giving rise to
the scattering grows and its size
exceeds the observation win-
dow of size scales amenable to
SAXS, the scattered intensity
apparently decreases over the
period t2 to t3. This structure,
however, is detectable by LT/LS
and is manifested as a cloud
9.3 Multiphase Materials 507
Figure 9-24. Structure development
during the formation of a rubber-
toughened epoxy resin system com-
prising DGEBA, 4,4'-diamino-3,3'-
dimethyldicyclohexylmethane, and an
epoxy-terminated butadiene-
acrylonitrile liquid rubber. The time-
resolved SAXS data, in the form of
integrated intensity versus pre-cure
time at 50 C, show three distinct
regions (I, II, III) of morphological
development, as depicted by the inset
schematic diagrams. [Adapted from
Chenetal. (1993).].
point in a plot of the scattered
light intensity versus reaction
time.
Region III: The SAXS scattered intensity
again increases and then
exceeds the values reached in
region I. At longer times (t
>500 min), the scattering curve
reaches a plateau and further
structure development is found
to be blocked by postcure.
The results were interpreted in terms of
the development of two topological levels
of morphology. These consisted of a glassy
matrix of epoxy resin in which there were
dispersed rubbery particles. Each of these
rubbery particles itself acts as a sub-matrix
and contains glassy sub-particles of epoxy
resin. The evolution of the two morpholog-
ical levels is shown schematically in Fig.
9-24 in relation to the three regions of
behavior described above. It was proposed
that the primary structure grows out of the
508 9 Structure Development in Reactive Systems

size-scale window amenable to SAXS and

is responsible for the decrease in the SAXS
scattered intensity in region II, and it is the
sub-structure that gives rise to the second
increase in intensity of the SAXS data, as
observed in region III.

9.3.5 Interpenetrating Networks A

S/DVB 1 PBMA
copolymer
Structure development during the forma-
tion of both full and semi-interpenetrating Figure 9-25. Schematic ternary phase diagram
polymer networks (IPNs) has been investi- for the system styrene/divinylbenzene (S/DVB)
monomer: S/DVB copolymer: poly(butylmethacry-
gated, usually through the use of light scat- late) (PBMA). The shaded area depicts the two-phase
tering techniques. Studies on various IPN region, and the reaction routes for miscible and immis-
systems have been reported, such as, for cible S-PBMA mixtures are represented by the lines
example, divinylbenzene-styrene copoly- AA, and B B b respectively.
mer and poly(butylmethacrylate) semi-
IPNs (Lipatov et al., 1985), polyurethane 10
16
20
and polystyrene semi-IPN s (He et al.,
1993 a, b), and IPNs based on unsaturated
10 u 1
polyester and polyurethane (Lee and Kim,
1993).
The formation of the semi-IPN com-
prising styrene-divinylbenzene (S/DVB) 2nd branch
copolymer and poly(butylmethacrylate)
(PBMA), studied by Lipatov et al. (1985),
is shown on the schematic ternary phase dia-
gram in Fig. 9-25. The reaction paths of two
compositions (A to Ax and B to Bx) are
shown. Initially the mixture of PBMA and
the monomers is homogeneous, but as the 1 st branch

polymerization proceeds, the system enters

104
the two-phase region of the diagram and 500 1000 1500 2000
phase separation occurs. Light scattering Time / s

was used to monitor the structure develop-
ment during IPN formation and Fig. 9-26
shows the scattered intensity at two repre-
sentative scattering angles (10 and 20)
plotted against time. The reaction-induced
phase separation process has two stages, and
the exponential growth of the scattered
intensity was interpreted as a signature of
spinodal decomposition. The two growth
regimes were interpreted qualitatively as
regions characterized by different interdif-
Figure 9-26. Phase separation during the formation
at 60 C of a semi-IPN from a 10% by weight solution
of PBMA in S/DVB monomer. The plots show time-
resolved, scattered light intensity data obtained at two
registration angles: 10 (o); and 20 ().
fusion coefficients, length scales, and acti-
vation energies. The data have been reana-
lyzed (Elwell et al., 1996b) in the context
of the Cahn-Hilliard theory for spinodal
decomposition. The slope of the plot \nl(q)

__ 40 ~
10"
o-h
0 10 20 30 40 50
10'8. q 2 /cm" 2
Figure 9-27. Plots of the amplification factor, R (q) q2,
versus q2, derived from the scattering data for the semi-
IPN defined in Fig. 9-26. Extrapolation of the plots
gives values of 13xl(T13 and 51xl(T 13 cm2 s"1 for the
interdiffusion coefficient Deff for the two stages (I and
II, respectively) of phase separation.
versus q is taken to give the amplification
factor R(q). The value of the cooperative
diffusion coefficient, Deff, for each of the
two growth processes is determined from
the intercept of the plot of R(q)/q2 versus q2
(see Fig. 9-27). Thus the cooperative diffu-
sion coefficient for the initial, slower pro-
cesses is estimated to be 13xl0~13 cm2 s -1 ,
and that for the second, faster process,
51xlO- 13 cm 2 s- 1 .
The reaction and phase separation kinet-
ics involved during the formation of
polyurethane-polystyrene semi-IPNs were
investigated by He et al. (1993 a, b). The net-
works were prepared via a single step route.
The polyurethane network was prepared by
the catalyzed reaction of polypropylene-
oxide) with pluriisocyanate in styrene at
room temperature. After a specified time,
the temperature of the reaction mixture was
9.4 Summary 509
raised to 70 C to promote polymerization
of the styrene. The reaction kinetics were
studied using FTIR spectroscopy in trans-
mission mode and the phase separation
kinetics were studied using light transmis-
sion. It was observed that if the system
underwent chemical gelation prior to phase
separation, the extent of phase separation
was limited and the samples remained opti-
cally clear. However, if phase separation
preceded chemical gelation, macrophase
separation occurred and the samples pro-
duced were turbid.
The phase separation behavior of unsatu-
rated polyester-polyurethane IPNs has been
studied (Lee and Kim, 1993) using light
scattering measurements during simultane-
ous polymerization at various temperatures.
The dominant phase separation process was
observed to be spinodal decomposition. The
change of the scattered light intensity with
time showed the formation of the dispersed
domains, and the average domain correla-
tion length could be calculated from the
angle of maximum scattering intensity. As
the reaction temperature increased, the
domain correlation length increased and the
scattering peak broadened, indicating a
greater size distribution of the heterogene-
ous structure present. As the reaction tem-
perature is increased, the rate of reaction
increases and gelation occurs earlier, thus
restricting the extent of phase separation.
9.4 Summary
The results presented in this chapter show
that the understanding of structure develop-
ment in reactive processing is well
advanced. The techniques required to gain
the necessary information to model reactive
processes are available. The quantitative
determination of polymerization reaction
kinetics requires spectroscopic techniques
510 9 Structure Development in Reactive Systems
such as NMR (nuclear magnetic resonance),
Raman, and FTIR, and these are well estab-
lished. The development of polymer mor-
phology is best studied by time-resolved
photon scattering techniques using either
lasers (for SALS) or synchrotron sources
(for S AXS). Physical property development
is studied by mechanical spectroscopy of the
rheological and modulus behavior.
The theoretical framework for reaction-
induced phase separation is also well estab-
lished. Once the routes through phase-
space are known, there are three basic
mechanisms of phase separation: spinodal
decomposition, nucleation, and growth for
liquid-liquid systems, and crystallization
for liquid-solid systems. Morphological
pinning occurs by crosslinking and/or vit-
rification in the liquid-liquid case. It is dif-
ficult (if not impossible) to define general
laws for reactive systems, because the
nature of reactive processes makes them
unique. There are well established laws
(models, theories) for polymerization kinet-
ics and statistics, and the thermodynamics
of phase separation and crystallization are
well established.
The kinetics of phase separation are also
well established for polymers with narrow
molar mass distributions. Reactive process-
ing couples, in a competitive manner, the
kinetics of polymerization and phase separ-
ation. The vast differences in behavior seen
by minor variations in the formulation are a
manifestation of the intrinsic instability in
the interactions between phase separation
and polymerization. A number of challeng-
es remain in the reactive processing of poly-
mers, and there are an endless number of
systems still to be studied experimentally.
Such studies will continue, but if significant
advances are to be made, there should be an
increased emphasis placed on the theory and
modeling of reactive processes. Predictive
modeling based on combined reaction kinet-
ics and thermodynamics may be possible in
only a few specific systems. Nevertheless,
it should be explored.
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30, 1839.
Yang, W. P., Macosko, C. W. (1989), Die Makromol.
Chem., Macromol. Symp. 25, 23.
General Reading
Binder, K. (1991), in: Phase Transitions in Materials:
Haasen, P. (Ed.), Materials Science and Technol-
ogy, Vol. 5. Weinheim: VCH, Ch. 7.
Hasegawa, H., Hashimoto, T. (1996), "Self-Assemb-
ly and Morphology of Block Copolymer Systems"
in: Comprehensive Polymer Science, 2nd Suppl.:
Aggarwal, S. L:, Russo, S. (Eds.). Oxford: Perga-
mon, Ch. 14, pp. 497-539.
Hashimoto, T. (1993), in: Structure and Properties of
Polymers: Thomas, E. L. (Ed.). Materials Science
and Technology, Vol. 12. Weinheim: VCH, Ch. 6.
Kuchanov, S. I., Panyukov, S. V. (1996), "Statistical
Thermodynamics of Copolymers and Their Blends"
in: Comprehensive Polymer Science, 2nd Suppl.:
Aggarwal, S. L., Russo, S. (Eds.). Oxford: Perga-
mon, Ch. 13, pp. 441-496.
Macosko, C. W. (1989), RIM: Fundamentals of Reac-
tion Injection Moulding. Munich: Hanser.
Stepto, R. F. T. (1992), in: Comprehensive Polymer
Science, 1st Suppl.: Aggarwal, S. L., Russo, S.
(Eds.). Oxford: Pergamon, Ch. 10, pp. 199-226.
10 Processing of Polymers Using Reactive Solvents
Piet J. Lemstra, Jenci Kurja and Han E. H. Meijer

Centre for Polymers and Composites, Eindhoven Polymer Laboratories,

Eindhoven University of Technology, The Netherlands

List of Symbols and Abbreviations 514

10.1 Introduction 516
10.2 Classification of Synthetic Polymers 518
10.2.1 Thermoplastics 519
10.2.2 Thermosets 520
10.2.3 Rubbers 521
10.3 Guidelines for the Selection of a Reactive Solvent 521
10.4 Basic Aspects of Processing with Reactive Solvents 523
10.4.1 Phase Behavior of Amorphous Polymers in Solution 523
10.4.2 Phase Behavior of Semicrystalline Polymers 525
10.4.3 Thermally Versus Chemically Induced Phase Separation 527
10.5 Example of an Intractable Polymer/Reactive Solvent System:
The Poly(phenylene ether) (PPE)/Epoxy System 529
10.5.1 Materials Choice: PPE/Epoxy 529
10.5.2 Phase Behavior of PPE/Epoxy Solutions 529
10.5.3 Curing of PPE/Epoxy Solutions 531
10.5.4 Morphology Development 533
10.5.5 Mechanical Properties 536
10.5.6 Composite Applications 538
10.6 Examples of Tractable Polymer/Reactive Solvent Systems 540
10.6.1 The Poly(methylmethacrylate)/Epoxy System 540
10.6.2 The Polyethylene/Styrene System 542
10.6.2.1 Miscibility of Polyethylene and Styrene 542
10.6.2.2 Morphology Development as Revealed by Small Angle X-Ray Scattering
(SAXS) and Wide Angle X-Ray Scattering (WAXS) 543
10.6.2.3 Morphology as Revealed by Electron Microscopy 545
10.7 Concluding Remarks and Future Outlook 545
10.8 References 546

Materials Science and Technology

Copyright WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
514 10 Processing of Polymers Using Reactive Solvents

List of Symbols and Abbreviations

critical interparticle distance
number-average particle diameter
weight-average particle diameter
Gc critical strain energy release rate
Glc fracture toughness
AH{ heat of fusion per mole of repeating units
Hq) intensity
weight-average molar mass
q scattering vector
Q experimental invariant
R gas constant
f
gel gelation time
vitrification time
temperature corresponding to the Berghmans point
dissolution temperature
glass transition temperature
T melting temperature of the crystals in the solvent
1
m equilibrium melting point of a pure crystal
1
m
polymerization temperature
room temperature
molar volume of solvent
molar volume of the monomer unit in the polymer chain

77* dynamic viscosity

e scattering angle (26)
i wavelength
electron density
p
(fo volume fraction of polymer in polymer-solvent mixture
volume fraction of solvent in polymer-solvent mixture
X Flory-Huggins interaction parameter

ABS acrylonitrile-butadiene-styrene graft copolymers

B.P. Berghmans point
CIPS chemically induced phase separation
CSAI compressive strength after impact
CTBN carboxyl-terminated butadiene-acrylonitrile
DGEBA diglycidyl ether of bisphenol-A
DGEPPO diglycidyl ether of polypropylene oxide
DMTA dynamic mechanical-thermal analysis
EPDM ethylene-propylene-diene monomer rubber
HDPE high density polyethylene
HIPS high-impact polystyrene
 List of Symbols and Abbreviations 515

IPN interpenetrating network

LCP liquid crystalline polymer
L-L liquid-liquid phase separation
L-S liquid-solid phase separation
M-CDEA 4,4/-methylene-bis(3-chloro-2,6-diethyl aniline)
MMA methylmethacrylate
PBT poly(butylene terephthalate)
PC polycarbonate
PE polyethylene
PEI polyetherimide
PES poly(ether sulfone)
PETP poly(ethylene terephthalate)
PMMA poly(methylmethacrylate)
PP polypropylene
PPE poly(2,6-dimethylphenylene ether)
PPO polypropylene oxide
PPTA poly-/?-phenylene-terephthalamide
PS polystyrene
PSU polysulfone
SAXS small angle X-ray scattering
SEM scanning electron microscopy
TEM transmission electron microscopy
TIPS thermally induced phase separation
UCST upper critical solution temperature
UHMWPE ultrahigh molecular weight polyethylene
WAXS wide angle X-ray scattering
516 10 Processing of Polymers Using Reactive Solvents
10.1 Introduction
Polymer science and technology is the
paradigm of a multidisciplinary area. The
path from monomer via polymer to func-
tional materials and products travels
through the various disciplines of macromo-
lecular science, polymer chemistry and
physics, thermodynamics, rheology, pro-
cessing, and design. The successful design
of novel and improved polymeric materials
and products requires an integrated
approach and a profound understanding of
the disciplines met en route. For example,
in the past two decades polymer chemists
have developed an impressive range of
novel polymeric materials, including intrin-
sically conductive polymers, high glass
transition temperature (Tg) polymers with
an increased temperature resistance, includ-
ing liquid crystalline polymers (LCPs), and
functional polymers for optical and medical
applications. The success of novel present
day and future 'speciality polymers', how-
ever, in terms of application potential and
product design will depend to a large extent
on their processability. In this respect many
pitfalls have been and will be encountered.
For example, intrinsically conductive poly-
mers are rather intractable materials, as well
as many newly developed high Tg polymers
developed by creative polymer chemists.
These intractable polymers often decom-
pose during processing owing to a limited
thermal stability at the elevated tempera-
tures required for processing.
As stated above, the successful design of
a novel polymeric material and product
requires an integrated approach and the
close cooperation of specialists from vari-
ous disciplines, in particular between chem-
ists and process engineers. In the past, sev-
eral methods have been developed for the
processing of intractable polymers. These
include blending [e.g., polystyrene with
poly(phenylene ether) (PPE)], copolymer-
ization (to reduce the melting or glass tran-
sition temperature), and the use of solvents.
All of these methods, however, have spe-
cific disadvantages. For example, PPE has
a r g of approximately 215 C, but it is tem-
perature-sensitive and susceptible to degra-
dation. The PPE/polystyrene system is a
classical example of a miscible polymer
pair. In practice, PPE is processed by blend-
ing with high-impact polystyrene (HIPS).
Owing to this miscibility, however, the pres-
ence of polystyrene lowers the Tg and con-
sequently the advantage of a high Tg is lost
in the final product. In the case of liquid
crystalline polymers, notably the aromatic
polyesters, copolymerization is commonly
used to lower the high melting points of the
homopolymers; processable aromatic poly-
esters are a compromise between ultimate
temperature stability and processability
(Blackwell and Biswas, 1987). If no chem-
ical compromise is made between the ulti-
mate properties and the processability, sol-
vents can be used to facilitate processing, as
in the case of the aromatic poly amides.
Poly-p-phenylene-terephthalamide (PPTA)
is the base material for the well-known Kev-
lar and Twaron high-performance fibers
which are obtained by spinning from nemat-
ic solutions (Ciferri, 1987). Other, more
classical, examples in this respect are fibers
based on polyvinyl alcohol and polyacry-
lonitrile. The use of solvents, however, is
generally limited to products with a high
surface-to-volume ratio, such as fibers,
coatings, and pre-impregnated (pre-pregs)
materials for composite applications, and
has one major disadvantage: the solvent
usually has to be removed completely after
processing, which is increasingly cumber-
some in view of environmental legislation.
Within the Centre for Polymer Compos-
ites of Eindhoven Polymer Laboratories, a
project was started in the early 1990s to

Reactive
Solvent Curing;
Phase Separation
Phase Inversion
explore the possibility of using reactive sol-
vents to facilitate the processing of intract-
able polymers. Figure 10-1 shows schemat-
ically the basic principles of processsing
with reactive solvents. A thermoplastic
polymer is dissolved, usually at elevated
temperatures, in a reactive solvent
(monomer). The homogeneous solution is
transferred into a mold or into a fabric, as in
the case of composites. Upon curing in the
mold, phase separation and phase inversion
occur since the two polymers are immis-
cible, and the polymer concentration in the
initially homogeneous solution is chosen
such that the originally dissolved polymer
becomes the continuous matrix phase. After
curing, the polymerized reactive solvent
(monomer) is dispersed as a particulate
phase in the matrix. For example, PPE dis-
solves in epoxy (resin) at elevated temper-
atures. The PPE/epoxy (resin) solution, con-
taining a hardener, can be transferred into a
mold where, upon curing, phase separation
and phase inversion occur and the cured
epoxy is dispersed as thermoset particles in
the continuous PPE matrix.
The obvious advantages of using reactive
solvents are discussed in detail in subse-
quent sections. The viscosity and process-
ing temperatures when using a reactive sol-
vent are low in comparison with the case of
pure PPE (see Fig. 10-2 and later), and con-
sequently thermal degradation can be pre-
vented. After curing, the continuous matrix
is PPE and hence the properties of the com-
posite system are dominated by this poly-
mer. The reactive solvent remains in the
system and there is no need for solvent
10.1 Introduction 517
Figure 10-1. Schematic
outline of processing with
reactive solvents.
o
o
> Temperature
Figure 10-2. Schematic temperature-viscosity dia-
gram.
removal! Moreover, the cured reactive sol-
vent can even be a useful constituent, for
example, if rubbery epoxies are used, the
dispersed phase can be used to toughen the
material (Venderbosch, 1995; Venderbosch
et al., 1995 a, b), see also Sec. 10.5.
During the course of our investigations,
we have found many polymer-reactive sol-
vent systems which have proved to be suit-
able for this novel processing technique. In
fact, processing with reactive solvents
showed not only to be of interest for intract-
able polymers, but also for standard tract-
able polymers like polyolefins and rubbers.
Dissolving polyethylene, for example, in a
reactive solvent like styrene renders it pos-
sible to obtain low viscosity 'pourable'
polyethylenes and to make very large and
complex-shaped parts, which cannot nor-
mally be obtained via injection molding.
As will be discussed in subsequent sec-
tions, epoxy resin is often used as a reactive
solvent in our processing route. Epoxy res-
ins are well-known solvents for many poly-
mers and thermoset epoxies are often tough-
518 10 Processing of Polymers Using Reactive Solvents
ened by dissolving rubbers or even high Tg
thermoplasts. Liquid rubbers, for example,
carboxyl-terminated butadiene-acryloni-
trile (CTBN) rubbers, can be dissolved in
epoxy resins and upon curing phase separ-
ation occurs (Garg and Mai, 1988; Levita,
1989). Instead of rubbers, thermoplastic
additives have been used to toughen cured
epoxy resins like poly(ether sulfone) (PES)
and poly (ether imide). The advantage of
high Tg polymers over rubbers is that tough-
ening is not achieved at the expense of the
stiffness of the cured epoxy resin. Howev-
er, compared with conventional rubber
toughening, the glassy thermoplastic dis-
persed particles are less capable of initiat-
ing yielding in the surrounding matrix. Con-
sequently, the use of high Tg thermoplastics
as additives in epoxy resins is limited to
densely crosslinked systems, since these
systems are not capable of yielding; conse-
quently, an increased toughness depends on
secondary toughening mechanisms, such as
particle tearing, crack bridging, and crack
bifurcation (Mlilhaupt, 1990; Pearson,
1993; Hedrick et al., 1993). The difference
between the method for toughening epoxies
and the novel processing route described
in this chapter, involving epoxy resin as a
solvent, is that in the former case phase
separation is induced chemically, but no
phase inversion is attempted; the thermoset
epoxy is and remains the continuous matrix
phase.
Last, but not least, a method that comes
close to the processing route with reactive
solvents is the synthesis of interpenetrating
networks (IPNs), notably the semi-IPNs,
where one polymeric constituent is cross-
linked and the other constituent remains lin-
ear (Sperling, 1994). However, an IPN
should possess, to some extent, a certain
degree of molecular interpenetration. In our
process of using reactive solvents, no
explicit attempts are made to pursue inter-
penetration of the various phases. In fact, in
the system PPE/epoxy (resin), the chemical-
ly induced phase separation is virtually
complete (Venderbosch, 1995). The use of
reactive solvents provides the potential to
extend the processing characteristics of
thermoplastic polymers beyond their exist-
ing limits. This concept can be employed for
both intractable and tractable polymers. In
principle, there are two major advantages,
as shown in Fig. 10-2.
The use of reactive solvents can reduce
the processing temperature (route 1), thus
preventing thermal degradation in the case
of intractable polymers, or reduce the vis-
cosity (route 2) in the case of tractable poly-
mers. In actual practice, route 3 is usually
followed, providing a reduction in both the
processing temperature and the viscosity.
The application of reactive solvents thus
enables alternative processing routes, such
as processing intractable polymers and
pouring or casting standard polymers, oper-
ations where a low viscosity is a prerequi-
site. In this chapter, the processing route
with reactive solvents will be discussed for
various systems, including PPE/epoxy res-
in (Sec. 10.5), poly(methylmethacrylate)/
epoxy (Sec. 10.6.1), and polyethylene/sty -
rene (Sec. 10.6.2).
10.2 Classification of Synthetic
Polymers
Synthetic polymers/plastics are typical
materials of the 20th century, and they have
displayed an enormous growth in produc-
tion in the past few decades. Currently,
approximately 100 million tonnes are pro-
duced annually. Considering their low spe-
cific mass (ca. 900-1500 kg/m3), plastics
are approaching steel in terms of production
volume. Based on their molecular structure,
synthetic polymers can be subdivided into
 10.2 Classification of Synthetic Polymers
three main categories: thermoplastics, ther-
mosets, and synthetic rubbers.
10.2.1 Thermoplastics
In terms of production volume, the major-
ity of present-day polymers belong to the
class of thermoplastics. The adjective ther-
moplastic is indicative of the processing of
these polymers. Thermoplastic polymers
are obtained from the chemical industry,
where specific monomers are polymerized
under controlled conditions and supplied to
the converter in the form of pellets and
sometimes powder. These are transformed
into products by the converter by heat-
ing/melting, shaping (extrusion/molding),
and cooling (crystallization/vitrification).
An impressive range of thermoplastic poly-
mers is available nowadays, and molecular
structures can be fine-tuned by proper con-
trol of the catalyst and the polymerization
in the reactor in order to obtain an optimum
structure and performance. It is beyond the
scope of this chapter to discuss in detail cur-
rent trends and product ranges, and conse-
quently we limit ourselves to a discussion
on polymers that are relevant to the novel
reactive processing technique. Thermoplas-
Polycarbonate, PMMA
Polyphenylene ether, ABS
AMORPHOUS SEMI-CRYSTALLINE
519
tic polymers can be subdivided into three
categories: bulk or commodity plastics,
engineering plastics, and speciality poly-
mers. In Fig. 10-3, these three classes are
represented in a product triangle.
The commodity plastics are the most
important class of present-day thermoplas-
tic polymers and constitute over 70% of the
total synthetic polymer production [approx-
imately 50 million tonnes of polyolefins (PE
and PP), and about 25 million tonnes of
poly vinyl chloride and polystyrene]. Poly-
ethylene (PE) and polypropylene (PP) are,
in fact, only generic names, representing an
entire family of polymers which usually dif-
fer in molecular characteristics, e.g., molar
mass distribution, homopolymers or copol-
ymers, stereoregularity (PP), etc. The com-
modity plastics may at first sight appear to
be rather low-tech and well-established
comprising a full range of types and sub-
types, tailored for the end-user and well-
defined application areas. However, the
field of commodity plastics is, after the dis-
covery of the stereospecific polymerization
of olefins by Ziegler and Natta in the mid-
1950 s, once again in a revolutionary stage
due to the introduction of metallocene
catalysis. After a developmental period of
Figure 10-3. The three classes
of thermoplastic polymers (See
the List of Symbols and Abbre-
viations for an explanation of
the different acronyms.)
520 10 Processing of Polymers Using Reactive Solvents
approximately 25 years (1970-1995), met-
allocene 'single-site' catalysts have been
introduced into the chemical reactor, pro-
viding the opportunity to produce novel
types of polyolefins (Thayer, 1995). For
example, very low density polyethylene
('plastomers') can be produced. Syndiotac-
tic polypropylene and syndiotactic polysty-
rene can be made on a technologically fea-
sible scale, whereas novel copolymers
based on ethylene and cyclic olefins pos-
sessing Tgs well above 100 C have recent-
ly been introduced.
At first glance, there seems to be no need
to use (reactive) solvents for processing
commodity plastics in view of the well-
established processing techniques and the
large range of (sub)types on the market,
which are tailored for specific applications.
However, there are a few exceptions, includ-
ing UHMWPE (ultrahigh molecular weight
polyethylene), which is a linear polyethy-
lene grade possessing, according to ASTM
definitions (D4020), a molar mass of at least
3000 kg/mol. UHMWPE products are usu-
ally obtained by machining semi-finished
stock, which is obtained by compression
molding (sintering) or ram extrusion. Sol-
vents are used, however, for UHMWPE
fibers produced by DSM (DYNEEMA) and
its licensee, Allied Signal (SPECTRA).
These high-performance polyethylene
fibers are obtained by solution(gel)-spin-
ning and are described in detail by Bastiaan-
sen in Chap. 11 of this Volume.
To the best of our knowledge, the use of
reactive solvents in processing commodity
plastics has not been exploited. Neverthe-
less, some preliminary results will be pre-
sented in Sec. 10.6.2 concerning the pro-
cessing of polyethylene using reactive sol-
vents.
Engineering plastics are typically poly-
meric materials with an improved tempera-
ture resistance (related to a higher Tg) and
mechanical response compared with com-
modity plastics. In the field of engineering
plastics, a distinction is usually made be-
tween amorphous and semicrystalline plas-
tics. Typical examples of semicrystalline
engineering plastics are the polyamides
(most notably nylon-6, -6,6, and -4,6) and
polyesters such as PETP and PBT. Well-
known amorphous engineering plastics are
ABS, PC, PMMA, and PPE (for an expla-
nation of the abbreviations, see the List of
Symbols and Abbreviations). In Sec. 10.5,
the use of reactive solvents with respect to
the processing of intractable polymers, most
notably PPE, will be discussed, aimed at
enhanced processability, while in Sec. 10.6,
the processing of tractable polymers, e.g.,
PMMA and HDPE will be discussed. In the
case of PMMA, the major aim is to intro-
duce specific product properties.
Speciality polymers are polymers with
very specific properties. Typical examples
of speciality polymers are high Tg polymers
such as PEI and PSU, and polymers which
become intrinsically conductive after dop-
ing (e.g., polyaniline and polypyrrole).
Owing to their high Tg, polymers like PEI
and PSU seem to be suitable candidates for
processing with reactive solvents. Up to
now, no significant literature data are avail-
able concerning the processing of high Tg
polymers with" reactive solvents.
10.2.2 Thermosets
Thermosets are obtained by polymerizing
(curing) low molar mass resins (monomers
with a functionality >2). For this reason, the
viscosity of thermoset resins before curing
is initially low. For example, the viscosity
of a standard bisphenol-A epoxy resin at
25 C is of the order of 10 Pa s. This low
initial viscosity is useful in applications
such as coatings, adhesives, and for impreg-
nation of pre-pregs in the preparation of
 10.3 Guidelines for the Selection of a Reactive Solvent
fiber-reinforced composites. Curing is often
achieved by the addition of curing agents
and/or initiators, and eventually a chemical
network is formed. Depending on the func-
tionality of the starting resin, a more or less
densely crosslinked system is obtained.
Typically, the curing procedure is per-
formed by the end-user during in-mold
shaping. In view of the fact that thermosets
are crosslinked systems after curing and
low viscosity resins before curing, process-
ing with reactive solvents is not of direct
interest. However, some resins, e.g., the
epoxies, can be very useful reactive solvents
themselves, as shown in (Sees. 10.5 and
10.6).
10.2.3 Rubbers
Rubbers are materials that possess elas-
tomeric properties, i.e., they can be
stretched reversibly to high extension ratios.
Elastomeric properties are related to the
flexibility of the polymer chains, which are
lightly crosslinked to prevent permanent
flow. The processing of green (uncross-
linked) rubbers using reactive solvents is
possible in principle [e.g., EPDM rubber
with styrene (pourable rubbers)]. To the best
of our knowledge, no data are available con-
cerning the processing of rubbers with reac-
tive solvents, at least not within the concept
of the present technique. Rubbers, howev-
er, are dissolved in reactive solvents
(monomers) in the reactor, and during poly-
merization, phase separation and inversion
take place, resulting in rubber-modified pel-
lets or powders. Two typical examples of
rubber-modified polymers are high-impact
polystyrene (HIPS) and ABS. HIPS is pre-
pared by dissolving polybutadiene in sty-
rene, after which the styrene is polymerized
under continuous agitation. This results in
a morphology in which polystyrene forms
the continuous phase and polybutadiene the
521
dispersed phase, containing small domains
of polystyrene. A similar procedure is
applied in the preparation of ABS copolym-
ers.
It is important to note that for these rub-
ber-modified polymers, which are formed in
the reactor, the morphology is stabilized by
grafting and crosslinking of the dispersed
rubbery phase. Consequently, upon subse-
quent processing, the induced morphology
does not change significantly. With respect
to the processing of polymers with reactive
solvents, however, the morphology is
obtained in the mold, which has important
consequences for handling and subsequent
processing (see Sec. 10.7).
10.3 Guidelines for the Selection
of a Reactive Solvent
Like polymers, reactive solvents can be
classified according to their potential use in
polymeric materials derived from them.
However, it is more common to classify
monomers according to the polymerization
mechanism that converts them into a poly-
mer, i.e., a chain-growth or a step-growth
polymerization mechanism (Bikales, 1985).
Among the important thermoplastics pro-
duced by a chain-growth type of polymer-
ization, are polymers such as polyethylene,
polypropylene, and polystyrene. Via the
nature of the propagating species, variations
in the polymer microstructure can be
achieved, such as block copolymers and
stereoregular polymers. During chain-
growth polymerization, the monomer
present adds to a propagating polymer
chain, thus extending the chain by one
monomeric unit per propagating step.
In the case of step-growth polymeriza-
tion, however, the polymer chain is formed
not exclusively via the addition of monomer
to a growing polymer chain, but also via the
522 10 Processing of Polymers Using Reactive Solvents
combination of monomer, oligomer, or
polymer molecules with other monomer,
oligomer, or polymer molecules. Step-
growth polymerizations can be performed
in the so-called condensation or addition
mode. During polycondensations, mole-
cules are linked via a condensation reaction,
upon which a small molecule is released,
e.g., water. In the case of polyadditions, on
the other hand, the separate monomers are
linked via addition reactions, resulting in a
polymer chain that is a perfect sum of all the
atoms in the monomers. Typical examples
of polycondensations are the formation of
polyesters and polyamides, while the reac-
tion between amines and epoxies, or diiso-
cyanates and diols can be designated as a
polyaddition.
The major differences between step-
growth and chain-growth polymerizations
are:
1. During step-growth polymerizations,
reactive groups are consumed during the
polymerization, whereas in chain-
growth polymerizations the reactive
groups are continuously generated dur-
ing the polymerization process. At any
instance, the chain-growth polymeriza-
tion system contains unreacted
monomer, while this is not necessarily
true for a step-growth polymerization.
2. The average molar mass of the polymer
formed during step-growth polymeriza-
tion is a function of the conversion, and
a high molar mass polymer is only
formed at very high conversions. The
polymer formed during a chain-growth
polymerization, on the other hand,
already has a high molar mass at low
monomer conversions. These differenc-
es between chain-growth and step-
growth polymerizations, especially the
difference in the development of the
molar mass of the polymer formed dur-
ing polymerization of the reactive sol-
vent, have a profound effect on the
phase behavior of the polymer-reactive,
solvent-polymerized, reactive solvent
system (see also Sees. 10.5 and 10.6).
Based on this, the following can be said
with respect to the mode of polymerization
by which the reactive solvent can be trans-
formed to polymer, and concomitantly the
choice of reactive solvent for a specific
system: Concerning step-growth polymer-
izations, polycondensations are less favor-
able than polyadditions, since the molecules
that are eliminated during a polycondensa-
tion can cause problems in the end products,
e.g., the small molecule released during
polymerization can act as a plasticizer for
the continuous and/or dispersed phase. Fur-
ther, chain-growth type polymerizations
offer greater possibilities for controlling the
molecular microstructure of the polymer
formed, e.g., semicrystalline, amorphous,
or rubbery, by changing the monomer(s),
and/or the mode of initiation/propagation,
than step-growth polymerizations.
For instance, epoxy resins fulfill the
above criteria very well, as has been dem-
onstrated by Venderbosch (1995) and Ven-
derbosch et al. (1994, 1995 a, b) (see also
Sec. 10.5). Some commercially available
epoxy resins are shown in Fig. 10-4;
DGEBA has an aromatic and DGEPPO an
aliphatic backbone. These epoxy resins can
be cured using different curing agents, for
example, poly(propylene oxide) diamine
(Jeffamine D-400) or the sterically hin-
dered, and thus slow, 4,4'-methylene-bis(3-
chloro-2,6-diethyl aniline) (M-CDEA) (see
Fig. 10-4). The curing utilizing aromatic
epoxy resins (A) results, at high crosslink
densities, in high Tg, brittle, thermoset epox-
ies, whereas the aliphatic epoxy resins (B)
exhibit elastomeric properties after curing
(see also Sees. 10.5 and 10.6).
 10.4 Basic Aspects of Processing with Reactive Solvents 523

CH3 OH -1 CH3
o
-CH2-CH-CH2
CH 3 -L = nn CH,

/\ r I CHC \
B ) CH2-CH-CH2-O-CH-CH2 O-CH2-CHhO-CH
1 2-CH-CH2
3 n ~ 5
CH, L CH^ -I _

C ) H2NCH-CH2- )-CH2-CHf-NH2
CH3

Cl C2H5
Figure 10-4. Structural formulae of: (A) DGEBA, (B) DGEPPO, (C) Jeffamine D-400, and (D) M-CDEA.

10.4 Basic Aspects of Processing 10.4.1 Phase Behavior of Amorphous

with Reactive Solvents
During the processing of polymers with
reactive solvents, it is of importance to know
the phase behavior of the particular poly-
mer/reactive solvent system. Processing of
the polymer and reactive solvent should pro-
ceed in the homogeneous state, i.e. the poly-
mer should be dissolved. In the mold, upon
curing, complex changes take place due to
chemically induced phase separation and
inversion. To some extent, these complex
morphological changes due to chemically
induced phase separation (CIPS) are simi-
lar to the morphology development during
thermally induced phase separation (TIPS).
Therefore, in this section, TIPS will be dis-
cussed first, for amorphous as well as
semicrystalline polymers, to provide the
basics for understanding the more complex
phenomena that occur during CIPS.
Polymers in Solution
In the case of an amorphous polymer, the
Tg will be lowered in the presence of a
(good) solvent. The solvent acts as a plasti-
cizer and the Tg decreases with increasing
solvent content. Couchman (1983) has
developed a thermodynamic approach for
predicting the glass transition temperature
of polymer mixtures, but in actual practice
the simpler Fox equation (Fox, 1956), [see
Eq. (10-1)] is often used to describe the Tg
reduction in the presence of a solvent. In Eq.
(10-1), cp represents the volume fraction of
the polymer in the polymer-solvent mix-
ture.
1 _ (1-cp) <P (10-1)
^Solvent j^Polymer
Depending on the solvent quality, various
situations can be encountered, as shown
schematically in Fig. 10-5 A and B.
524 10 Processing of Polymers Using Reactive Solvents

In the case of a good solvent (Fig.

10-5 A), the r g decreases with increasing
solvent concentration and below (px a homo-
geneous solution is obtained at room tem-
perature, TR. Above <px, the solution will vit-
rify into a homogeneous glass upon cooling
to room temperature. In the case of a poor
solvent, the phase diagram can become
more complex. The Tg curve often interferes
with a liquid-liquid demixing curve, as
shown in Fig. 10-5B. The intersection
point, where the Tg composition curve inter-
sects with the L-L demixing or cloud-point
curve, is called the Berghmans point, B. P.
B in Fig. 10-5 B, named after Prof. H. Bergh-
mans (KU-Leuven), who noticed the impor-
tance of this intersection point for the phase
behavior of polymer solutions (Arnauts
et al., 1993). At a concentration cp higher
than %, the homogenous solution vitrifies
upon cooling below the Tg curve, as dis-
cussed previously for Fig. 10-5 A. At con-
centrations lower than (jOg, the homogene-
ous solution will become metastable upon
cooling into the L-L demixing region. From
a purely thermodynamic point of view, the
most favorable and final equilibrium situa-
tion will be the separation into two coexis-
tent macroscopic phases, respectively a
Homogeneous Solution dilute and a concentrated polymer/solvent
T1
<PA <PC <PD phase. This process, however, is rather slow
in polymer systems. If the temperature,
upon cooling, passes, TB (the temperature
corresponding to the Berghmans point) the
metastable solution will vitrify if continuity
of the glassy phases (domains) is present in
the system, usually at higher polymer con-
centrations, or vitrified particles will separ-
ate from solution at lower concentrations.
s <p ^B P The formation of a vitrified gel or the pre-
Figure 10-5. Phase diagrams of an amorphous poly- cipitation of vitrified particles is, as men-
mer (P) and a solvent (S) for (A) a system with a poly- tioned earlier, dependent on the polymer
mer and a good solvent and (B) a system with a poly- concentration in solution.
mer and a poor(er) solvent. (C) Illustration of the mor-
phology development during different phase separa- Although a detailed thermodynamic
tion mechanisms. description is beyond the scope of the
 10.4 Basic Aspects of Processing with Reactive Solvents
present chapter, we will briefly address
some details. In the case of thermally
induced phase separation, a distinction must
be made between binodal and spinodal
decomposition. In practice, we are dealing
with multicomponent systems, since poly-
mers are usually polydisperse materials
with a broad molar mass distribution. In
these polydisperse systems, the critical
point is not on the top of the cloud-point
curve but shifted somewhat to the right, and
the cloud-point curve is usually indented, as
shown in Fig. 10-5 B (Koningsveld et al.,
1996).
In order to illustrate the morphology
development and its dependence on the
mechanism of phase separation, i.e., bino-
dal or spinodal, Fig. 10-5 C shows that in the
case of a binodal system (monodisperse
polymer and solvent), the critical point is at
the top of the cloud-point curve, where the
binodal and spinodal curves meet. Upon
cooling from the homogeneous solution,
either spinodal (through the critical point)
or binodal demixing occurs.
In the case of binodal demixing, phase
separation proceeds through nucleation and
growth of the minor phase. Cooling a solu-
tion with a polymer concentration (pA, into
the binodal region will result in the precip-
itation of (spherical) particles. The overall
polymer concentration is too low to provide
material continuity. Upon cooling a solution
with a polymer concentration, (jCfo, the con-
centrated polymer phase will form the con-
tinuous matrix which will then vitrify at the
temperature corresponding to the Bergh-
mans point, TB. In the case of spinodal
decomposition (<pcX spontaneous phase
separation occurs via concentration fluctu-
ations. The word spontaneous does not
mean that phase separation via spinodal
decomposition is an instantaneous process.
According to the Cahn-Hilliard theory
(Cahn, 1963), concentration fluctuations
525
develop and the fluctuation length with the
highest growing rate (the most dominant
wavelength) results in the most-frequently
found domain size. At the start of the dem-
ixing process, interconnectivity (co-contin-
uous structure) prevails, but gradually the
texture coarsens, approaching an ultimate
separation into two macroscopic phases
(Fujita, 1990). However, this situation is not
reached, since the system vitrifies upon
cooling below the temperature correspond-
ing to the Berghmans point.
10.4.2 Phase Behavior of Semicrystalline
Polymers
In the case of semicrystalline polymers,
we have to focus on the melting temperature
Tm instead of Tg. The melting point depres-
sion due to the presence of solvent(s) is usu-
ally described by the well-known melting
point depression relationship, which reads
for high molar mass polymers (Flory, 1956)
^ ^ ^ ^ ^ s - m 2
) dO-2)
V
In Eq. (10-2), Tm represents the melting
temperature, or equivalently the dissolution
temperature, of the crystals in the solvent,
T^ is the equilibrium melting point of the
pure crystal, R is the gas constant, <ps the vol-
ume fraction of solvent, x th e Flory-Hug-
gins interaction parameter, Vu the molar vol-
ume of the monomer unit in the polymer
chain, Vs the molar volume of the solvent,
and AHf is the heat of fusion per mole of
repeating units.
Figure 10-6 A shows the melting point
depression of a polymer crystal in equilib-
rium with the surrounding solution. Equa-
tion (10-2) is only applicable to concentrat-
ed and semidilute systems, and consequent-
ly the far left part of the phase diagram is
represented by a dotted line. The melting
point of the polymer is lowered by the pres-
526 10 Processing of Polymers Using Reactive Solvents
Homogeneous
Crystallization Lin
<p
B
Homogeneous
/ schematically in Fig. 10-6 A should
TmP)
^ ^
- \
Crystallization
Line
B.P.
S (p
Figure 10-6. Phase diagrams of a semicrystalline
polymer and a low molar mass solvent for (A) a system
in which the solvent is a good solvent for the polymer
and (B) a system in which the solvent is a poor(er) sol-
vent for the polymer.
ence of a solvent, and vice versa, i.e., the
melting point of the solvent is lowered by
the presence of the polymer. Consequently,
a eutectic point is to be expected. However,
as shown by Smith (1976), a eutectic point
is not observed if the difference between the
melting point of the polymer and the solvent
exceeds 100 K. In Fig. 10-6 A, the melting
point of the solvent is not indicated in view
of the fact that in the systems to be discussed
below, the melting point of the solvent is far
below room temperature and the difference
between the melting point of the polymer
and the solvent is > 100 K.
It is important to note that the equilibri-
um curve Tm(<p) in Fig. 10-6 A is never
obtained experimentally. Equilibrium refers
to perfect, large crystals, i.e., so-called
extended-chain crystals in the case of poly-
mers. In practice, however, polymer crys-
tals consist of folded-chain crystals and the
fold length, or equivalently the thickness of
the folded-chain crystals is of the order of
10-30 nm. These imperfect and small crys-
tals melt or dissolve at a lower temperature,
as indicated in Fig. 10-6 A by the curve
rm(<p); in the literature the melting point is
given as Tm to distinguish it from the equi-
librium melting point, T^.
The experimental Tm((p) curve as drawn
approach the melting point of the pure sol-
vent when the polymer concentration
approaches zero. In Fig. 10-6 A, the inter-
section of the experimental melting (disso-
lution) Tm((p) curve with the temperature
axis is represented by an open circle. Melt-
ing (dissolution) of polymer crystals at low
P concentrations is currently, yet again a mat-
ter of debate (Nies and Berghmans, 1996).
When the polymer concentration approach-
es zero, the melting point Tm should
approach the melting point of the solvent.
However, it is found in practice that the
melting point Tm becomes independent of
the polymer concentration when <p
approaches zero. The reason for this is prob-
ably that upon melting (dissolution) of a
polymer crystal, the polymer chain goes
from a folded-chain conformation within
the crystal to a random-coil chain in solu-
tion. The random coil in solution has its own
local concentration, i.e., upon dissolution
the chain experiences a low but finite local
concentration of the order of a few percent,
related to the coil dimensions. Consequent-
ly, the melting (dissolution) temperature
remains constant at low <p, i.e., the local con-
centration of a random coil.
 10.4 Basic Aspects of Processing with Reactive Solvents 527

Crystallization is a nucleation-controlled domains will crystallize upon cooling below

process and only occurs at a certain degree
of supercooling, as indicated by the crystal-
lization line in Fig. 10-6 A. For crystalliz-
able polymers in solution, crystallization
can also interfere with liquid-liquid demix-
ing. This is depicted schematically in
Fig. 10-6 B. The L-L demixing curve can be
located above or below the equilibrium
melting curve, T^((p). The latter case is
shown in Fig. 10-6B. Even if the L-L dem-
ixing curve is below the equilibrium disso-
lution curve, T^((p), L-L demixing usually
occurs before crystallization, since the crys-
tallization process is a slower process and
requires a certain degree of undercooling.
Instead of vitrification, the concentrated
the temperature TB.
10.4.3 Thermally Versus Chemically
Induced Phase Separation
As noted before, the morphology develop-
ment during thermally induced phase separ-
ation (TIPS) is very similar to the morphol-
ogy development during chemically induced
phase separation (CIPS) (see Fig. 10-7 A and
B, respectively). The reason is that upon cur-
ing a polymer/reactive solvent system, the
polymerized reactive solvent becomes
immiscible with the dissolved polymer and
phase separation should occur at some stage
during the curing (polymerization) step.

Reactive
Solvent
One Phase Region
A / /-\ (Homogeneous)

Figure 10-7. Schematic representation of

the changes in miscibility of a polymer in
a poor solvent in the case of (A) cooling
from 7] to T2 (TIPS), (B) isothermal
polymerization of the reactive solvent
from tx to t2 (CIPS), and (C) a ternary
phase diagram of the polymer-polymeriz-
A
ing reactive solvent system. Lines A-A',
Polymer C Polymerized B-B', and C - C represent polymerization
Reactive lines, and the horizontal line is a tie line
Two Phase Region
(Heterogeneous)
Solvent connecting the coexisting phases.
528 10 Processing of Polymers Using Reactive Solvents
There is, however, one important difference
between TIPS and CIPS. In the case of TIPS,
a two-phase system will be formed, consist-
ing of a dilute and a concentrated polymer
phase, either in the form of two separate mac-
rophases or in microdomains if vitrification
occurs, i.e., cooling below the Berghmans
point. In the case of CIPS, liquid-liquid dem-
ixing will occur due to immiscibility of the
originally dissolved polymer and the poly-
mer that is formed during polymerization
(curing). Coarsening of the structure is
strongly surpressed by an increase in the vis-
cosity, induced by phase separation and the
polymerization reaction. Moreover, fixation
of the structure via vitrification, crystalliza-
tion, or crosslinking will prevent the forma-
tion of two macrophases. Another important
difference from TIPS is that phase separation
is complete, or at least should be attemped,
not in the sense of the formation of two mac-
rophases but in terms of 100% conversion of
the reactive solvent into polymer.
Considering the morphology develop-
ment upon curing, an important distinction
has to be made between step-growth and
chain-growth polymerizations. In all cases
curing (polymerization) should start from
homogeneous solutions in view of process-
ability and morphology control. In the case
of step-growth polymerization, the molar
mass of the polymerizing reactive solvent
changes continuously with conversion. At
50% monomer conversion, the number-
average degree of polymerization is 2, i.e.,
the main products present are dimers (see
Sec. 10.3). Suppose a polymer (P)/reactive
solvent (S) system with an upper critical
solution temperature (UCST) phase behav-
ior as depicted schematically in Fig. 10-7B
is cured at temperature Tp. The phase behav-
ior will change during the polymerization
process due to the increasing molar mass of
the polymerizing reactive solvent, i.e., the
formation of dimers, trimers, etc. Concom-
itantly, the L-L demixing curve will shift
upwards. Phase separation will occur when
the L-L demixing curve shifts to tempera-
tures above Tp. This situation is encoun-
tered, for example, in the system PPE/epoxy
(see Sec. 10.5).
Let us consider a polymer-reactive sol-
vent system where the reactive solvent is
polymerized via a chain-growth polymer-
ization mechanism. Initially, the polymer-
reactive solvent system can be considered
as a binary system, with a phase diagram
as represented by the dashed line in Fig.
10-7 C. Upon polymerization of the reactive
solvent, a polymer is formed with a high
molar mass, which will not change signifi-
cantly during polymerization. Concomi-
tantly, a ternary system is formed consisting
of polymer-reactive solvent-polymerized
reactive solvent (see Fig. 10-7 C). Although
the reacting system is not in equilibrium due
to the continuous formation of polymer, and
moreover because we are dealing with poly-
disperse polymers, the use of a simple (equi-
librium) ternary phase diagram, as shown in
Fig. 10-7 C, might be useful for the discus-
sion on the morphology development. The
initial composition of the homogeneous
solutions is located on the polymer-reactive
solvent axis. Upon polymerization, a reac-
tion line is followed as indicated by the
dotted-dashed lines (A-A', B-B' and C-C)
in Fig. 10-7 C. After a small amount of con-
version of the reactive solvent, the binodal
line (solid line) is crossed and the system
becomes metastable. This might lead to
phase separation. However, when the spino-
dal line (dashed line) is crossed, the system
will phase separate. The positions of the
binodal and spinodal curves depend on the
molar mass of the polymer and polymerized
reactive solvents and the interaction param-
eters between the polymers and the reactive
solvent. Considering the case where the
interactions between the solvent and both
 10.5 Example of an Intractable Polymer/Reactive Solvent System
polymers are identical, the critical point is
located at the maximum of the binodal and
the corresponding tie lines are horizontal
when the polymers have equal molar mass-
es. The examples given above show that for
these reactive systems the morphology
depends not only on the thermodynamics,
but more importantly on the relative rate of
phase separation and the rate of polymeriza-
tion. In the case where the dissolved poly-
mer is amorphous, vitrification can interfere
with L-L demixing (see Sec. 10.4.1), while
in the case of a semicrystalline polymer,
crystallization can interfere with L-L dem-
ixing. The occurrence of vitrification/crys-
tallization enables fixation of the nonequi-
librium morphologies. When all the reactive
solvent has been transformed into polymer,
the system can be considered as a binary
system again, containing the polymer and
the polymerized reactive solvent.
10.5 Example of an Intractable
Polymer/Reactive Solvent System:
The Poly(phenylene ether)
(PPE)/Epoxy System
10.5.1 Materials Choice: PPE/Epoxy
Epoxy resins prove to be surprisingly
effective solvents for many polymers, as can
be concluded from a literature survey by
Venderbosch (Venderbosch, 1995). PPE is
chosen for its interesting mechanical prop-
erties in terms of a high Tg, a relatively high
intrinsic impact strength, and average val-
ues for the modulus, yield stress, and break-
ing strength. Given its high Tg of 220 C, the
processing temperature should be around
350 C. This, in combination with its limit-
ed thermal and oxidative stability, results in
severe degradation, and consequently PPE
can be considered as a classical example of
an intriguing, but intractable polymer.
529
10.5.2 Phase Behavior of PPE/Epoxy
Solutions
In order to estimate the processing win-
dow of PPE/epoxy solutions, the phase dia-
gram was investigated first. The phase dia-
gram of PPE-DGEBA was constructed
from a combination of light scattering
experiments, dynamic mechanical thermal
analysis (DMTA), and rheology [for further
details see Venderbosch (1995) and Vender-
bosch et al. (1994, 1995 a, b) and referenc-
es cited therein]. The resulting phase dia-
gram is presented in Fig. 10-8, from which
it can be seen that rather high temperatures
are required to reach the region of homoge-
neous solutions.
The cloud-point curves exhibit a typical
upper critical solution temperature (UCST)
behavior, commonly observed for poly-
225
20 40 60 80 100
Polymer Content
Figure 10-8. Phase diagram of PPE/epoxy solutions
as derived from light scattering experiments (closed
circles, triangles, and squares), DMTA (open circles),
and rheology (closed chevrons). Open and closed cir-
cles and closed chevrons: Mw = 30 kg/mol; open and
closed triangles: Mw = 18 kg/mol; closed squares: Mw =
10 kg/mol. The solid lines indicate the onset of phase
separation, the dashed lines on the right the ^-com-
position line of the homogeneous solutions, and the
horizontal dashed line with closed chevrons the
^-composition line of the heterogeneous solutions.
530 10 Processing of Polymers Using Reactive Solvents

mer-solvent systems. As expected, a
decrease in the PPE molar mass enhances
the miscibility of the system and results in
a considerable shift of the cloud-point surve
to lower temperatures. Since PPE as well as
the epoxy resin is polydisperse, the cloud-
point curves may not be regarded as bino-
dal curves. The inflection in the curves
clearly reveals the influence of the molar
mass distribution, i.e., the critical point is
not situated at the top of the curves. The
rg-composition lines, as determined by
DMTA, and as calculated with the Fox equa-
tion (using a Tg of 222 and 213 C for PPE
with a molar mass of 30 and 18 kg/mol,
respectively, and a Tg of -18 C for the
epoxy monomer), are also given in Fig.
10-8 and they intersect the cloud-point
curves at a PPE content of approximately
70%. Thus solutions with less than 70 wt.%

80 wt.%

70 wt.%

60 wt.%

50 wt.%

40 wt.% -

30 wt.%

lOkg.mol"1 30 kg.mol"1

Figure 10-9. Scanning electron micrographs of PPE/epoxy solutions with a PPE molar mass of 10 and 30 kg/mol
and a PPE content of 30-80 wt.%, after cooling from 200C to room temperature at a rate of 1 C/min.
 10.5 Example of an Intractable Polymer/Reactive Solvent System
PPE will phase separate upon cooling; how-
ever, phase separation is not complete but
arrested as soon as the PPE-rich phase vit-
rifies at this intersection point (the Bergh-
mans point, see also Sec. 10.4). As a result
of this phenomenon, which can be regarded
as a thermo-reversible gelation (TIPS), all
of the phase-separated solutions will exhib-
it a Tg of ~ 100 C, as indicated by the dashed
horizontal line in Fig. 10-8 and confirmed
by rheological experiments. The morpholo-
gies resulting from the TIPS (thermally
induced phase separation) process are
shown in Fig. 10-9. In accordance with the
phase diagram in Fig. 10-8, a homogene-
ously vitrified material is found above
70wt.% PPE. Below 70 wt.% PPE, dis-
persed epoxy droplets are observed in a con-
tinuous PPE matrix. The size of the dis-
persed epoxy phase is relatively uniform
and depends on the PPE fraction. With
increasing PPE content, the viscosity of the
solution increases, and consequently during
phase separation (TIPS), the coarsening
process is retarded with increasing viscos-
ity.
In order to verify the concept of enhanced
processability of PPE via the application of
epoxy as a reactive solvent, the rheology of
PPE/epoxy was investigated. The dynamic
rheological behavior of the homogeneous
solutions was studied using a Rheometrics
6
5 30 wt.% epoxy
V)
cd 4
CL
c 3 50 wt.% epoxy
68 wt.% epoxy
-1
- 3 - 2 - 1 0 1
Reduced Frequency
531
RDSII spectrometer [experimental details
are mentioned elsewhere, see Venderbosch
(1995), and Venderbosch et al. (1994,
1995 a, b) and references cited therein]. The
dynamic viscosity as a function of the
reduced frequency for the PPE/epoxy solu-
tions with various epoxy contents is shown
in Fig. 10-10. The plot shows typical shear
thinning behavior, which is commonly
observed for semidilute solutions. The
expected strong dependence on the volume
fraction of the PPE is confirmed. Moderate-
ly high zero shear viscosities were found at
200 C; these are comparable to those of
standard thermoplastic polymers. The suc-
cess of the original aim for intractable PPE
is demonstrated by the fact that the process-
ing temperature of PPE was lowered from
>300C to <200C, thus introducing pro-
cessable PPE.
10.5.3 Curing of PPE/Epoxy Solutions
Curing of PPE/epoxy solutions requires
the incorporation of a curing agent which
should be compatible with the solution.
Aromatic diamines are particularly suitable
because of their excellent compatibility
with the PPE/epoxy solution. Owing to the
addition of a curing agent, which enhances
the miscibility of the system, the phase dia-
gram, as shown in Fig. 10-8, is no longer
Figure 10-10. Dynamic viscosity versus
reduced frequency of PPE/epoxy solu-
tions with epoxy contents of 30, 50, and
68 wt.%, while the molar mass of the PPE
used was 30 kg/mol, at 170 C.
2 3 4 5 6
532 10 Processing of Polymers Using Reactive Solvents
valid. However, it remains useful for indi-
cating the minimal miscibility of the system.
Ternary solutions of PPE/epoxy/curing
agent still reveal UCST behavior and the
absence of phase separation upon cooling at
high PPE contents (see Fig. 10-7 B). In ter-
nary solutions, the main driving force for
phase separation is the increase in molar
mass of solvent into dimer, trimer, etc.,
induced via step-growth polymerization
(curing) (see also Sec. 10.3). As shown by
Verchere and co-workers [Verchere et al.
(1991) and references cited therein] and de
Graaf (1994) for epoxy systems toughened
with (in order to prevent phase inversion)
relatively small volume fractions of car-
boxyl-terminated butadiene-acrylonitrile
copolymer (CTBN rubber) and polyether-
sulfone, respectively, minor increases in the
molar mass of the solvent significantly
reduce the miscibility of the system and
phase separation is initiated at relatively low
conversions. CIPS can be regarded as induc-
ing a shift and a concurrent change in the
shape of the cloud-point curves on the phase
diagram towards higher temperatures. The
coarseness of the final morphology is con-
trolled, on the one hand, by the competition
between the rates of phase separation and
coalescence (i.e., diffusion-Ostwald ripen-
ing and hydrodynamically driven break-up
and coalescence processes), and on the other
hand by the rates of vitrification and chem-
ical gelation.
The required compatibility of the curing
agents with the PPE/epoxy solutions ren-
ders it difficult to estimate their appropriate
concentration. For aromatic diamines, the
concentration should be equal to the stoi-
chiometric ratio, but an excess is likely to
be required in order to compensate for any
loss of curing agent due to dissolution in the
PPE phase. For this reason the optimal con-
centration, which is defined as the concen-
tration that results in the highest Tg of the
30 40 50
Curing agent content [phr]
Figure 10-11. Glass transition temperatures versus
curing agent concentration of epoxy phase (open tri-
angles) and PPE phase (closed triangles), as deter-
mined by DMTA (frequency 1 Hz) for cured blends
containing 35 wt.% epoxy, while the molar mass of
the PPE was 30 kg/mol.
epoxy phase, was determined using DMTA.
Figure 10-11 demonstrates that virtually
complete phase separation is obtained, at
least for the polymerization temperatures
used. This is of essential importance, not
only for the expected mechanical properties,
but also for the nontoxicity of the final prod-
uct. The latter is clearly illustrated by the
optimal concentration of (generally toxic)
curing agent which proves to be very close
to, or even equal to, the stoichiometric ratio,
as revealed by the pronounced maximum in
the epoxy Tg. This can be explained by the
fact that a deficiency (incomplete curing) as
well as an excess (yielding a more linear
polymerization) results in a lower Tg. The
morphology of the cured samples is shown
in Fig. 10-12 for four volume fractions in
the relevant mid-region, prepared by extrac-
tion of the PPE matrix. Relatively monodis-
perse epoxy spheres with a particle size
distribution of Dw/Dn~1.2 are found (see
also Fig. 10-13). This is not a general rule,
however, since for some other poly-
mer-reactive solvent systems, such as those
recently being investigated in our laborato-
 10.5 Example of an Intractable Polymer/Reactive Solvent System 533

^ ^ ^ ^ ^ ^ ^

/ V:

Figure 10-12. Scanning electron micrographs of the dispersed epoxy phase isolated from PPE/epoxy cured at
225 C with initial compositions of (a) 60, (b) 50, (c) 40, and (d) 20 wt.% epoxy.

1.50
interferes with phase separation (see also
Sec. 10.6.2).

10.5.4 Morphology Development

0.0(
00 150 200 250
Curing temperature (C)
Figure 10-13. Number-average particle size (Jim) of
PPE/epoxy system as a function of the initial curing
temperature for a constant composition of 40 wt.%
epoxy.
ry, a distinct dependence on curing temper-
ature and curing rate is sometimes found.
This effect becomes increasingly important
for semicrystalline polymers, where lock-
ing-in of the morphology by crystallization
In order to study morphology develop-
ment, the chemo-rheology of PPE/epoxy/
M-CDEA (see Fig. 10-4) was investigated.
The dynamic viscosity and loss angle ver-
sus time of an isothermally cured PPE/
epoxy system are presented with the curing
temperature (Fig. 10-14) and the blend
composition (Fig. 10-15) as parameters
(Yenderbosch, 1995; Venderbosch et al.,
1994, 1995 a, b).
The onset of phase separation (arrows)
and the gradual increase in viscosity due to
the formation of a PPE-rich continuous
phase are apparent (I). Accordingly, vitrifi-
cation of this phase (II) and gelation of the
534 10 Processing of Polymers Using Reactive Solvents

15
- ^ (+8)
(a)
IV

- III >*
(+6)
12 - II y-
I (+4)
/ III f
237 C

cd I / II & I i /
(+2)
a. 9 -- 2 1 5 C J
o - II & HI/ IV
195 c w '

6 - 175 c 3>
i J
152 c
.

i I I I l i i i i

Log(t/s)

450

Figure 10-14. Rheology

upon isothermal curing of
PPE/epoxy (50 wt.%
epoxy) versus temperature:
(a) dynamic viscosity; (b)
loss angle (strain 2%, fre-
quency = 10 rad/s, plate
diameter = 8 mm). The
arrows indicate the onset of
phase separation. (For clar-
ity the curves are shifted
upwards by the values indi-
cated in parentheses.)

dispersed epoxy phase (III) are found, the final morphology can be expected. At
although they are usually difficult to distin- high temperatures this could be the case,
guish as they happen almost simultaneous- although basically only in the case where
ly, followed by the vitrification of the epoxy reaction rates exceed the rate of phase sep-
phase (IV). At a low temperature, vitrifica- aration, can a pronounced influence be
tion of PPE occurs before gelation of the anticipated. In the slow curing system with
epoxy and no interference of the gelation on M-CDEA, this is not the case, and the mor-
 10.5 Example of an Intractable Polymer/Reactive Solvent System 535

16

00

Q_
8 -
O)
o

gelation

Log(t/s) Figure 10-15. Rheology

upon isothermal curing of
PPE/epoxy at 200 C versus
450 composition (as indicated
in the separate figures): (a)
dynamic viscosity; (b) loss
angle (strain <2%; 10 rad/s;
360 the plots are a combination
of measurements with a
plate diameter of 50 mm (-
closed circles); 8 mm in the
case (+) of the system with
39 wt.% epoxy). The drawn
line in Fig. 10-15 a was
obtained on a Brookfield
rheometer. For clarity the
curves are shifted by the
values in parentheses. The
times, fgel and /vitr of
epoxy/M-CDEA are given
as reference points.
gelation

Log(t/s)

phology depends uniquely on the viscosity
of the matrix at the moment of phase separ-
ation.
The composition data in Fig. 10-15 a and
b clearly reveal that the minimum time for
phase separation occurs with 78 wt.%
epoxy, in accordance with UCST behavior,
and phase inversion is detected at between
90 and 78 wt.% epoxy, accompanied by a
large rise in the viscosity, yielding early
matrix vitrification (most pronounced at
intermediate polymer concentrations be-
tween 78 and 60 wt.% epoxy), and hence the
potential for early demolding. In conclu-
536 10 Processing of Polymers Using Reactive Solvents

sion, rheological measurements prove to
provide a useful tool for monitoring the
morphology development upon isothermal
curing of PPE-epoxy-M-CDEA.
In this system, the morphology is mainly
controlled by the formation of a highly
viscous, PPE-rich continuous phase during
the early stages of the reaction-induced
phase separation process. Only at polymer-
ization rates considerably higher than the
rate of phase separation is a pronounced
influence on the final morphology anticipat-
ed.
10.5.5 Mechanical Properties
In order to systematically vary the
mechanical properties of the dispersed
epoxy phase, the flexibility of the epoxy net-
work was tuned by blending aromatic
DGEBA (stiff) and aliphatic DGEPPO
(flexible) epoxies (see Fig. 10-4). The glass
transition temperatures of the DGEBA/
DGEPPO mixtures; 110/0, 80/20, 60/40,
40/60, 20/80, and 0/100, cured with
M-CDEA or Jeffamine D-400, are shown in
Fig. 10-16. The Tg of the resulting epoxy
material gradually decreases from 200 C to
-30 C, as a unique function of the total
polypropylene oxide content. The tensile
properties of the final epoxy network reveal
the great flexibility obtained by tuning the
properties of the epoxy phase from a brittle
glass to a ductile or relatively brittle rubber,
depending on the position of Tg relative to
room temperature [for further details see
Venderbosch (1995) and Venderbosch et al.
(1994, 1995 a, b) and references cited there-
in].
The above-mentioned mixtures of
DGEBA/DGEPPO were applied as reactive
solvents for PPE. The miscibility of

250 250

-5 -50
100/0 80/20 60/40 40/60 20/80 0/100 20 40 60 80 100
DGEBA/DGEPPO ratio total PPO content [wt.%]

Figure 10-16. Glass transition temperatures, as determined by DMTA, of mixtures of DGEBA and DGEPPO
resin cured using M-CDEA (closed triangles) or Jeffamine D-400 (open triangles) versus (a) the DGEBA/DGEP-
PO ratio and (b) the total polypropylene oxide (PPO) content. Solid lines: Fox equation.
 10.5 Example of an Intractable Polymer/Reactive Solvent System 537

12
(a) (C)

0/100
10 -
D
3 - \

100/0 & 60/40 8 -

20/80
2 6

T 100/0
4 - T
(D
D
O %
V
2 - 1
_L
60/40

20 40 60 80 100 20 40 60 80
epoxy content [wt.%] epoxy content [wt.%]

100 PPE-DGEPPO proved to be decreased rel-

20 40 60
epoxy content [wt.0/
Figure 10-17. Tensile properties of PPE/epoxy ver-
sus the epoxy content for DGEB A/DGEPPO ratios of
100/0 (closed triangles), 60/40 (open triangles), 20/80
(closed squares), and 0/100 (open squares): (a)
Young's modulus; (b) yield stress; and (c) fracture
toughness (Glc) (testing speed of 1 m/s).
ative to PPE-DGEB A, but only a very small
shift in the cloud-point curve towards high-
er temperatures resulted. The morphology
of the cured systems proved to be very sim-
ilar to what we had already found, i.e.,
micrometer-sized droplets of epoxy in a
continuous PPE phase. The main mechani-
cal properties of the total system are sum-
marized in Fig. 10-17, listing the modulus,
yield stress, and (high speed) fracture tough-
ness values as a function of the amount of
epoxy added, and with the ratio of
DGEBA/DGEPPO as a parameter. Indeed
the properties can be tuned to requirements
but, more interestingly, the reactive solvent,
i.e., after being used as a processing aid, is
80
locked up as an integral part of the resulting
product, inside the thermoplastic matrix. Its
usefulness as a structural element is clearly
illustrated by the remarkable toughness
enhancement obtained in the already tough
PPE when rubbery epoxies are used (see
Fig. 10-17C).
538 10 Processing of Polymers Using Reactive Solvents
10.5.6 Composite Applications
Making use of these newly developed
polymer systems, high Tg thermoplastic
composites were prepared using the film
stacking technology. By introducing epoxy
resin(s) as a reactive solvent, the flow
became sufficiently high to fully wet and
impregnate the fibers, yielding composite
materials of high quality (Venderbosch,
1995; Venderbosch et al., 1994, 1995 a, b).
Microscopic analysis revealed an interest-
ing composite morphology, i.e., the epoxy
phase tends to accumulate at polar surfaces
such as those of glass and surface-treated
carbon fibers (see Fig. 10-18). Remarkably,
this phase segregation is almost complete in
Figure 10-18. SEM micrographs of fracture surfac-
es of short-fiber-reinforced composites (17 vol.%
fibers) based on PPE/epoxy (56 wt.%, 25 phr Etha-
cure 100): (a) Grafil X-AS carbon fiber; (b) E-glass
fiber.
the case of high fiber loadings, and, for a
fiber volume fraction of 50%, a morpholo-
gy of epoxy-coated fibers in a pure PPE
matrix is found (see Fig. 10-18). This
(unique) morphology is not only of great
importance with respect to the possibility of
drastically improving the strength of the
interphase or the level of adhesion between
fibers and matrix, but also offers the poten-
tial to individually coat fibers with a thick
and adjustable (e.g., glassy or completely
rubbery) interphase. Apart from the appar-
ent influence of the fiber volume fraction or
the fiber spacing, a prerequisite for com-
plete phase separation to occur is that suffi-
cient mobility and time exist for completion
of this diffusion process. For the fixed reac-
tion rate of the system, the viscosity of the
matrix plays a dominant role. If more than
30% epoxy is present, complete phase sep-
aration to the fiber surface is achieved and
a nearly neat PPE matrix results (see
Fig. 10-19). This is confirmed by transverse
flexural strength tests on unidirectional
composites which show that the maximum
properties are obtained as soon as a contin-
uous epoxy interphase is formed (see
Fig. 10-20).
Figure 10-19. SEM micrographs of the fracture sur-
face in a fiber-rich area of PPE/epoxy-based (40 wt.%
epoxy, 55 phr M-CDEA) carbon-fabric reinforced
composite (50 vol.% fiber): (a) fiber (imprint); (b)
epoxy layer; (c) PPE matrix.
 10.5 Example of an Intractable Polymer/Reactive Solvent System
150
20 40 60 80
Epoxy content (wt.%)
Figure 10-20. Transverse flexural strength (MPa) of
unidirectional PPE/epoxy composites with a fiber vol-
ume fraction of 50 (open triangles) and 60% (closed
triangles) versus the epoxy (DGEBA) content (wt.%)
of the matrix.
20 40 60 80 100
Epoxy content (wt.%)
Figure 10-21. Critical strain energy release rate GIc
of carbon-fabric reinforced composites (50 vol.%
fibers) versus the matrix composition: mode I (closed
circles) and mode II (open circles).
Of all the properties measured [with typ-
ical values for the flexural moduli of 40 GPa
and strength values of 0.7 GPa for this high
Tg (220 C), thermoplastic, 50% carbon-
fabric-reinforced composite], the impact
properties proved to be the most interesting,
as shown by the mode I and II critical strain
energy release rates given in Fig. 10-21, and
539
the C-scan results after impact (see Fig.
10-22). The synergy found in the mode II
results can be explained by an apparent opti-
mal combination of brittle and ductile
matrix components. The brittle epoxy
phase, enclosing all the fibers, not only
yields a strong and well adhering interphase,
but also induces an increase of the deforma-
tion area of the crack and, consequently, of
the level of toughness, assuming that cracks
in the epoxy coating can initiate yielding in
the adjacent PPE matrix. Since the mode II
results of the interlaminar fracture tough-
ness tests relate linearly to the values of the
practical (Boeing) compressive strength
after impact (CSAI) (Cantwell and Morton,
1991), they are of great practical impor-
tance. Possibly, by the introduction of these
brittle interphases, a method has been found
to toughen fiber-reinforced composites,
with a ductile thermoplastic matrix, beyond
the usual limits imposed by the presence of
rigid fibers.
The continuous variation of the proper-
ties of the interphases from glassy to rub-
bery can be realized by mixing DGEBA
with DGEPPO. Consequently, the macro-
scopic properties of the composites are
strongly influenced. Glassy interphases
were shown to be in favor of structural appli-
cations (mode II fracture toughness). On the
other hand, by increasing the ductility of the
interphases, mode I fracture toughness is
favored; superior Charpy impact values
were obtained and the transverse strength
and strain-at-break were significantly
improved. However, these ultimate trans-
verse properties were obtained at the
expense of the compressive properties, due
to the low shear modulus of the interphase.
By changing the viscosity and the chemis-
try of the systems employed, e.g., by using
end-modified, low molar mass PPEs which
can co-react with the reactive solvent, the
existing limits with respect to the diffusion-
540 10 Processing of Polymers Using Reactive Solvents
a)
b)
Figure 10-22. Tensile face damage and schematic representation of C-scan images of carbon-fabric laminates
(50 vol.% fibers) impacted at an energy level of 9 J: (a) epoxy matrix; (b) PPE/epoxy matrix (40 wt.% epoxy).
controlled, complete phase separation could
be surpassed, and thinner interphases could
be realized.
10.6 Examples of Tractable
Polymer/Reactive Solvent
Systems
In this section, two polymer-reactive sol-
vent systems will be discussed, in which the
polymer is either amorphous (PMMA) or
semicrystalline (HDPE), while the reactive
solvent is polymerized via a step-growth
(epoxy resin) or a chain-growth (styrene)
polymerization, respectively.
10.6.1 The Poly(methylmethacrylate)/
Epoxy System
Poly(methylmethacrylate) (PMMA) is an
amorphous glassy polymer possessing a Tg
of approximately 110 C. Like polystyrene,
V 2 cm
PMMA is brittle, with a low strain-at-break
and a poor impact performance. Upon de-
formation of PMMA and PS, crazing occurs
on a microscale and the small cracks which
appear in the material, perpendicular to the
stress direction, are bridged by numerous
fibrils. The maximum elongation of these
craze fibrils approaches the theoretical limit
estimated from the maximum draw ratio of
an entanglement network, as shown by
Kramer and Donald (1982). For example,
the molar mass between entanglements in
the case of polystyrene is approximately
20 kg/mol and, assuming that no chain slip-
page occurs through entanglements, the
maximum draw ratio should be of the order
of 4, or equivalently a strain-at-break of
300%. In practice, however, polystyrene is
the paradigm of a brittle material with a
macroscopic strain-at-break of 1 - 3 % . This
paradox, a polymer possessing a loose
entanglement network and a low macro-
scopic strain-at-break, is discussed exten-
 10.6 Examples of Tractable Polymer/Reactive Solvent Systems
sively by van der Sanden in Chap. 12 of this
Volume. For the present discussion, we sim-
ply summarize that polystyrene is ductile
below a certain critical thickness, or equiv-
alently below a certain interparticle distance
(D Ic ).InChap. 12, Sec. 12.9, it is mentioned
that submicrometer engineering foams, i.e.,
materials possessing holes, or equivalently
nonadhering submicrometer (rubbery) par-
ticles, with an interparticle distance below
Dlc, are a great challenge for the future
for toughening brittle glassy polymers. In
this respect, PMMA was mentioned as an
interesting candidate in addition to polysty-
rene (see Chap. 12, Sec. 12.9).
In a recent Dutch patent application (Jan-
sen and van der Sanden, 1996), the process-
ing route involving reactive solvents was
T = 60 C ;:v:."
541
used to make tough and transparent PMMA
via two routes. In route 1 PMMA was dis-
solved in an epoxy resin, and in route 2 the
monomer MMA was dissolved in epoxy
resin. In order to obtain finely dispersed rub-
bery particles in a PMMA matrix via route
1, the polymerization temperature proved to
be crucial. It was stated that the polymeriza-
tion temperature Tp should be limited by
Tg (PMMA/epoxy) -20 C < Tp <
r g (PMMA/epoxy) +20 C (10-3)
As shown by Eq. (10-3), the Tgs of solu-
tions depend on the composition, i.e., in the
case of epoxy/PMMA solutions, the Tg will
increase during polymerization as a conse-
quence of the conversion from epoxy resin
(the solvent for PMMA) into a thermoset
Figure 10-23. The effect of curing tem-
perature on the morphology of the final
blend of 70 wt.% PMMA and 30 wt.%
epoxy.
542 10 Processing of Polymers Using Reactive Solvents
100 150
curing temperature [C]
Figure 10-24. Macroscopic strain-at-break of
PMMA-epoxy (70/30) blend for different curing tem-
peratures.
epoxy which is immiscible with PMMA.
The morphology is the result of the rate of
polymerization versus the rate of coales-
cence of the dispersed polymerizing epoxy
phase. The more viscous the solution, i.e.,
the closer to its 7\, the less coalescence is
to be expected. In actual practice, it is rath-
er difficult to follow the Tg of the system
from the reaction temperature profile, and,
as a compromise, the curing of epoxy in the
case of PMMA/epoxy systems is performed
at a low temperature, i.e., at a relatively high
viscosity. The effect of the curing tempera-
ture is striking. This is demonstrated in
Fig. 10-23, where the lower the polymeriza-
tion temperature, the finer the particle sizes
of the dispersed epoxy particles. In Fig.
10-24, the corresponding mechanical prop-
erties are shown and it can be seen that the
strain-at-break increases with decreasing
particle size, or equivalently a smaller inter-
particle distance.
10.6.2 The Polyethylene/Styrene System
In contrast with the polyphenylene
ether/epoxy system, where a reactive sol-
vent is used to lower the processing temper-
ature, the use of a reactive solvent in the case
of high-density polyethylene (PE) is aimed
at lowering the viscosity. In this case, the
low viscosity solution can be cast or even
poured into a mold, which might be advan-
tageous for making large and complex struc-
tures, e.g., connectors for the cable indus-
try. The system polyethylene/styrene is dis-
cussed below, but we hasten to add that the
PE/styrene system is only used to serve the
purpose of demonstrating the structural
changes that take place as a result of CIPS
(L-L) combined with crystallization (L-S).
In actual practice, styrene is not a desirable
solvent in view of environmental legisla-
tion, but other solvent systems are possible,
e.g., methacrylates. A detailed study con-
cerning the system PE/styrene has been car-
ried out Goossens and co-workers and is
published extensively in his Ph.D. thesis
(Goossens et al., 1996). Some salient fea-
tures are described below.
10.6.2.1 Miscibility of Polyethylene
and Styrene
As discussed in Sec. 10.4, it is of impor-
tance to know the phase behavior of the
polymer/solvent system to be processed.
The experimental melting (dissolution) and
crystallization curves of polyethylene (in
this case a linear polyethylene possessing a
molar mass, Mw, of 75 kg mol"1) in styrene,
as a function of the composition, are shown
in Fig. 10-25. Experimental melting or dis-
solution curves are commonly analyzed
using the well-known melting point depres-
sion relationship based on the Flory-Hug-
gins lattice theory [see Eq. (10-2)].
As can be discerned from Fig. 10-25,
there is no indication of interference with
L-L demixing, as reported by Richards
(1946), Roginova and Slonimskii (1974),
and Nakajima et al. (1966) for several
PE-solvent systems. In conclusion, styrene
is a good solvent for PE at elevated temper-
atures (Goossens et al., 1996).
 10.6 Examples of Tractable Polymer/Reactive Solvent Systems
140
20 40 60 80 100
PE content [wt.%]
Figure 10-25. Experimental (V) and calculated (T)
equilibrium melting temperatures as a function of the
composition using literature values for the various
parameters in Eq. (10-2).
10.6.2.2 Morphology Development
as Revealed by Small Angle X-Ray
Scattering (SAXS) and Wide Angle
X-Ray Scattering (WAXS)
In situ simultaneous SAXS and WAXS
data collected during isothermal polymer-
ization at the Synchroton Radiation Source
(SRS) in Daresbury (U.K.), during isother-
mal polymerization, are shown in Fig.
10-26 at two temperatures, 120 and 125 C,
respectively. At a polymerization tempera-
ture, Tp, of 125 C, no crystallization is
expected (see also Fig. 10-25), since Tp is
above the crystallization curve and only
L-L demixing can occur during polymeriza-
tion. At a polymerization temperature of
120 C, crystallization can occur at a later
stage of the polymerization process when
the crystallization temperature of PE in
residual styrene exceeds Tp (see also
Fig. 10-25).
The SAXS data (see Fig. 10-26 A, C, E,
and F) are presented as three-dimensional
plots of intensity, /(#), versus the scattering,
vector, q = (4n/X) sin 0, where 26is the scat-
tering angle, as a function of the polymer-
ization time. The WAXS data for the poly-
merization temperature of 120C are pre-
543
sented in Fig. 10-26B and D as three-
dimensional plots of intensity, 1(26), versus
the scattering angle 20, versus time. All the
SAXS patterns in Fig. 10-27 A, C, E, and F
initially show little scattering, indicative of
homogeneous solutions, as is to be expect-
ed from the phase diagram (Fig. 10-25).
During polymerization, all of the scattering
patterns gradually change. At a polymeriza-
tion temperature of 120 C, the WAXS pat-
tern observed at a later stage of the polymer-
ization process shows the characteristics
110 and 200 reflections and the reflections
of the higher orders of the orthorhombic PE
unit cell (see Fig. 10-26 B and D). No
WAXS pattern is observed at 125 C, as
explained above. There is a noticeable dif-
ference between the development of the
scattering patterns of the 20 and 60 wt.%
PE/styrene solutions at 120 C. For the
20 wt.% systems, amonotonically decaying
pattern is observed, and careful analysis
showed (Goossens et al., 1996) that the
intensity is linearly dependent on the square
of time, indicative of a nucleation and
growth mechanism (binodal decomposi-
tion), according to Lipatov et al. (1985).
The 60 wt.% solution, on the other hand,
shows a distinct maximum moving to lower
q values with increasing polymerization
time. This periodic microstructure could be
indicative of a spinodal-type of phase-sep-
aration process. According to the (linear-
ized) Cahn-Hilliard theory (Cahn, 1963),
concentration fluctuations with a dominant
wave number will grow giving rise to a peri-
odic microstructure. More detailed informa-
tion was obtained by Goossens by analyz-
ing the data based on a simple two-phase
model and making use of the experimental
invariant g, defined as <2 = 0i<?V(Pi~P2)2>
where 0 is the volume fraction and p is the
electron density. For the 20 wt.% PE
systems, a maximum in the experimental
invariant is found in the early stages of the
544 10 Processing of Polymers Using Reactive Solvents

110

120

- 40
20 10 60
Time [min]
q [I/A]
Time [min]

x10

Time [min]

x10 x10

=i 0.8-
f; o.6~
w 0.4-
0.2-
100 c 100
oJ 80
0.01 0.01
20
0.02
Time [min] 0.03 Time [min]
0.04 0.04
q [I/A]
Figure 10-26. SAXS (A, C, E, and F) and WAXS (B and D) data collected during isothermal polymerization at
120C (A, B, C, and D) and 125 C (E and F) for different polyethylene contents (20 wt.% PE in A, B, and E,
and 60 wt.% in C, D, and F).

L-L phase separation. Because the electron
density contrast, (P1-P2X between the PE-
rich and PS-rich regions only increases dur-
ing the polymerization, the maximum must
be attributed to changes in the volume frac-
tions of the two phases. The volume frac-
tion of the PE-rich phase ranges from 1.0
before the onset of L-L phase separation to
final value of 0.2. The invariant reaches a
maximum close to equal phase volumes. For
the polymerization at 120 C, a second max-
imum in the invariant is observed. This orig-
inates from the crystallization of PE. The
experimental invariants of the 60 wt.% PE
systems do not show a maximum, because
the phase volumes do not become equal.
 10.7 Concluding Remarks and Future Outlook
;\
14
Figure 10-27. Transmission electron micrographs
showing the polyethylene/polystyrene blends after
complete polymerization at 120 and 125C, respec-
tively: (A) polystyrene particles dispersed in a poly-
ethylene matrix obtained by polymerization at 120 C
with 20 wt.% PE in styrene; (B) as (A), but at a high-
er PE concentration of 60 wt.% and (C) 60 wt.% at
125 C.
545
10.6.2.3 Morphology as Revealed
by Electron Microscopy
Some representative TEM micrographs
of PE/PS blends are presented in Fig.
10-27 A, B, and C. The micrograph of the
20 wt.% PE system (Fig. 10-27 A) clearly
shows a phase-separated and phase-invert-
ed morphology of dispersed PS particles in
a matrix of PE. Considering the polydisper-
sity of the PS particles size, the morpholo-
gy is the result of a binodal type of phase
separation, as discussed in the previous sec-
tion. The micrographs of the 60 wt.% PE
systems clearly show the difference be-
tween the phase-separation mechanisms
(see Fig. 10-27B and C). For this system,
the PS is not dispersed as isolated particles,
but the co-continuous-like structures con-
firm the X-ray observations of spinodal-like
phase separation.
10.7 Concluding Remarks
and Future Outlook
The processing of polymers using reac-
tive solvents (monomers) is an extremely
versatile technique with respect to the crea-
tion of unique morphologies. In the case of
amorphous polymers, as illustrated previ-
ously for the PPE/epoxy system, the dis-
persed epoxy phase can migrate to the fiber
surface upon curing the PPE/epoxy resin in
the presence of (polar) fibers. In the case of
PMMA/epoxy, the particle size of the dis-
persed thermoset epoxy phase can be con-
trolled by optimizing the polymerization
temperature, resulting in tough and trans-
parent PMMA/epoxy blends. In the case of
a crystalline polymer, as shown for the poly-
ethylene/styrene system, a multitude of
structures can be created by the proper
choice of the phase-separation processes,
i.e., liquid-liquid or liquid-solid demixing.
546 10 Processing of Polymers Using Reactive Solvents
In this chapter, although only a few exam-
ples were presented, it is clear that in the
near future many more systems will be
explored in view of the many possibilities
for dissolving both intractable and tractable
polymers in reactive solvents. In addition,
the process is not limited to polymers/reac-
tive solvents but monomers can be consid-
ered as well, for example, MMA/epoxy (res-
ins) or caprolactam/PPE (where nylon-6
forms the continuous phase). Moreover, the
ultimate need for complete conversion, as is
essential in standard reactive processing
techniques, is altered in the present process-
ing techniques. After molding, the system
can usually be vitrified and postcured out-
side the mold, permitting the feasibility of
short(er) cycle times.
At present, the processing of polymers
with reactive solvents is limited to in mold
casting and curing (polymerization). The
process is based on CIPS and phase inver-
sion, which take place in the mold during
polymerization. This in-mold operation dif-
ferentiates our processing route from seem-
ingly identical processes, at least from a
physical chemistry point of view, involving
chemically induced phase separation and
phase inversion, which occur in the reactor.
For example, a classical approach to tough-
en glassy polymers like polystyrene is to
dissolve polybutadiene rubber in styrene
monomer (high-impact polystyrene) (Rod-
riguez, 1983). During polymerization,
grafting and phase separation occur. Due to
grafting, the morphology is fixed, which is
essential in view of the fact that the mor-
phology within the pellets should survive
the subsequent processing step by the con-
verter (see also Sec. 10.2.3).
10.8 References
Arnauts, J., Berghmans, H. (1987), Polymer 28, 66.
Arnauts, J., Berghmans, H., Koningsveld, R. (1993),
Makromol Chem. 194, 11.
Berghmans, H., Arnauts, J. (1987), Polymer 28, 97.
Bikales, N. M. (1985), in: Encyclopedia of Polymer
Science and Engineering, 2nd ed., Vol. 3: Mark,
H. F., Bikales, N. M., Overberger, C. G., Menges,
G. (Eds.). New York: Wiley, p. 549.
Blackwell, J., Biswas, A. (1987), in: Developments in
Oriented Polymers-2: Ward, I. W. (Ed.). Amster-
dam: Elsevier Applied Science, pp. 153-199.
Cahn, J. W. (1963), /. Chem. Phys. 42, 93.
Cantwell, W. J., Morton, J. (1991), Composites 22,
347.
Ciferri, A. (1987), in: Developments in Oriented Poly-
mers-2: Ward, I. M. (Ed.). Amsterdam: Elsevier
Applied Science, p. 79.
Couchman, P. R. (1983), Macromolecules 16, 1924.
de Graaf, L. (1994), Ph. D. Thesis, University of
Twente, The Netherlands.
Flory, P. J. (1956), Principles of Polymer Chemistry.
Ithaca, NY: Cornell University Press.
Fox, T. G. (1956), Bull. Am. Phys. Soc. 2, 123.
Fujita, H. (1990), in: Studies in Polymer Science,
Vol. 9. Amsterdam: Elsevier.
Garg, A. C , Mai, Y. (1988), Compos. Sci. Technol. 31,
179.
Goossens, H., Rastogi, S., Meijer, H. E. H., Lemstra,
P. J. (1996), unpublished.
Hedrick, J. C , Patel, N. M., McGrath, J. E. (1993),
Adv. Chem. Ser. 223, 293.
Jansen, B. J. P., van der Sanden, M. C. M. (1996),
Dutch Patent Application.
Koningsveld, R., Stockmayer, W., Nies, E. L. F.
(1996), Thermodynamics of Polymer Systems,
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Kramer, E. J., Donald, A. M. (1982), Polymer 23, 461;
23, 1183.
Levita, G. (1989), Adv. Chem. Ser. 222, 93.
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Shilov, V V, Sergryeva, L. M. (1985), Makromol.
Chem. 186, 1401.
Mulhaupt, R. (1990), Chimia 44, 43.
Nakajima, A., Fujiwara, H., Hamada, F. J. (1966),
Polym. Sci.: Part A2, 4,501.
Nelissen, L., Meijer, E. W., Lemstra, P. J. (1992), Poly-
mer 33, 3734.
Nies, E., Berghmans, H. (1996), private communica-
tions.
Pearson, R. A. (1993), Adv. Chem. Ser. 223, 405.
Richards, R. B. (1946), Trans. Faraday Soc. 42, 10.
Rodriguez, F. (1983), Principles of Polymer Systems.
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Roginova, L. Z., Slonimskii, G. L. (1974), Russian
Chem. Rev. 43, 1102.
Smith, P. (1976), Ph. D. Thesis, Groningen.
Sperling, L. H. (1994), Adv. Chem. Ser. 239,3.

Stoks, W., Berghmans, H. (1991), J. Polym. ScL: Part
B: Polym. Phys. 29, 609.
Stoks, W., Berghmans, H., Moldenaers, P., Mewis, J.
(1988), Br. Polym. J. 20, 361.
Thayer, A. M. (1995), Chem. Eng. News 11, 15.
Vandeweerdt, P., Berghmans, H., Tervoort, Y. (1991),
Macromolecules 24, 3547.
Venderbosch, R. W. (1995), Ph. D. Thesis, Eindho-
ven.
10.8 References 547
Venderbosch, R. W., Meijer, H. E. H., Lemstra, P. J.
(1994), Polymer 35, 4349.
Venderbosch, R. W., Meijer, H. E. H., Lemstra, P. J.
(1995a), Polymer 36, 1167.
Venderbosch, R. W., Meijer, H. E. H., Lemstra, P. J.
(1995 b), Polymer 36, 2903.
Verchere, D., Pascault, J. P., Sautereau, H., Moschiar,
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/. Appl. Polym. ScL 43, 293.
11 High-Modulus and High-Strength Fibers Based
on Flexible Macromolecules
Cees W. M. Bastiaansen

Eindhoven Polymer Laboratories/Centre for Polymers and Composites,

Eindhoven University of Technology, Eindhoven, The Netherlands
and
ETH Zurich, Institut fur Polymere, Zurich, Switzerland

List of Symbols and Abbreviations 552

11.1 Introduction 554
11.2 The Ultimate Stiffness, Strength, and Drawability
of Flexible Polymers 556
11.2.1 The Theoretical Young's Modulus 556
11.2.2 The Theoretical Tensile Strength 558
11.2.3 The Theoretical Maximum-Attainable Draw Ratio 559
11.3 Spinning, Ultradrawing, and Properties of Linear Polyethylene 560
11.3.1 The Spinning Process 560
11.3.2 The Drawing Behavior of Linear Polyethylenes 562
11.3.3 The Young's Modulus of Ultradrawn Polyethylenes 565
11.3.4 The Tensile Strength of Ultradrawn Polyethylenes 566
11.3.4.1 The Morphological and Molecular Approach 566
11.3.4.2 Other Approaches 568
11.3.4.3 Remarks 569
11.3.5 Miscellaneous Properties 569
11.4 The Drawing Behavior and Properties
of Flexible Semicrystalline Polymers 570
11.4.1 The Drawing Behavior and Properties of Semicrystalline Apolar Polymers 570
11.4.2 The Drawing Behavior and Properties of Semicrystalline Polar Polymers . 570
11.4.3 The Drawing Behavior and Properties of Semiflexible Polyimides 573
11.5 Outlook 574
11.6 Acknowledgements 574
11.7 References 574

Materials Science and Technology

Copyright WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
552 11 High-Modulus and High-Strength Fibers Based on Flexible Macromolecules

List of Symbols and Abbreviations

A cross-sectional area
C modulus
d diameter
E Young's modulus
F force
I length
A/ length change
original length
m constant
M molecular weight
Mn number-average molecular weight
Mw weight-average molecular weight
n constant
An birefringence
Q polydispersity
s compliance
t thickness
T temperature
T glass transition temperature
Ug internal energy

e strain
9 angle
X draw ratio
2 maximum-attainable draw ratio
'hnax
(7 stress
tensile strength
polymer concentration in solution

BPDA biphenyltetracarboxylic dianhydride

HP high performance
ILSS interlaminar shear strength
i-PP isotactic polypropylene
PA polyamide
PAN polyacrylonitrile
PE polyethylene
PECO polyketone
PEEK polyetheretherketone
PEO polyethyleneoxide
PET polyethyleneterephthalate
PI polyimide
POM polyoxymethylene
PP polypropylene
 List of Symbols and Abbreviations 553

PPTA poly(/?-phenylene terephthalamide)

PPX polyparaxylylene
PTFE polytetrafluorethylene
PVOH, PVAL poly(vinylalcohol)
RT room temperature
TTM taut-tie molecules
UHMW-PE ultrahigh molecular weight polyethylene
UHS ultrahigh strength
UV ultraviolet
554 11 High-Modulus and High-Strength Fibers Based on Flexible Macromolecules
11.1 Introduction
Conventional polymers like polyolefins,
polyamides, and polyesters consist of flex-
ible macromolecules which adopt a random-
coil conformation in the (quiescent) melt or
solution. In the solid state, the random coil
is preserved in the case of amorphous poly-
mers. In the case of semicrystalline poly-
mers, the coils tend to adopt a folded-chain
conformation. One of the main characteris-
tics of polymers is that the chemical bond-
ing is strong along the chain, whereas weak
interactions (van der Waals bonds, hydro-
gen bonds) usually exist between the chains.
As a consequence, the Young's modulus of
isotropic, flexible macromolecules is not
impressive compared to those of inorganic
materials such as metals, glasses, and
ceramics (Table 11-1). However, over the
past two decades impressive progress has
been made in exploiting the intrinsic
properties of the macromolecular chain,
especially in the field of (almost) one-
dimensional objects such as fibers. Two dif-
ferent routes have been used to produce
fibers with properties that approach the
inherent stiffness and strength of the mac-
romolecular backbone of polymers.
Table 11-1. Stiffness (Young's modulus) of mate-
rials.
Material Young's modulus
(GPa)
Rubber <0.1
Amorphous thermoplast, T<Tg 2-4
Semicrystalline thermoplasts 0.1-4
Wood (fiber direction) 15
Bone 20
Aluminum 70
Glass 70
Steel 200
Ceramics 500
Carbon fiber 500-800
Diamond 1200
The first route was discovered by Kwo-
lek(Kwolek, 1972;Kwoleket al., 1977) and
is based on the experimental observation
that intrinsically rigid macromolecules,
such as PPTA [poly(p-phenylene tereph-
thalamide)], form liquid crystalline nemat-
ic solutions above a certain critical concen-
tration; these can be spun and oriented in an
elongational flow field. After quenching
and extraction of the solvent, highly orient-
ed fibers are obtained with excellent me-
chanical properties. Nowadays, PPTA
fibers are produced on an industrial scale by
Dupont (Kevlar) and Akzo Nobel (Twaron),
possessing Young's moduli and tensile
strengths of approximately 75-150 GPa
and 2.5-3.5 GPa, respectively.
The second approach to produce high
modulus and high strength fibers is based
on intrinsically flexible macromolecules. A
large variety of techniques has been devel-
oped to orient these flexible macromole-
cules and to obtain high modulus and high
strength structures (Fig. 11-1). References
to typical examples of techniques to produce
high stiffness and high strength structures
are listed in the footnote. A large range of
synthetic polymers were investigated in the
described processes l.
1
Typical examples of techniques to produce high
stiffness and high strength structures are: solid-state
(co-)extrusion (Southern, 1970 a, b; Southern et al.,
1972; Zachariades and Porter, 1979; Zachariades
et al., 1979; Kanamoto and Porter, 1983; Kanamoto
et al., 1988; Kanamoto, 1990), surface growth tech-
niques (Zwijnenburg and Pennings, 1975, 1976 a, b),
zone-drawing techniques (Kunugi et al., 1979, 1981,
1982 a, b), drawing of as-polymerized, nascent poly-
mers (Smith et al., 1985, 1987; Rotzingeret al., 1989;
van der Werff and Pennings, 1988), swell-spinning
and ultradrawing (Mackley and Solbai, 1987), melt-
spinning and ultradrawing (Capaccio and Ward, 1973,
1974, 1975 a, b, 1976; Wu and Black, 1979, 1980),
and solution-spinning and ultradrawing (Smith and
Lemstra 1979a, b, 1980a, b, c, 1981; Smith et al.,
1979 a, b, 1981). Flexible semicrystalline polymers,
which were investigated in the above-described tech-
niques, are polyethylene (PE, see references above),
 11.1 Introduction 555

melt
/ processing
conventional
polymerization
\ solution (gel)
processing

x low temperature ^g=p|^p virgin polymer processing

polymerization drawing

liquid crystal J||1|

(3) polymerization
formation
HIGH MODULUS
MONOMER
POLYMER
(4) crystallization solid-state polymerization

polymerization/
crystallization

Figure 11-1. Schematic representation of techniques to generate oriented and chain-extended structures based
on flexible polymers. (Courtesy of P. Smith, ETH, Zurich, Switzerland; in part after S. Minami, Toray.)

This research effort resulted in several
commercial high modulus and high strength
fibers which are produced by Hoechst-
Celanese (Tenfor), DSM/Toyobo (Dynee-
ma), and Allied (Spectra). Particularly in the
case of Dyneema and Spectra, the proper-
ties of these fibers, with respect to the
Young's modulus (100-150GPa) and the
strength ( 3 - 4 GPa), surpass even those of
Kevlar and/or Twaron (Fig. 11-2).
polypropylene (PP) (Williams, 1973; Kunugi et al.,
1983; Peguy and St. J. Manley, 1984), polyoxymethy-
lene (POM) (Clark and Scott, 1974; Nakamea et al.,
1990a), poly(ethyleneterephthalate) (PET) (Pereira
and Porter, 1983a, b; Kunugi et al., 1981, 1986),
poly(vinylalcohol) (PVOH) (Schellekens et al., 1986;
Mokveld and Schellekens, 1986; Kunugi and Kawa-
sumi, 1988), polyamides (PA) (Gogolevski and Pen-
nings, 1985; Hofman et al., 1989), polyethyleneoxide
(PEO) (Kim and Porter, 1985; Mitchell and Porter,
1985; Roberts and Jenekhe, 1990), polyetheretherke-
tone (PEEK) (Lee et al., 1988), polyketone (PECO)
(Lommerts, 1994), polyparaxylylene (PPX) (van der
Werff and Pennings, 1988), polyimides (PI) (Kaneda
etal., 1986a, b; Cheng et al., 1991) and polytetra-
fluorethylene (PTFE) (Matsuo et al., 1993).
A complete and detailed overview of all
the studies would be an enormous task and
is considered outside the scope of this chap-
ter. We will limit ourselves to basic princi-
ples and highlights from a fundamental or
applied point of view. The main part of this
chapter focuses on a single polymer, i.e., lin-
ear polyethylene. This choice was made
partly because linear polyethylenes are by
far the most extensively studied materials,
and partly because the principles as derived
for this polymer are, to some extent, appli-
cable to other semicrystalline polymers.
Moreover, we will limit ourselves to melt-
and solution-spinning techniques in combi-
nation with ultradrawing. This latter choice
was made based on purely practical consid-
erations, e.g., (i) the processes resemble
conventional fiber spinning operations, and
(ii) multifilament fibers can be produced on
an industrial scale. First, the ultimate prop-
erties of linear polyethylene with respect to
modulus, strength, and drawability are dis-
cussed (Sec. 11.2). Subsequently, experi-
556 11 High-Modulus and High-Strength Fibers Based on Flexible Macromolecules
50 100 150
mental routes to approach the ultimate
properties and to produce high modulus and
high strength fibers are discussed (Sec.
11.3). Finally, developments concerning
high modulus and high strength fibers based
on polymers other than linear polyethylene
are discussed in Sec. 11.4.
11.2 The Ultimate Stiffness,
Strength, and Drawability
of Flexible Polymers
11.2.1 The Theoretical Young's Modulus
The theoretical Young's modulus of a per-
fectly oriented polymer is usually derived
from semi-empirical or ab initio theoretical
calculation (Treloar, 1960; Shimanouchi
etal., 1962; Odajima and Madea, 1966;
Frank, 1970; Wobser and Blasenbrey, 1970;
Perepelkin, 1972; Tashiro et al., 1978). The
theoretical Young's modulus of a complete-
ly extended polymer chain can be calculat-
ed from the change in the internal energy
Figure 11-2. Specific
strength versus specific
modulus of high perfor-
mance fibers (Lemstra
etal., 1987 a). (Specific
strength = strength/density;
specific modulus = mod-
ulus/density.)
200 250
(At/) associated with a length change (A/)
in the chain direction. The force (F) required
to maintain a certain length change is given
by the gradient of the internal energy func-
tion [Eq. (11-1)]. The modulus is calculat-
ed from the ratio of the stress (a = F/A) to
the strain (e = Al/l0) at a strain which
approaches zero
F = dU
d/
(11-1)
E = dd
dill o dl2
The values of the theoretical Young's
modulus of polyethylene exhibit consider-
able scatter (180-340 GPa) which is main-
ly caused by assumptions with respect to the
internal energy function.
Estimates of the maximum Young's mod-
ulus of semicrystalline polymers can also be
derived from X-ray diffraction studies on
oriented fibers during mechanical load-
ing (Nakamea et al., 1988, 1990a, b, 1991;
Nakamea and Nishino, 1991). The strain in
the oriented polymeric crystal is derived
 11.2 The Ultimate Stiffness, Strength, and Drawability of Flexible Polymers
from the change in 001 spacing of the crys-
tal upon loading. The Young's modulus (E)
is calculated from the ratio of the macro-
scopic stress (a) to the strain () in the crys-
tal (E=a/e), i.e., a homogeneous distribu-
tion of stress is assumed in the fibers. Usu-
ally, the Young's modulus calculated from
X-ray measurements (-240 GPa) is low in
comparison to the theoretical values. How-
ever, it is obvious that the theoretical
Young's modulus of polyethylene in the
chain direction is indeed extremely high
(>200 GPa).
Theoretical Young's moduli (based on X-
ray diffraction) of a range of semicrystalline
flexible polymers are listed in Table 11-2.
This table shows that the theoretical
Young's modulus of polyethylene is high in
comparison to most other flexible polymers,
which is primarily due to the small cross-
sectional area of the polyethylene chain and
to the planar zig-zag configuration of the
polyethylene backbone. However, polyeth-
ylene is far from unique, i.e., polymers such
as poly(vinylalcohol) and polyamide-6 also
possess a high theoretical Young's modulus.
In principle, the theoretical Young's mod-
ulus of polymeric crystals is calculated
assuming a continuous, defect-free crystal
which is perfectly oriented in the test direc-
tion. This highly idealized structure cannot
be mimicked in reality, and consequently it
Table 11-2. X-ray diffraction moduli of some semi-
crystalline polymers.
Material X-ray Reference
modulus
(GPa)
PE 235 Nakameaetal. (1991)
PVOH 230 Nakamea and Nishino (1991)
PET 110 Nakameaetal. (1988)
PA-6 174 Matsuoetal. (1993)
PP 40 Sawatari and Matsuo (1989)
POM 73 Nakameaetal. (1990a)
557
is useful to consider the influence of, for
instance, misalignment and crystal discon-
tinuity on the theoretical modulus of orient-
ed structures. The complete stiffness matrix
of polyethylene single crystals was calcu-
lated by Tashiro et al. (1978) [Eq. (11-2)]
7.99 3.28 1.13 0 0 0
3.28 9.92 2 .14 0 0 0
1.13 2.14 3 .16 0 0 0
GPa
0 0 0 3 .19 0 0
0 0 0 0 1.62 0
0 0 0 0 0 3.62
(11-2)
From the stiffness matrix, the angular de-
pendence of the Young's modulus of a sin-
gle crystal can be calculated [Eq. (11-3)]
(Ward, 1985)
= (S nsin4 0 + 2 Sl3cos2 0 sin2 6
+ S33cos40- 2S35cos36 sin 0 (11-3)
3 2 2
- 5 15 cos 0 sin 6 + S55 cos 0 sin 0)
A typical result of such calculations is
shown in Fig. 11-3. This figure shows that
polyethylene single crystals are highly
anisotropic with respect to the Young's
modulus, which is primarily caused by the
low shear and transverse moduli of the
crystal [Eq. (11-2)]. The low shear and
transverse moduli originate from the weak
intermolecular interactions (van der Waals
bonds) in polyethylene crystals. Moreover,
this figure illustrates the need for a low mis-
match angle between the chain and test
directions (or a high orientation) to obtain
structures with a high Young's modulus.
Usually, it is assumed that oriented fibers
are discontinuous with respect to the crys-
tal structure (Fischer and Goddar, 1969;
Peterlin, 1978; Dijkstra and Pennings, 1988;
Prevorseket al., 1993). Moreover, it is often
assumed that a homogeneous distribution of
stress exists between separate structural ele-
558 11 High-Modulus and High-Strength Fibers Based on Flexible Macromolecules

400 1985). The result of such an averaging pro-

CO
Q_
300
CD
200
3
O
> 100
30 60 90
angle [degree]
Figure 11-3. Young's modulus of polyethylene crys-
tals as a function of the angle between chain and test
direction (Bastiaansen, 1991).
ments (Irvine and Smith, 1986; Dijkstra and
Pennings, 1988). In Fig. 11-4, a hypotheti-
cal structure is shown consisting of discon-
tinuous, defect-free crystals with an imper-
fect uniaxial orientation. In the case of uni-
form stress distribution, the Young's mod-
ulus of an aggregate of crystals can be
calculated by averaging the compliances of
the separate elements (Reuss, 1929; Ward,
Figure 11-4. Hypothetical aggregate of oriented sin-
gle crystals with an imperfect uniaxial orientation.
cedure is strongly influenced by the largest
compliance or lowest Young's modulus of a
separate structural element. Of course, this
further emphasizes the need for a high
degree of structural perfection and orienta-
tion to generate structures with Young's
moduli that approach the theoretical values.
11.2.2 The Theoretical Tensile Strength
In the past, a variety of studies has been
devoted to the theoretical tensile strength of
oriented and chain-extended structures in
the chain direction (Zhirnov et al., 1969;
Mark, 1971; Perepelkin, 1972; Boudreaux,
1973; Kausch, 1978; He, 1986; Kelly and
Macmillan, 1986). The theoretical tensile
strength of a single extended polymer chain
can be calculated directly from the C-C
bond energy. These calculations show that
the theoretical tensile strengths are extreme-
ly high (19-66 GPa). These values for the
theoretical tensile strength are, in general,
considered to represent the absolute upper
limit. In an array of chain-extended polyeth-
ylene macromolecules, these theoretical
values are only approached if all C-C bonds
fracture simultaneously and this requires a
(virtually) defect-free, fully chain-extended
structure.
A more realistic approach was used in
studies on the theoretical tensile strength of
a perfectly oriented array of macromole-
cules with a finite molecular weight (Ter-
monia et al., 1985, 1986), i.e., one type of
defect (chain ends) is present in the struc-
ture. Termonia and co-workers used Monte-
Carlo simulations to model the fracture
behavior of both low and high molecular
weight, perfectly oriented continuous crys-
tals. Both chain slippage and chain rupture
were considered by introducing a stress-
dependent activation barrier for rupture of
both inter- and intramolecular bonds. It was
 11.2 The Ultimate Stiffness, Strength, and Drawability of Flexible Polymers
found that the molecular weight (or number
of chain ends) has a profound influence on
both the fracture mechanism and the theo-
retical tensile strength of these hypothetical
structures. It was shown that chain slippage
prevails at a low molecular weight, and
this results in a low theoretical tensile
strength (Mn = 20 kg/mol, C7t = 1 - 3 GPa).
At high molecular weights, fracture was
initiated by the rupture of C-C bonds in the
vicinity of a stress concentration (chain end)
and this resulted in high tensile strength
(Mn = 300 kg/mol, crt= 10-12 GPa). Inter-
mediate fracture mechanisms combining
chain slippage and chain rupture are ob-
served at intermediate molecular weights.
Several approaches to estimate the theo-
retical tensile strength of solution-spun,
ultradrawn UHMW-PE fibers from experi-
mental data were also proposed. For in-
stance, experimental results on the influ-
ence of the fiber diameter on the tensile
strength of UHMW-PE fibers were extra-
polated to zero fiber diameter, and it
was estimated that the theoretical tensile
strength of drawn UHMW-PE is approxi-
mately 26 GPa (Smook et al., 1984). Also,
the influence of the fraction of taut-tie
molecules on the tensile strength was inves-
tigated, and a theoretical tensile strength of
approximately 30 GPa was obtained using
certain extrapolation procedures (Penning
et al., 1990; Penning, 1994). Both estimat-
ed values for the theoretical tensile strength
are within the range of the theoretical
values for a single chain-extended poly-
ethylene chain.
11.2.3 The Theoretical Maximum-
Attainable Draw Ratio
The requirements to produce high mod-
ulus and high strength fibers with respect to
a high degree of chain orientation and exten-
sion are virtually undisputed. Traditionally,
559
orientation and chain extension are generat-
ed in melt- and solution-spun fibers by two
different methods: (i) applying a drawdown
to the fibers during or immediately after
spinning, and (ii) the solid-state drawing of
fibers at temperatures below the melting or
dissolution temperature. A drawdown is
applied to the polymer in the melt or solu-
tion and, consequently, nonaffine deforma-
tion and relaxation of the orientation occur,
which reduce the effectiveness of the draw-
ing process (Mackley and Keller, 1975;
Mackley and Sapsford, 1982; Lemstra and
Kirschbaum, 1985). In the case of solid-
state drawing, relaxation phenomena are
restricted by the presence of polymeric crys-
tals and, consequently, solid-state draw-
ing is considered far more effective at gen-
erating orientation and chain extension in
fibers.
Usually, it is assumed that the molecular
and macroscopic deformation are identical
in solid-state drawing, i.e., it is assumed that
the (pseudo-)affine deformation scheme
is valid. The (pseudo-)affine deformation
scheme was originally derived for chemi-
cally crosslinked rubbers and relates the
average orientation of statistical chain seg-
ments (cos2 6) to a single external parame-
ter: the macroscopic draw ratio [Eq. (11-4)]
(Grim and Kuhn, 1942)
(11-4)
-arctan((A 3 -l) l/2 )
In Eq. (11-4), the draw ratio (X) is defined
as the ratio of the length of a fiber after draw-
ing (/) to the original length of the fiber (/0).
The (pseudo-)affine deformation scheme
simplifies the quest for obtaining a high
orientation and chain extension to a single
objective, i.e., the sole requirement for a
high degree of chain orientation is a high
560 11 High-Modulus and High-Strength Fibers Based on Flexible Macromolecules
maximum-attainable draw ratio (see foot-
note in Sec. 11.3.3).
The maximum-attainable draw ratio of
semicrystalline polymers was calculated on
the basis of the ratio of the thickness of
chain-folded lamellae (t) to the effective
chain diameter (d) (Peterlin, 1978). In the
case of linear polyethylene, t and d are
respectively 200 and 5 A (20 and 0.5 nm)
and, consequently, this results in a maxi-
mum-attainable draw ratio of approximate-
ly 40. In a second approach, it is assumed
that the theoretical maximum-attainable
draw ratio is determined by the ratio of the
extended-chain length of the polymer to the
root mean square end-to-end distance of an
unperturbed random coil. The extended-
chain length of a polymer scales with the
molecular weight and the end-to-end dis-
tance with the square root of the molecular
weight and, consequently, it is predicted that
the theoretical maximum-attainable draw
ratio scales with the molecular weight
[Eq. (11-5)] (Kanamoto et al., 1983; Smith
et al., 1984; Irvine and Smith, 1986)
M 0.5 CH-5)
The theoretical maximum-attainable
draw ratio of linear polyethylene is plotted
in Fig. 11-5 as a function of the molecular
weight of the polymer. A rather large dis-
crepancy is observed in the theoretical esti-
mates of the maximum-attainable draw
ratio, especially at high molecular weights.
However, in both cases the theoretical
maximum-attainable draw ratio is high in
comparison with the draw ratios that are
applied in conventional fiber-spinning oper-
ations for polyamides, polyesters, polypro-
pylene, etc. (3<A<10).
150
S 100
03
o
E
1 50
100 1000
Molecular weight [kg/mol]
Figure 11-5. Theoretical maximum-attainable draw
ratio: (a) unperturbed random coils, (b) chain-folded
lamellae. The two horizontal lines indicate the esti-
mated range (Lemstra and Kirschbaum, 1985).
11.3 Spinning, Ultradrawing,
and Properties
of Linear Polyethylene
In the previous sections, the ultimate
properties of polyethylene with respect to
modulus, strength, and draw ratio were dis-
cussed on the basis of a variety of hypothet-
ical structures. On purpose, virtually all
experimental procedures to approach these
ultimate properties were omitted. In this
section, topics such as spinning, drawabil-
ity, stiffness, and strength are discussed
again, but this time from a more experimen-
tal point of view.
11.3.1 The Spinning Process
Polymers such as poly(vinylalcohol) and
poly(acrylonitrile) possess a degradation
temperature below the melting temperature
and, consequently, are traditionally spun
from solutions (dry or wet spinning)
 11.3 Spinning, Ultradrawing, and Properties of Linear Polyethylene
(Mclntyre and Denton, 1986). In general,
these polymers possess a rather low mo-
lecular weight and homogeneous solutions
can be produced quite easily. In the case
of linear polyethylene, extremely high mo-
lecular weight polymers [ultrahigh molec-
ular weight polyethylene (UHMW-PE)
M w > 8 x 105 g/mol] are used to obtain high
modulus and high strength fibers (see Sec.
11.3.2, 11.3.3, and 11.3.4); these polymers
cannot be spun from the melt due to their
high melt viscosity. The production of ho-
mogeneous solutions of UHMW-PE in sol-
vents like xylene, decalin, or paraffin oil/wax
in a conventional batch-scale fiber spinning
operation is extremely laborious. Moreover,
the solutions have a high viscosity and are
strongly viscoelastic even at low polymer
concentrations in solution (5 < </)< 15 %
wt./wt.), which further increases the tech-
nological difficulties encountered in con-
ventional dry- or wet-spinning operations.
In Figure 11-6, a schematic representa-
tion is shown of a typical spinning process
Continuous extrusion/solutions
Twin-screw / co-rotating
metering pump
spinneret
quenching/extraction bath
Figure 11-6. Schematic representation of the gel-spinning process (Lemstra et al., 1987 a).
561
used in the production of high modulus and
high strength UHMW-PE fibers. A co-
rotating twin-screw extruder is used to ob-
tain homogeneous solutions of UHMW-PE
in xylene, decalin, or paraffin oil/wax (res-
idence time in the extruder 5-20 min). The
highly viscous and viscoelastic UHMW-PE
solutions can be spun quite easily at high
spinning speeds, provided that care is taken
in the design of the spinnerets to prevent
any of the typical viscoelastic flow distur-
bances that can occur in this kind of solu-
tion. Moreover, both wet and dry spinning
can be performed, depending on the choice
of solvent (or other desirable features of the
spinning process) (Bulters and Meijer,
1990).
The use of UHMW-PE in combination
with solution spinning complicates the spin-
ning operation in comparison to conven-
tional melt spinning. Of course, this should
be counterbalanced by a bonus in the fiber
properties and this is indeed the case, as will
be explained in the following sections.
suspension
UHMW-PE
oven fibre
562 11 High-Modulus and High-Strength Fibers Based on Flexible Macromolecules
11.3.2 The Drawing Behavior
of Linear Polyethylenes
The relationship between solid-state
drawing and orientation/chain extension has
been investigated extensively in the past. In
retrospect, one of the most remarkable
observations was that the previously dis-
cussed (pseudo-)affine deformation scheme
(Sec. 11.2.3) is indeed valid in the case of
solid-state drawing at temperatures below
the melting temperature (Ward, 1985;
Pazur etal., 1993; Dirix et al., 1995). In
Fig. 11-7, the birefringence of drawn poly-
ethylene fibers is plotted as a function of
the draw ratio. Experimental data are pre-
sented on melt-spun fibers with large dif-
ferences in molecular weight, branch con-
tent, and type of branches. A single master
curve is observed which is independent of
the molecular architecture of the polymer.
Moreover, an excellent agreement is ob-
served between the experimental data
and theoretical predictions based on the
(pseudo-)affine deformation scheme (Sec.
11.2.3) (see footnote in Sec. 11.3.3).
o
o be obtained with melt-crystallized poly-
Draw ratio [-]
Figure 11-7. Birefringence of drawn polyethylenes
with different molecular weights and molecular archi-
tectures (Dirix et al., 1995).
The influence of solid-state drawing on
the root mean square end-to-end distance of
polyethylene macromolecules was investi-
gated by Sadler and Barham (1990 a, b, c).
The root mean square end-to-end distance
was determined using neutron scattering
experiments on (partly) deuterated, linear
polyethylene. It was found that the root
mean square end-to-end distance of the
macromolecular coil after drawing is direct-
ly related to the macroscopic draw ratio, and
it was concluded that the (pseudo-)affine
deformation scheme also applies with
respect to the degree of chain extension after
drawing.
Since the early days of synthetic fibers, it
has been realized intuitively that solid-state
drawing is highly effective at generating a
high degree of chain orientation and exten-
sion. Consequently, research efforts into
producing high modulus and strength fibers
almost automatically focused on obtaining
a high draw ratio. The first systematic
studies concerning the drawing behavior,
the maximum-attainable draw ratio, and the
properties of melt-crystallized polyethylene
were performed by Capaccio and Ward
(1973, 1974, 1975 a, b) and Capaccio et al.
(1976) (see also Chap. 15 of this Volume).
It was discovered that high maximum-
attainable draw ratios (Amax = 20-30) could
ethylene with a weight-average molecular
weight of approximately 102 kg/mol. More-
over, fibrous structures with a Young's mod-
ulus and tensile strength of respectively
70 GPa and 1.5 GPa could be produced
using specific crystallization procedures
prior to drawing (Wu and Black, 1979,
1980). Capaccio and co-workers also found
that the maximum-attainable draw ratio of
melt-crystallized polyethylene decreases
systematically with increasing molecular
weight (Fig. 11-8). Of course, this was a
rather disappointing experimental observa-
 11.3 Spinning, Ultradrawing, and Properties of Linear Polyethylene
O
03
CO
E
E
x entanglements. In principle, this model is
CO
Molecular weight [kg/mol]
Figure 11-8. Maximum-attainable draw ratio of
melt-crystallized polyethylene (Capaccio et al.,
1976).
tion, especially since the theoretical maxi-
mum-attainable draw ratio increases with
increasing molecular weight (Fig. 11-5).
In the late 1970s, it was discovered that
the gap between the theoretical (Fig. 11-5)
and experimental maximum-attainable
draw ratio (Fig. 11-8) of high molecular
weight polyethylene can be bridged, to a
large extent, by spinning and casting from
semi-dilute solutions (Smith and Lemstra,
1979 a, b, 1980 a, b, c; Smith et al., 1979 a,
b). It was also found that the excellent solid-
state drawing behavior of solution-spun
UHMW-PE fibers could be preserved even
after complete removal of solvent from the
fibers, i.e., the observed phenomena are not
simply related to a plasticizing effect of the
solvent but are related to some kind of struc-
tural or topological phenomena. In subse-
quent studies, the influence of the initial
polymer concentration in solution was
systematically investigated (Smith et al.,
1981) and it was found that the maximum-
attainable draw ratio scales with the initial
563
polymer concentration
LO.5
(11-6)
The above-described experimental ob-
servations inspired Smith et al. (1981) to
formulate a semi-empirical model to de-
scribe the drawing behavior of polyethylene
in terms of topological constraints such as
derived from classical rubber elasticity the-
ory. It is assumed that entanglements are
trapped in polyethylene upon crystallization
and act as semi-permanent crosslinks upon
solid-state drawing. Upon dissolution, the
entanglement density is reduced and conse-
quently the maximum-attainable draw ratio
is enhanced in comparison with that of melt-
crystallized polyethylene. On this basis, the
experimentally observed dependence of the
maximum-attainable draw ratio on the
initial polymer concentration in solution
was theoretically predicted [Eq. (11-6)].
Based on Eq. (11-6), it might be tempting
to conclude that the maximum-attainable
draw ratio of solution-spun UHMW-PE
fibers is solely determined by the polymer
concentration in solution, which is, of
course, an oversimplification (Bastiaan-
sen, 1990). In Fig. 11-9, the maximum-
attainable draw ratio of solution-spun
UHMW-PE fibers, at a fixed polymer
concentration in solution, is plotted as a
function of the weight-average molecular
weight. A rather strong molecular weight
dependence is observed, and it was shown
that the maximum-attainable draw ratio
scales with the so-called Bueche parameter
(0, Mw) as
A m a x oc(0M w ) 0 5 (11-7)
The maximum-attainable draw ratio of
polyethylene is also strongly influenced
by drawing conditions (temperature, strain
rate). In particular, drawing in a tempera-
ture gradient is an effective tool to further
564 11 High-Modulus and High-Strength Fibers Based on Flexible Macromolecules
E
Molecular weight [kg/mol]
Figure 11-9. Maximum-attainable draw ratio of
solution-spun, ultradrawn UHMW-PE fibers as a
function of the weight-average molecular weight: ()
melt-crystallized PE, (+) 0=10% w/w, () 0 = 2.5%
w/w (Bastiaansen, 1990).
enhance the maximum-attainable draw
ratio. Solution-spun UHMW-PE fibers pos-
sess a rather unique melting behavior
(Kirschbaum et al., 1986; Lemstra et al.,
1987 a, Bastiaansen and Lemstra, 1989).
Undrawn isotropic fibers have a melting
temperature of approximately 136 C, and
the (unconstrained) melting temperature
increases to approximately 142 C upon
solid-state drawing. An additional increase
in the melting temperature is observed upon
keeping the drawn fibers at a fixed length
(constraining) to approximately 155 C. The
fibers are, of course, constrained during
solid-state drawing, and consequently the
constrained melting temperature is the rel-
evant upper limit in temperature for ultra-
drawing. Therefore solution-spun UHMW-
PE fibers are usually drawn in a tempera-
ture gradient which starts at a low tempera-
ture (80-120 C) and increases to a ceiling
temperature of approximately 150 C, i.e.,
the drawing temperature is increased grad-
ually and more or less follows the increase
in melting temperature upon drawing. The
influence of this multistage drawing in a
temperature gradient on the maximum-
attainable draw ratio is illustrated in Fig.
11-10 (Bastiaansen, 1991). It is shown that
multistage drawing in a temperature gradi-
ent enhances the maximum-attainable draw
ratio and reduces to a certain extent the need
for a low polymer concentration in solution
in order to obtain a high draw ratio, i.e., high
draw ratios can be obtained with fibers spun
from quite concentrated solutions (0> 10%
wt./wt.).
In this section, it was shown that the draw
ratio uniquely determines the degree of
chain orientation and extension in ultra-
drawn polyethylene fibers. Moreover, it was
shown that the maximum-attainable draw
ratio can be tuned to a large extent by a
proper choice of raw materials (molecular
weight), spinning conditions (initial poly-
o
I
E
I
"x
Molecular weight [kg/moll
Figure 11-10. Maximum-attainable draw ratio of
solution-spun ((/)= 10% wt./wt.), ultradrawn UHMW-
PE fibers: Influence of multistage drawing in a tem-
perature gradient: () isothermal drawing at 100C,
(+) multistage drawing 100-130C () multistage
drawing 100-150C (Bastiaansen, 1991).
 11.3 Spinning, Ultradrawing, and Properties of Linear Polyethylene
mer concentration in solution), and drawing
conditions (drawing in a temperature gradi-
ent). In the following sections (Sees. 11.3.2
and 11.3.3), the relationships between solid-
state drawing and the properties of fibers in
terms of stiffness and strength are discussed.
11.3.3 The Young's Modulus
of Ultradrawn Polyethylenes
The influence of solid-state drawing on
the Young's modulus of melt-spun poly-
ethylene fibers was systematically investi-
gated by Cappacio and Ward (1973, 1974,
1975 a, b) and Capaccio et al. (1976). Based
on experimental results (Fig. 11-11), it was
concluded that the Young's modulus of
drawn, melt-crystallized polyethylene is
uniquely related to the draw ratio and inde-
pendent of the molecular weight and the
molecular architecture (content and type of
branches) of the polymer. The existence of
this unique Young's modulus versus draw
ratio curve was confirmed in subsequent
studies on the properties of solution-spun,
CO
Q.
CD
o have been reported. A variety of studies was devoted
>
10 20 30 40
Draw ratio [-]
Figure 11-11. Young's modulus versus draw ratio
curves of melt-spun, ultradrawn polyethylene fibers
(Capaccio et al., 1976).
565
drawn UHMW-PE fibers (Irvine and Smith,
1986). It was shown that the Young's mod-
ulus versus draw ratio curve is identical for
melt- and solution-spun polyethylene fibers
and that the Young's modulus versus draw
ratio curve is independent of, for instance,
the initial polymer concentration in solution
(Bastiaansen, 1991)2.
The ability to tune the maximum-
attainable draw ratio (Sec. 11.3.2) in com-
bination with unique relationships between
the draw ratio, birefringence (Sec. 11.3.2),
2
In both the theoretical (Sec. 11.2) and experimen-
tal (Sec. 11.3) sections of this chapter, it was claimed
that 'unique' relationships exist between the draw
ratio, the degree of orientation/extension, and the
Young's modulus of ultradrawn polyethylene. More
specifically, it was shown that the birefringence and
Young's modulus of drawn fibers depend solely on the
draw ratio and are independent of the initial polymer
concentration in solution, molecular weight, molecu-
lar weight distribution, and type and content of
branches. These observations were interpreted in
terms of the (pseudo-)affine deformation scheme
which relates the orientation of the drawn polymer to
a single parameter: the macroscopic draw ratio. More-
over, aggregate models relate the Young's modulus of
a drawn polymer directly to the birefringence (and
thus also the draw ratio) (Irvine and Smith, 1986). The
above-described relationships are not truly unique,
i.e., certain prerequisites for (pseudo-)affine deforma-
tion, for instance, with respect to drawing conditions
and starting morphology, should be met. The prime
prerequisites are that: (i) solid-state drawing is per-
formed at temperatures below the melting tempera-
ture, (ii) solid-state drawing is performed under opti-
mized conditions with respect to the drawing speed
and temperature, and (iii) the fibers possess a random
orientation prior to drawing (Capaccio et al., 1976;
Irvine and Smith, 1986). Frequently, these prerequis-
ites are not met and large deviations in the birefrin-
gence or Young's modulus versus draw ratio curve
to determining the effective draw ratio of oriented
polymers from shrinkage measurements performed at
temperatures slightly above the melting temperatures.
It was shown that truly unique relationships exist
between the draw ratio, birefringence, and Young's
modulus if the effective draw ratio is determined. In
this particular case, the experimental relationships are
also independent of, for instance, the drawing condi-
tions and starting morphology (Candia et al., 1985;
Hadziioannou et al., 1982; Watts et al., 1980; Wang
and Porter, 1981).
566 11 High-Modulus and High-Strength Fibers Based on Flexible Macromolecules
and Young's modulus (Sec. 11.3.3), has pro-
vided a powerful tool for bridging the gap
between the experimental and theoretical
Young's modulus of oriented polyethylene
fibers. In retrospect, it seems that the quest
for a high Young's modulus has been
extremely successful. Nowadays, drawn,
solution-spun UHMW-PE fibers with
Young's moduli of approximately 150 GPa
are commercially available. Moreover, so-
lution-spun, ultradrawn UHMW-PE fibers
were produced in labscale experiments with
Young's moduli in excess of 200 GPa (van
der Werff and Pennings, 1991), and these
values start to approach the theoretical val-
ues (Table 11-2).
11.3.4 The Tensile Strength
of Ultradrawn Polyethylenes
Until the late 1970s, the maximum ten-
sile strength of textile and technical yarns
based on flexible macromolecules was lim-
ited to approximately 1 GPa. This situation
was drastically altered with the discovery
that solution-spun UHMW-PE fibers could
be ultradrawn to extremely high draw ratios
(Smith and Lemstra, 1979 a, b; Smith et al.,
1979 a, b). In Fig. 11-12, the tensile strength
of solution-spun UHMW-PE fibers is plot-
ted as a function of the Young's modulus
(Smith and Lemstra, 1982). This graph illus-
trates that the tensile strength of solution-
spun, drawn UHME-PE fibers rapidly
increases with increasing draw ratio
(Young's modulus) and that fibers with a
high tensile strength (>3 GPa) can be ob-
tained. Nowadays, UHMW-PE fibers with
a tensile strength of 3 - 4 GPa are produced
industrially and fibers with a strength of
6 - 8 GPa (van der Werff and Pennings,
1991) were obtained in lab-scale experi-
ments.
It is obvious that the experimental values
for the maximum tensile strength of so-
05
CL
(3
c
(D
c
0 20 40 60 80 100 120
Young's modulus [GPa]
Figure 11-12. The tensile strength of solution-spun,
ultradrawn UHMW-PE fibers (Smith and Lemstra,
1982).
lution-spun, ultradrawn UHMW-PE fibers
(6-8 GPa) are low in comparison to the
theoretical values for a chain-extended
polyethylene chain with an infinite molec-
ular weight (>20 GPa). In the past, differ-
ent approaches have been used to describe
and interpret the origin(s) of this low experi-
mental tensile strength. In the following sec-
tions, these approaches are roughly subdi-
vided into two groups which are discussed
separately.
11.3.4.1 The Morphological
and Molecular Approach
The influence of the weight-average
molecular weight on the tensile strength of
melt- and solution-spun, ultradrawn poly-
ethylene fibers was systematically investi-
gated by Smith et al. (1981) and Smith and
Lemstra (1982). In these studies, the tensile
strength of the fibers was compared at a
fixed Young's modulus in order to eliminate
the influence of degree of orientation and
chain extension on the tensile strength. It
 11.3 Spinning, Ultradrawing, and Properties of Linear Polyethylene 567

was shown that the tensile strength of drawn .uu

fibers increases with increasing molecular
weight, and an empirical relationship be- 2 .50
o

tween the tensile strength, Young's mod- (0

+

ulus, and molecular weight was derived 2. 2 .00 o

>trengt
crtoc EnM
o +
(11-8) o*
1 .50
where ft = 0.7 and m = 0A.
o
The influence of the molecular weight

distribution on the tensile strength of solu-
tion-spun, ultradrawn UHMW-PE fibers
was also investigated by Smith et al. (1981)
and Smith and Lemstra (1982), and it was
found that a reduction in the polydispersity
(Q = MV//Mn) enhances the tensile strength
at a fixed Young's modulus and weight-
average molecular weight.
The above-described studies focus on the
influence of morphological and molecular
parameters on the tensile strength of solu-
tion-spun, ultradrawn UHMW-PE fibers.
The morphology of drawn UHMW-PE
fibers is characterized in terms of the bire-
fringence or the Young's modulus of the
drawn fibers and both are assumed to be
uniquely related to the draw ratio. The influ-
ence of defects such as chain-ends on the
tensile strength is emphasized based on the
experimentally observed dependence of the
tensile strength on the molecular weight
(Smith et al., 1981; Smith and Lemstra,
1982).
The influence of the propylene co-mono-
mer content on the tensile strength of solu-
tion-spun, ultradrawn UHMW-PE fibers
was investigated by Bastiaansen (1992 b).
The methyl side groups of ethylene-
propylene copolymers restrict intermolecu-
lar chain slippage (Bastiaansen, 1992 b) in
drawn fibers, and it was found that the ten-
sile strength of drawn UHMW-PE fibers is
independent of the propylene co-monomer
content if proper precautions are taken to
eliminate the influence of molecular weight
and Young's modulus on the tensile strength
nsi
1 .00
CD o
I
i
0 .50 y
n on
0 20 40 60 80 100 120
Young's modulus [GPa]
Figure 11-13. Tensile strength of solution-spun,
ultradrawn UHMW-PE fibers: () 0.5 CH3/1000 C-
atoms, (+) 2.5 CH3/1000 C-atoms, (o) 5 CH3/1000 C-
atoms, (O) 13 CH3/1000 C-atoms (Bastiaansen,
1992b).
(Fig. 11-13). Based on these experiments, it
was assumed that C-C bond rupture domi-
nates the fracture mechanism of drawn
UHMW-PE fibers, and the proposed frac-
ture mechanism closely resembles the
mechanism of Termonia et al. (1985, 1986)
for high molecular weight, perfectly orient-
ed structures with a finite molecular weight.
The theoretical estimates of the tensile
strength of structures with a number-
average molecular weight of 300 kg/mol is
approximately 10-12 GPa and the highest
experimental values for the tensile strength
of solution-spun UHMW-PE with a similar
number-average molecular weight seem to
approach these values (6-8 GPa). In other
words, the experimental maximum values
for the tensile strength start to approach the
theoretical values for an array of chain-
extended macromolecules with a finite
molecular weight.
568 11 High-Modulus and High-Strength Fibers Based on Flexible Macromolecules
11.3.4.2 Other Approaches
A variety of studies has been devoted to
the influence of macroscopic fiber dimen-
sions on the tensile strength of solution-
spun, ultradrawn UHMW-PE fibers. In the
first set of studies, it is assumed that the ten-
sile strength of ultradrawn UHMW-PE
fibers depends on the fiber diameter (Smook
et al., 1984; Wagner and Steenbakker,
1989). This diameter effect was observed
experimentally, shown by Fig. 11-14 a. In a
second set of studies, the influence of fiber
dimensions on the tensile strength was dis-
puted, i.e., it was found that the tensile
strength is independent of the fiber diame-
ter (Fig. 11-14 c) if the fibers are compared
at an identical Young's modulus (Bastiaan-
sen, 1992 a). Recently, it was found that
diameter effects only occur for a certain
range of fiber properties, i.e., diameter
effects are only observed above a Young's
modulus of 150 GPa (Fig. ll-14d and e)
Fibre diameter [a.u.]
Figure 11-14. Influence of the fiber diameter on the
tensile strength: (a) Smook et al. (1984), (b) Wagner
and Steenbakker (1989) (c) Bastiaansen (1992a),
(d) Penning (1994) (E > 150 GPa), and (e) Penning
(1994) (<150 GPa).
(Penning, 1994). The influence of the fiber
length on the tensile strength was also in-
vestigated (Penning, 1994; Schwartz et al.,
1986). Again, conflicting experimental ob-
servations were reported, although less pro-
nounced than in the case of diameter effects
on the tensile strength.
The influence of the fraction of taut-tie
molecules (TTMs) on the tensile strength
of solution-spun, ultradrawn UHMW-PE
fibers was investigated by Penning et al.
(1990), and Penning (1994). The fraction of
taut-tie molecules was derived from the
crystallinity of the drawn fibers, and a direct
relationship between the tensile strength
and the fraction of taut-tie molecules was
observed (Fig. 11-15).
The above-described studies focus on the
influence of fiber dimensions or on the
influence of taut-tie molecules on the ten-
sile strength. Models to describe the experi-
mental observations were derived and an
excellent agreement between experimen-
tal data and theoretical predictions was
observed. The models were used to estimate
0.00 0.04 0.08 0.12 0.16 0.20
TTM fraction [-]
Figure 11-15. Influence of the fraction of taut-tie
molecules on the tensile strength of solution-spun,
ultradrawn UHMW-PE fibers (Penning, 1994).
 11.3 Spinning, Ultradrawing, and Properties of Linear Polyethylene
the theoretical tensile strength of solution-
spun, ultradrawn UHMW-PE fibers and
absolute values were obtained which close-
ly approach the theoretical tensile strengths
as derived for an array of infinitely long,
chain-extended, polyethylene chains.
11.3.4.3 Remarks
The approaches to describe the fracture
mechanism and tensile strength of solution-
spun, ultradrawn UHMW-PE fibers are to
some extent mutually incompatible, i.e.,
experimental parameters that are considered
dominant in a certain approach are ignored
in a second approach, and vice versa. For
instance, the influence of the molecular
weight is considered of prime importance
by Smith et al.(Sec. 11.3.4.1) and is ignored
by Pennings et al (Sec. 11.3.4.2). Also,
experimental studies on the influence of
fiber dimensions (diameter/length) on the
tensile strength exhibit some serious
discrepancies (Fig. ll-14a, b). Moreover,
theoretical models to describe the fracture
behavior of solution-spun, ultradrawn
UHMW-PE fibers and/or to predict the theo-
retical tensile strength suffer from similar
drawbacks. The current situation with
respect to the understanding of the fracture
behavior of solution-spun, ultradrawn
UHMW-PE fibers seems undesirable from
a fundamental and an applied point of view.
11.3.5 Miscellaneous Properties
In the previous sections the properties
of solution-spun, ultradrawn UHMW-PE
fibers were discussed in terms of their
Young's modulus and tensile strength.
These properties are, of course, relevant in
a large number of applications, such as fish-
ing nets and/or lines, ropes, and compos-
ites. Solution-spun, ultradrawn UHME-PE
fibers also possess a number of other favor-
569
able properties, such as a high impact resis-
tance, cutting resistance, a low dielectric
constant, a low dielectric loss, low stretch,
high heat conductivity, and a high sonic
modulus. In particular, these 'secondar'
properties are an important advantage in
applications such as bullet-proof vests
(impact), helmets (impact), hybrid compos-
ites (impact), gloves (cutting resistance),
fishing lines (low stretch), loudspeaker
cones (sonic modulus), and radomes/sonar
domes (dielectric properties).
Of course, solution-spun, ultradrawn
UHMW-PE fibers also possess a few disad-
vantages, such as creep under static loading
conditions, a low melting temperature, and
a low compressive strength. The time/tem-
perature dependence of the mechanical
properties of UHMW-PE fibers has been
extensively investigated (Leblans et al.,
1989; Govaert, 1990; Govaert and Lemstra,
1992;Govaertet al., 1991,1993;Peijset al.,
1994 a). It was found that the properties of
these fibers are strongly nonlinear visco-
elastic and can be mathematically described
by a combination of a linear viscoelastic
contribution and a nonlinear plastic flow
process. In recent studies (Peijs et al.,
1990a, 1994b; Peijs and Venderbosch,
1991), it was shown that the low interlami-
nar shear strength (ILSS) of composites
containing UHMW-PE fibers originates
from their poor off-axis properties (Table
11-3). However, it was also found that
Table 11-3. ILSS of unidirectional epoxy-based com-
posites a.
Fiber [ILSS (Pa)]
PE (untreated) 13
PE (corona/plasma treated) 20-30
Aramid 45-70
E-glass 75-95
Carbon 80-120
a
Peijs etal. (1993).
570 11 High-Modulus and High-Strength Fibers Based on Flexible Macromolecules
hybrid composites based on, for instance,
carbon fibers and UHMW-PE fibers can
possess an optimal balance of impact prop-
erties and creep and fatigue resistance (Peijs
etal., 1990a, b, 1993; Peijs and Vender-
bosch 1991; Peijs and Klinken, 1992; Peijs
anddeKok, 1993).
11.4 The Drawing Behavior
and Properties of Flexible
Semicrystalline Polymers
11.4.1 The Drawing Behavior
and Properties of Semicrystalline
Apolar Polymers
The drawing behavior and properties of a
rather wide range of apolar polymers, other
than linear polyethylene, have been investi-
gated in the past. In particular, the drawing
behavior and properties of isotactic poly-
propylene and polyoxymethylene were
investigated extensively. The prime motiva-
tion for using these polymers to produce
high modulus and high strength fibers is
(probably) their enhanced melting temper-
ature in comparison to that of linear poly-
ethylenes. In Table 11-4, the Young's
moduli of melt- and solution-spun, drawn
polypropylene and polyoxymethylene are
compared with estimates of the maximum
Young's moduli based on X-ray measure-
ments. The experimental values for the
Table 11-4. The experimental and X-ray Young's
moduli of melt- and solution-spun polypropylene and
polyoxymethylene fibers.
Polymer Process Modulus (GPa)
(exp.) (X-ray)
i-PP melt-spinning 22 40
solution-casting 36
POM melt-spinning 60 73
Young's modulus approach the maximum
Young's moduli, which illustrates that the
concepts derived for linear polyethylenes
can be used for other apolar polymers.
11.4.2 The Drawing Behavior
and Properties of Semicrystalline
Polar Polymers
Almost immediately after the discovery
of the gel-spinning process for the produc-
tion of high modulus and strength UHMW-
PE fibers, it was realized that these fibers
possess some intrinsic disadvantages, such
as a low melting temperature, creep under
static loading conditions, and a low com-
pressive strength (Leblans et al., 1989;
Govaert, 1990; Covaert andLemstra, 1992;
Govaert et al., 1993; Peijs et al., 1990a, b,
1994b, 1995). These disadvantages are vir-
tually irrelevant in applications such as
bullet-proof vests, gloves, and fishing nets.
However, they are a serious limitation in,
for instance, ropes and structural compos-
ites. An extensive research effort has been
performed to produce high modulus and
strength fibers from 'polar' polymers, i.e.,
polymers that possess intermolecular inter-
actions such as hydrogen bonds. The prime
objective was to use the concepts developed
for solution-spun, ultradrawn UHMW-PE
fibers to produce high performance fibers
from polymers such as poly(vinylalcohol)
(PVOH), polyamides (PA), polyketones
(PECO, and polyacrylonitrile (PAN). How-
ever, attempts to produce these fibers were
at best partly successful and the problems
encountered will be discussed briefly in the
following sections.
In the case of linear polyethylene, the
combination of a high weight-average
molecular weight with a low initial polymer
concentration in solution results in a high
maximum-attainable draw ratio. The avail-
ability of high molecular weight, linear
 11.4 The Drawing Behavior and Properties of Flexible Semicrystalline Polymers
polyethylene proved to be of prime impor-
tance in order to obtain a high maximum-
attainable draw ratio. In the case of low
molecular weight polymers such as poly-
amide-6, polyamide-6,6, and polyethylene-
terephthalate (PET), the maximum-attain-
able draw ratio is intrinsically limited by the
molecular weight (Irvine and Smith, 1986).
Moreover, an additional barrier to obtaining
a high draw ratio is present, as will be dis-
cussed in the next section.
In Fig. 11-16, the maximum-attainable
draw ratio of solution-spun poly(vinylalco-
hol) and polyethylene fibers is plotted as a
function of the Bueche parameter (Schelle-
kens and Bastiaansen, 1991). As discussed
previously, the maximum-attainable draw
ratio of polyethylene can be tuned to a large
extent by a proper choice of the initial
polymer concentration in solution and the
weight-average molecular weight. This tun-
ability is to a large extent lost in the case of
PVOH and a rather low ceiling value for the
maximum-attainable draw ratio is observed
(Fig. 11-16).
a drawing. In the case of linear polyethylene,
E the a-relaxation temperature hardly in-
10
C . Mw [-]
Figure 11-16. Maximum-attainable draw ratio of PE
() and PVOH (O) fibers as a function of the Bueche
parameter (CAfw) (Schellekens and Bastiaansen,
1991).
571
In polyethylene, relatively weak inter-
molecular interactions (van der Waals
bonds) are present within the polymeric
crystal lattice and it is usually assumed that
the crystals hardly restrict the unfolding
of lamellae upon solid-state drawing, i.e.,
the maximum-attainable draw ratio is sole-
ly determined by topological constraints
such as entanglements (Smith et al., 1981).
In the case of polymers such as poly(vinyl-
alcohol) and polyamides, hydrogen bonds
are present within the crystal lattice and it
is usually assumed that these hydrogen
bonds have a detrimental influence on the
drawability, i.e., they restrict the unfolding
of crystals upon solid-state drawing and
limit the maximum-attainable draw ratio
(Garrett and Grubb, 1988; Bastiaansen,
1991).
One way to illustrate the influence of
intermolecular interactions on the maxi-
mum-attainable draw ratio is briefly de-
scribed in this section. Semicrystalline
polymers often exhibit a so-called a-
transition temperature which is related to a
certain degree of translational mobility of
the polymeric chains within the crystal lat-
tice. Usually, solid-state drawing is per-
formed in a temperature window between
the a-relaxation temperature (~80C) and
the melting temperature to facilitate the
unfolding of chain-folded crystals upon
creases upon solid-state drawing (Gibson
et al., 1978; Smith et al., 1975; Saw atari and
Matsuo, 1985), and the mobility and de-
formability are preserved within the crys-
tal. The a-relaxation temperature, of, for
instance, PVOH rapidly increases with
increasing draw ratio, and the maximum-
attainable draw ratio is reached as soon as
the a-relaxation temperature approaches the
melting and/or drawing temperature, i.e.,
the translational mobility in the crystal lat-
572 11 High-Modulus and High-Strength Fibers Based on Flexible Macromolecules
tice is lost, intermolecular slip is strongly
hindered, and fracture of the fibers occurs
(Garrett and Grubb, 1988).
A second approach to interpret the above-
described phenomena with respect to the
limited drawability of polar polymers was
recently proposed by Lommerts (1994). It
was shown that the maximum-attainable
draw ratio of semicrystalline polymers is
related to their cohesive energy density (Fig.
11-17), which, in principle, represents the
total energy of all intermolecular interac-
tions in a polymer. The experimentally
observed relationship between the maxi-
mum-attainable draw ratio of semicrystal-
line polymers and the cohesive energy den-
sity further illustrates that enhanced inter-
molecular interactions in polar polymers
dominate their solid-state drawing behavior.
In the case of polymers with an inter-
mediate cohesive energy density, such as
PVOH and PECO, this results in moderate
maximum-attainable draw ratios (Amax =
= 15-30). For polymers with high cohesive
energy density levels, such as polyamide-6
CO
Cohesive energy/RTdraw [-]
Figure 11-17. Maximum-attainable draw ratio of a
series of flexible chain polymers as a function of the
cohesive energy density (Lommerts, 1994).
and polyamide-6,6, the maximum-attain-
able draw ratio is even less (5 < Amax < 7)
(Lommerts, 1994).
The tensile strength of poly(vinylalcohol)
fibers is plotted in Fig. 11-18 as a function
of the draw ratio, and a comparison is made
with drawn, linear polyethylene (Schellek-
ens and Bastiaansen, 1991). The tensile
strength of PVOH fibers, at a fixed degree
of polymerization, is high in comparison to
that of linear polyethylene. Probably, this
comparatively high tensile strength also
originates from the presence of hydrogen
bonds which, at a comparatively low molec-
ular weight, induces a transition from a
slippage-dominated fracture mechanism to
a C-C bond rupture type of fracture mech-
anism. The favorable influence of an
enhanced intermolecular interaction on the
tensile strength was theoretically predicted
by Termonia et al. (1986) based on Monte-
Carlo simulations of an array of chain-
extended polymers with a finite molecular
weight (Fig. 11-19).
CO
Q_
(5
c
CD
1 10
Maximum draw ratio [-]
Figure 11-18. Tensile strength of PE () and PVOH
(O) fibers as a function of the draw ratio (degree of
polymerization ~ 3500) (Schellekens and Bastiaansen,
1991).
 11.4 The Drawing Behavior and Properties of Flexible Semicrystalline Polymers
1.00
Aramid
0.80
c
CD
- 0.60
0.40
0.20
0.00
Molecular weight
Figure 11-19. Theoretical tensile strength of a chain-
extended array of polymer chains with a finite molec-
ular weight. The arrow indicates the direction of
increased strength of the secondary bonds. (Courtesy
of P. Smith, ETH, Zurich, Switzerland.)
The above-described observations dimin-
ish, to a certain extent, the need for a high
maximum-attainable draw ratio and a high
molecular weight in order to obtain high
strength fibers based on polymers with an
intermediate polarity (cohesive energy den-
sity), such as PVOH and PECO. PVOH
fibers with a Young's modulus and tensile
strength of, respectively, -70 GPa and
-2.5 GPa can be produced (Kwon et al.,
1984; Schellekens and Bastiaansen, 1991;
Schellekens and Ketel, 1990; Schellekens et
al., 1991; Mokveld and Schellekens, 1986),
and PECO fibers with a Young's modulus
and tensile strength of, respectively,
~50GPa and 3.5 GPa were produced by
Lommerts (1994). These fibers indeed pos-
sess a strongly reduced creep (Lommerts,
1994), an enhanced melting temperature
(Lommerts, 1994), and an enhanced com-
pressive strength (Peijs et al., 1995). More-
over, these fibers potentially open a new
range of applications for high modulus and
high strength fibers.
573
11.4.3 The Drawing Behavior
and Properties
of Semiflexible Polyimides
A series of studies on the processing and
properties of high modulus and high
strength polyimide fibers was published by
Kaneda et al. (1986 a, b) and Cheng et al.
(1991). In these studies, new polyimides
were prepared in a single step by the reac-
tion of 3,3',4,4'-biphenyltetracarboxylic
dianhydride (BPDA) with several aromatic
diamines. Subsequently, solutions of the
polymers were spun into an coagulation
bath and wound on a bobbin. Then the fibers
were drawn at a temperature of 300 - 500 C
to a maximum-attainable draw ratio of ap-
proximately 7 - 8 . Fibers with a Young's
modulus and a tensile strength of, respec-
tively, 150 GPa and 3 GPa were obtained.
Moreover, these fibers possessed an en-
hanced solvent resistance, UV resistance,
and temperature resistance in comparison
with Kevlar (Kaneda et al., 1986 a, b; Cheng
etal., 1991).
In general, polyimides are rather rigid and
intractable polymers. However, solutions of
the above-described polyimides are homo-
geneous, i.e., liquid crystalline structures,
such as observed in PPTA solutions, are not
obtained. The as-spun fibers possess a low
Young's modulus (<20GPa) and strength
(<1 GPa). However, high modulus and
strength fibers are obtained after solid-state
drawing despite a low maximum-attainable
draw ratio. The above-described fibers pos-
sess excellent properties in comparison to
'conventional' high modulus and strength
fibers based on flexible (PE, PVOH, PECO)
and rigid polymers (PPTA). Moreover, the
spinning process combines features of the
process for PPTA fibers (rigid polymers, air-
gap spinning) with features of the process
for flexible polymers (homogeneous solu-
tions, drawing), which was the prime moti-
574 11 High-Modulus and High-Strength Fibers Based on Flexible Macromolecules
vation for briefly discussing these high per-
formance fibers.
11.5 Outlook
Over the past two decades, tremendous
progress has been made in exploiting the
intrinsic high modulus and high strength of
the polymer backbone of semicrystalline
flexible polymers. Fibers are produced both
in lab-scale experiments and in industrial
processes with moduli and strengths ap-
proaching the theoretical values. This suc-
cess in bridging the gap between experimen-
tal and theoretical values for the stiffness
and strength is, however, restricted to apo-
lar polymers such as polyolefins. Attempts
to produce high modulus and high strength
fibers from polymers such as polyamides,
polyesters, polyketones, poly(vinylalco-
hol), and polyacrylonitrile were at best part-
ly successful. In retrospect this was rather
disappointing since high stiffness and high
strength fibers based on these polymers
should possess a number of advantages
compared to polyolefinic fibers, such as: (i)
a high melting temperature, (ii) reduced
creep, (iii) enhanced compressive strength,
etc. The limitations encountered are related
to the chemical structure of the polymers
(low molecular weight/intermolecular hy-
drogen bonds), which restricts the attainable
draw ratio, modulus, and strength. Conse-
quently, new processes, other than simply
spinning from solution and ultradrawing,
should be developed to induce orientation
and chain extension in these polymers.
A first experimental approach in this
direction are fibers based on certain semi-
rigid polyimides which possess a modulus
and strength of, respectively, >120 GPa and
>3 GPa. These fibers are produced from
homogeneous solutions despite their com-
paratively rigid polymer backbone and are
drawn in the solid state at elevated temper-
atures. Such fibers indeed possess enhanced
high temperature and creep properties in
comparison to polyolefinic high modulus
and high strength fibers. A second approach
involves fibers based on a new generation
of polyolefins such as syndiotactic polypro-
pylene and syndiotactic polystyrene. These
polymers possess a high molecular weight
and a high melting temperature. Moreover,
the maximum-attainable draw ratio is prob-
ably not limited by strong intermolecular
interactions. Unfortunately, it is usually
expected that the properties of the above-
described fibers, in a best case scenario,
resemble conventional PPTA fibers or car-
bon fibers. This latter prospect explains to
some extent the reduced academic and
industrial interest and activity in the field of
new high modulus and strength fibers.
11.6 Acknowledgements
The author thanks T. Tervoort, T. Peijs,
P. J. Lemstra, P. Smith, and H. E. H. Meijer
(TUE, Eindhoven, The Netherlands) for
correcting the manuscript and for their stim-
ulating discussions. The author appreciates
the permission of P. Smith (ETH, Zurich,
Switzerland) to use some of his unpub-
lished results (Figs. 11-1 and 11-20) in this
chapter. Also, he thanks G. Calis (DSM
Research, Geleen, The Netherlands), M.
Jacobs, and J. van Dingenen (DSM High
Performance Fibres, Heerlen, The Nether-
lands) for their suggestions and comments.
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Treloar, L. R. G. (1960), Polymer 1, 95.
van der Werff, H., Pennings, A. J. (1988), Polym. Bull.
19, 587.
van der Werff, H., Pennings, A. J. (1991), Colloid
Polym. Sci. 747, 63.
Wagner, H. D., Steenbakker, L. W. (1989), Phil Mag.
Lett. 59, 11.
Wang, L. H., Porter, R. S. (1981), J. Appl. Polym. Sci.
26, 2373.
Ward, I. M. (1985), Mechanical Properties of Solid
Polymers, 2nd ed. New York: Wiley, p. 286.
Watts, M. P. C, Zachariades, A. E., Porter, R. S. (1980)
J. Mater. Sci. 75,4261.
Williams, T. (1973), J. Mater. Sci. 8, 59.
Wobser, G., Blasenbrey, S. (1970), Kolloid Z. Z.
Polym. 241, 895.
Wu, T., Black, H. (1979), Polym. Eng. Sci. 19, 163.
Wu, T., Black, H. (1980), U.S. Patent 42228 118.
Zachariades, A. E., Porter, R. S. (1979) J. Appl. Polym.
Sci. 24, 1371.
Zachariades, A. E., Sherman, E. S., Porter, R. S.
(1979), J. Appl Polym. Sci. 24, 2137.
Zhirnov, N. I., Koryak-Dorenko, Y. G., Bartenev,
G. M. (1969), Polym. Sci. USSR 11, 1396.
Zwijnenburg, A., Pennings, A. (1975), /. Colloid
Polym. Sci. 253, 452.
11.7 References 577
Zwijnenburg, A., Pennings, A. (1976 a), /. Polym.
Sci., Polym. Lett. Ed. 14, 339.
Zwijnenburg, A., Pennings, A. (1976 b), /. Colloid
Polym. Sci. 254, 858.
General Reading
Capaccio, G., Ward, I. M. (1973), Nature (Phys. Sci.)
243, 143.
Grun, E, Kuhn, W. (1942), Kolloid Z. 101, 248.
Irvine, P. A., Smith, P. (1986), Macromolecules 19,
240.
Kelly, A., Macmillan, N. H. (1986), Strong Solids, 3rd
ed. Oxford: Clarendon.
Smith, P., Lemstra, P. J., Booij, H. C. (1981), J. Polym.
Sci., Polym. Phys. Ed. 19, 877.
Termonia, Y, Meakin, P., Smith, P. (1985), Macro-
molecules 18, 2246.
Termonia, Y, Meakin, P., Smith, P. (1986), Macro-
molecules 19, 154.
Ward, I. M. (Ed.) (1982), Developments in Oriented
Polymers. London: Applied Science.
Ward, I. M. (Ed.) (1987), Developments in Oriented
Polymers 2. Amsterdam: Elsevier.
12 Deformation and Toughness of Polymers
Marco C. M. van der Sanden

DSM Research Geleen, The Netherlands

List of Symbols and Abbreviations 580

12.1 Ultimate Properties 582
12.2 Molecular Network Structure and Natural Draw Ratio 583
12.3 Deformation Mechanisms 586
12.3.1 Crazing 586
12.3.2 Shear Yielding 587
12.3.3 Crazing Versus Shear Yielding 588
12.4 Natural Draw Ratio Versus Local Strain 589
12.5 Toughness Improvement in Practice 590
12.5.1 Plasticization 590
12.5.2 Rubber Modification 590
12.5.2.1 Multiple Crazing 591
12.5.2.2 Multiple Shear Deformation 592
12.6 The Concept of a Critical Thickness 593
12.7 The Critical Thickness of Polystyrene 594
12.7.1 Multilayered Tapes 594
12.7.2 Mechanical Properties of Polystyrene (PS) Tapes 595
12.7.3 Rubber-Modified Polystyrene 597
12.7.4 Local Thickness 600
12.8 Critical Thickness and Network Density 600
12.8.1 Entanglement Density 601
12.8.2 Multilayered Polystyrene-Poly(2,6-Dimethyl-1,4-Phenylene Ether)/
Polyethylene (PS-PPE/PE) Tapes 603
12.8.3 Rubber-Modified PS-PPE Blends 604
12.8.4 Theoretical Considerations 605
12.8.4.1 Macroscopic Strain 605
12.8.4.2 Critical Microscopic Thickness 606
12.9 Concluding Remarks 608
12.10 Acknowledgements 611
12.11 References 611

Materials Science and Technology

Copyright WILEY-VCH Verlag GmbH & Co KGaA. All rights reserved.
580 12 Deformation and Toughness of Polymers

List of Symbols and Abbreviations

aT frequency factor
C^ characteristic ratio
d root mean square end-to-end distance between junction points in a network
dl2 diameter
dp particle or hole diameter
Dl average interparticle distance
DIc critical matrix ligament thickness (critical intercellular distance)
Ex Young's modulus
G lc fracture toughness
GNO storage modulus of plateau
G' storage modulus
h diameter
k, kl2 constant
/e chain contour length
lQ average projected length of a chain segment
M molecular weight
Mc molecular weight between crosslinks
Me molecular weight between entanglements
Mn number-average molar mass
Mw weight-average molecular weight
Mcr critical molecular weight
Mo molecular weight of chain segment
NA Avogadro's number
p 'packing length', i.e., actual volume occupied by the chain divided by its mean
end-to-end distance
R gas constant
(R2) root mean square end-to-end distance of the polymer
T reference temperature
rg glass transition temperature
U polymer backbone energy
f/av available elastic energy per ligament
UrQ energy required to create a brittle fracture
V volume
Vo initial volume

7 van der Waals surface energy

F surface energy of the polymeric matrix material
8 loss angle
ADZ extension ratio in a shear deformation zone
^craze craze fibril extension ratio
^macr m a x i m u m macroscopic strain-to-break/draw ratio
Amax m a x i m u m draw ratio
^max, after ^max after craze formation
 List of Symbols and Abbreviations 581

crosslink density
entanglement density
P density
Of fracture stress
CJy yield stress
polymer volume fraction in solution
weight fraction
CO angular frequency

ABS acrylonitrile-butadiene-styrene
DSC differential scanning calorimetry
EPDM ethylene-propylene-diene monomer
EPR ethylene-propylene rubber
HIPS high impact polystyrene
PC polycarbonate
PE polyethylene
PIB polyisobutylene
PMMA poly(methylmethacrylate)
PP polypropylene
PPE poly(2,6-dimethyl-1,4,-phenylene ether)
PPTA poly(/7-phenylene terephthalamide)
PS polystyrene
SAN styrene-acrylonitrile
SEM scanning electron micrograph
582 12 Deformation and Toughness of Polymers
12.1 Ultimate Properties
The main feature that sets polymers apart
from other materials is the constituting ele-
ments, i.e., the long chain macromolecules.
The main characteristic of the macromolec-
ular chain is that the chemical bonding is
strong and directional along the chain,
whereas usually only weak, secondary (e.g.,
van der Waals) interactions exist between
the chains in the case of apolar polymers, or
occasionally hydrogen bonding, in poly-
amides, for example.
Polymeric materials were not usually
associated with impressive mechanical
properties for engineering purposes. In fact,
the generic term "plastic" for (thermoplas-
tic) polymeric materials is indicative of the
generally expected mechanical perfor-
mance.
However, in the past two decades impres-
sive progress has been made in exploiting
the intrinsic properties of the macromolecu-
lar chain by producing high strength/high
stiffness structures such as fibers and tapes.
Amongst the various developments in the
area of these so-called high performance
fibers, two major routes can be discerned
which are completely different in respect of
the base materials, i.e., rigid chain molecules
as opposed to flexible macromolecules. The
prime examples of rigid chain polymers are
the aromatic polyamides, notably poly
(/?-pheny lene terephthalamide) (PPTA).
Fibers based on aligned PPTA macromole-
cules are produced by DuPont (Kevlar) and
AKZO (Twaron) with Young's moduli of
90 GPa and tensile strengths of 3 GPa. The
prime example of a high performance fiber
based on flexible macromolecules is (high
molecular weight) polyethylene. For a
detailed discussion of the properties of both
classes of fibers see Chap. 13 of Vol. 12 of
this Series. High strength polyethylene
fibers are produced by DSM (Dyneema) via
solution spinning of ultrahigh molecular
weight polyethylene followed by an
(ultra)drawing process. The paramount fac-
tors controlling drawability and the related
tensile properties are understood in molecu-
lar terms. Upon dissolution of ultrahigh
molecular weight polyethylene, the long
chain macromolecules become disentangled
and the disentangled structure is retained
upon quenching/crystallization in the gel or
solid state. Ultradrawing in the solid state,
in a temperature range close to but below the
melting point, is feasible since the polyeth-
ylene crystals do not resist deformation and
the number of entanglements that act as
physical crosslinks on the time scale of the
drawing operation have to a large extent been
removed during the dissolution procedure.
The maximum draw ratio, A^a*, is related to
the square root of the molecular weight
between entanglements Me, i.e., A^^ooMg72,
whereas Me is inversely proportional to the
polymer volume fraction q> in solution; see
Eq. (12-1) for the dependence of Amax on Me
and (p (Smith et al., 1981)
(12-1)
In contrast to the ultimate properties, e.g.,
stiffness and strength, the ultimate tough-
ness of polymeric materials, another impor-
tant engineering property, is poorly under-
stood, as demonstrated by numerous papers
with conflicting views and often system-
related specific results which lack general-
ity. The current state of our understanding
is reviewed in Chap. 15 of Vol. 12 of this
Series.
Toughness can be considered, to a first
approximation, as the work to break during
(tensile) deformation, i.e., the area of the
stress-strain curve during loading the spec-
imen to failure. In this respect, toughness
should be related to the deformation of an
entanglement network, similar to tensile
 12.2 Molecular Network Structure and Natural Draw Ratio
drawing for obtaining high strength/high
modulus, oriented fibrous structures.
In contrast with crystallizable polymers
like polyethylene and polypropylene, the
entanglement network in the case of amor-
phous polymers cannot be changed via a dis-
solution procedure. Disentanglement can be
achieved by dissolving the amorphous poly-
mer, but the disentangled state cannot be
made permanent via crystallization and,
consequently, upon removal of the solvent,
reentanglement occurs. Hence, in the case
of amorphous, glassy polymers, the entan-
glement network is dictated by the macro-
molecular chemical structure (see Sec.
12.2). Information concerning the entangle-
ment network structure in the solid state can
be obtained via equilibrium rheological
measurements, since the molecular weight
between entanglement nodes, Me, can be
derived from the rubber plateau modulus in
the melt (Ferry, 1980)(seeSec. 12.2).In this
respect, polystyrene can be considered as a
rather loose network, the value for Me is
approximately 20 kg mol"1, compared with
polycarbonate and polyethylene where Me
is approximately 2 kg mol"1 (Wu, 1989).
Transferring the basic principles of draw-
ing (disentangled) semi-crystalline poly-
mers (e.g., polyethylene), polystyrene
would be expected to be a rather tough poly-
mer in comparison with polycarbonate. The
maximum or natural draw ratio can be esti-
mated from Me and is expected to be approx.
4 or an elongation at break of about 300%
(Kramer and Berger, 1990). In the early
1980s, Kramer (1983) performed pioneer-
ing and elegant experiments which showed
that the maximum extension ratios in craze
fibrils and shear deformation zones in amor-
phous glassy polymers, including polysty-
rene and polycarbonate, corresponded with
the natural draw ratio calculated from Me
using Eq. (12-1), i.e., <p=\. These important
experiments demonstrate that the basic prin-
583
ciple, i.e., that the maximum draw ratio is
determined by fully stretching the molecu-
lar strands between entanglement nodes,
can be applied during the deformation of
glassy amorphous polymers.
In actual practice, however, polystyrene
is the paradigm of a brittle polymer with a
macroscopic elongation at break of 1-3%,
whereas polycarbonate is considered to be
a tough engineering plastic. This paradox
initiated the present study and is the main
issue for this chapter. It will be demonstrat-
ed that the apparent paradox can be solved
by tailoring the morphology of the compos-
ite through polymer processing, resulting in
the ultimate toughness of an amorphous
polymer system on a macroscopic level.
In Sec. 12.2 the molecular network struc-
ture of amorphous polymers will be ana-
lyzed briefly, followed by an estimation of
the maximum (natural) draw ratio based on
this network structure. Sections 12.3 and
12.4 mainly deal with a literature review of
the two deformation mechanisms that occur
in glassy amorphous polymers, i.e., crazing
and shear yielding, and the relationship
between these localized deformation mech-
anisms and the polymer network structure.
Before discussing the importance of mor-
phology (i.e., processing) in achieving ulti-
mate macroscopic toughness (the concept of
a critical thickness; see Sees. 12.6,12.7, and
12.8), the classical toughening concepts will
be reviewed in Sec. 12.5. Finally, some con-
cluding remarks will be made in Sec. 12.9
emphasizing the importance of polymer
processing in achieving the ultimate tough-
ness of a polymeric system.
12.2 Molecular Network
Structure and Natural Draw Ratio
Using small-angle neutron scattering,
Kirste et al. (1973) demonstrated that the
584 12 Deformation and Toughness of Polymers

conformation of macromolecules of amor-

phous polymers in the glassy state is equal
to their conformation in a theta solvent (and
in the melt), i.e., the so-called unperturbed
chain.
From viscosity measurements performed
on melts of polystyrene it is known that
above a certain critical molecular weight of
polystyrene the viscosity suddenly increas-
es strongly: see Fig. 12-1 (Porter and John-
son, 1966). This effect is attributed to entan-
glement coupling; above a certain critical
molecular weight (Mcr) entanglements are
Log M w (g mol" 1 )
formed. The formation of entanglements
above this critical molecular weight can also Figure 12-1. Log-log plot of reduced melt viscosity
be noticed in an evaluation of the storage as a function of weight-average molar mass for poly-
modulus, G', of narrow distribution polysty- styrene [reproduced with permission from Porter and
Johnson (1966)].
renes with varying molecular weight as a
function of the reduced frequency (see
Fig. 12-2) (Onogi et al., 1970).
The storage modulus reveals a plateau
region above the glass transition. This so-
called rubbery plateau becomes more pro-
nounced with increasing molecular weight,
i.e., longer relaxation times of the polymer
chains. However, the height of this plateau,
GN0, remains unchanged upon increasing
the molecular weight above the critical
value. Similar to the rheological behavior of
crosslinked rubbers above their glass tran-
sition temperature, GN0 can be related to an
average molecular weight between nodes
of enhanced friction (i.e., entanglements in Log(coaT) (s 1)

the case of thermoplastic polymers, and
crosslinks for chemically cured thermo-
sets).
Also in the glassy state the effect of entan-
glement coupling can be noticed. In Fig.
12-3 the dependence of the fracture stress
upon molar mass is shown for poly(methyl-
methacrylate) (PMMA) according to Vin-
cent (1960b).
At a number-average molecular weight of
approximately 50 kg mol"1, a rather abrupt
increase can be observed in the fracture
Figure 12-2. Storage modulus of narrow distribution
polystyrenes, plotted logarithmically against the fre-
quency (co) reduced to 160 C as a function of the
viscosity-average molecular weight: (A) 59; (B) 215;
(C) 580 kg mor 1 [reproduced with permission from
Onogi etal. (1970)].
stress. The molecular weight at which this
sudden increase in fracture stress occurs
is experimentally found to be correlated
with the value of Me (Gent and Thomas,
1972).
 12.2 Molecular Network Structure and Natural Draw Ratio
250
0.00 0.50 1.00 1.50
6 1
Mn (10 g mole )
Figure 12-3. Dependence of the fracture stress, <7t, of
poly(methylmethacrylate) (PMMA) upon the
number-average molar mass measured at -196 C
[reproduced with permission from Vincent (I960)].
Wu (1989, 1990) proposed a correlation
between the chain stiffness (characteristic
ratio C^) and the average molecular weight
between entanglement nodes, Me. Wu's
theoretical evaluation and interpretation of
the data, however, is highly speculative with
respect to the physical reality, especially the
assumption of a binary hooking type of
entanglement nodes; see also discussion in
Bastiaansen et al. (1990). Recently, Fetters
et al. (1994) proposed a more straightfor-
ward approach to a correlation between the
entanglement density and the molecular
structure of the polymer. They define a
'packing length' p
M (12-2)
P=
(R2)pNA
where M is the molecular weight of the poly-
mer, (R2) the root mean square end-to-end
distance of the polymer, p the density of the
polymer, and NA Avogadro's number. As
demonstrated in Fetters et al. (1994), a very
simple physical argument can be given for
the correlation between the entanglement
molecular weight [or the entanglement den-
sity, v e ;seeEq. (12-8)] and/? (the actual vol-
585
o.oo 0.25
Figure 12-4. Entanglement density versus 'packing
volume' p~3 [reproduced from Fetters et al. (1994)].
ume occupied by the chain divided by its
mean square end-to-end distance)
vQocp~3 (12-3)
In Fig. 12-4 this correlation is illustrated
for a large set of polymeric data, as taken
from Fetters et al. (1994).
It has been pointed ount that the molecu-
lar conformation of amorphous glassy poly-
mers can be characterized by a certain aver-
age molecular weight between the network
nodes. These network nodes can be both
physical and chemical in nature. Follow-
ing the principles of network drawing, as
discussed in Sec. 12-1, a theoretical maxi-
mum draw ratio of a single strand in the
polymer network, assuming no chain slip-
page or breakage takes place, can be given
by (Kramer and Berger, 1990; Kramer,
1983)
^max=Jr (12-4)
where /e is the chain contour length and d
the root mean square end-to-end distance
between junction points in the network (i.e.,
the mesh size). According to Kramer
586 12 Deformation and Toughness of Polymers
(Kramer and Berger, 1990; Kramer, 1983),
the value of /e is given by
_/ Q M e
e (12-5)
M,
where l0 and Mo are the average projected
length of a chain segment along the chain
and its molecular weight, respectively. The
value of d is related to the polymer network
structure via (Kramer and Berger, 1990;
Kramer, 1983)
d=k(MQ) 1/2
(12-6)
where k is a constant that can be determined
from neutron scattering measurements of
the radius of gyration of molecular coils in
the glass. Combining Eqs. (12-4), (12-5),
and (12-6) results in
fl/2
(12-7)
0 A craze can be described as a microcrack
which can be related to the network density
via
v e = ^ (12-8)
resulting in
k (12-9)
kMovl 1/2
in which p is the density and NA is
Avogadro's number. Equation (12-7) is a
more detailed version of Eq. (12-1).
Typical values of the theoretical draw
ratio of amorphous glassy polymers vary
from 4.8 for poly(tezt-butylstyrene) (Don-
ald and Kramer, 1982 a), i.e., an elongation
to break of 380%, to less than 1.2 (Henkee
and Kramer, 1984), i.e., an elongation to
break of 20% for a densely crosslinked ther-
mosetting polymer. For the latter type of
amorphous polymers Eqs. (12-7) and (12-9)
are still applicable if Me and ve are replaced
by Mc (i.e., the molecular weight between
crosslinks) and vc (i.e., the crosslink den-
sity), respectively.
12.3 Deformation Mechanisms
The experimentally derived (macroscop-
ic) elongation to break is often much lower
than the theoretical value, Amax. The macro-
scopic elongation to break of polystyrene
for instance is only 1-3% compared to the
300% expected from its network (density
(see Sec. 12.1). The reason for this contra-
diction is related to the fact that deforma-
tion only occurs in localized areas in the
sample, in the so-called deformation areas.
Two types of localized deformation mecha-
nisms are known for the group of amorphous
glassy polymers: crazing and shear yielding
(see Sec. 12.3.3 for a classification).
12.3.1 Crazing
bridged by polymer fibrils. Within the craze
structure many microvoids can be found.
These microvoids develop in a plane per-
pendicular to the maximum principal stress.
In contrast to a true crack, crazes are load
bearing due to the presence of bridging
fibrils. The thickness of these fibrils strong-
ly depends on the type of polymer, e.g., air-
grown crazes in polystyrene (PS) have typ-
ical fibril diameters of 5-20 nm (Lauter-
wasser and Kramer, 1979). In Fig. 12-5 a
transmission electron micrograph of a craze
structure in a styrene-acrylonitrile copol-
ymer is shown.
The craze structure consists of numerous
fibrils running across from one craze inter-
face to the other. These main fibrils are inter-
connected by somewhat thinner, so-called
cross-tie fibrils (Miller et al., 1991). Since
crazing involves the formation of micro-
voids, it is always accompanied by an
increase in volume and is favored by a large
dilatational component of the stress tensor
(Kinloch and Young, 1985). This latter con-
dition can often be found ahead of a crack

Figure 12-5. Transmission electron micrograph of a
craze in styrene-acrylonitrile copolymer [reproduced
with permission from Bos (1989)].
tip or in the vicinity of dust or other foreign
particles, sharp edges, and other types of
inhomogeneities. Several types of crazes are
reported in the literature with varying
coarseness of the microfibrillar structure,
as reviewed extensively by Michler
(1990a-c). In principle, the size of the
crazes is not limited since the growth of a
craze occurs via drawing unfibrillated
polymeric material from the bulk into the
craze structure (Kramer and Berger, 1990).
Therefore the classification of crazes by
length or thickness as proposed by Michler
(1990 a - c) seems to be wrong in retrospect.
The maximum thickness of a craze is limit-
ed only in front of a crack tip due to the pres-
ence of cross-tie fibrils, as explained by
Brown (1991).
Recently, several studies have been
reported in the literature on the prediction
of the macroscopic fracture toughness GTc
from a molecular point of view where local-
ized deformation is considered (Brown,
1991; DeGennes, 1991). Brown (1991) cal-
culated the fracture toughness of polymers
that tend to form crazes ahead of a crack tip.
He derived an analytical equation for the
value of GIc that scales with the square of
12.3 Deformation Mechanisms 587
the breaking force of the chain molecules
and the square of the density of entangled
strands at the crack-tip interface.
12.3.2 Shear Yielding
Shear yielding involves plastic deforma-
tion that can either be very localized or quite
homogeneous, and occurs without any vol-
ume change. Localized shear deformation
arises from instabilities during homogene-
ous yielding which are induced by geomet-
ric irregularities (Haward, 1973; Nadai,
1950; Vincent, 1960 a) (neck formation as a
consequence of slight variations in the
cross-sectional area) and/or the supposed
intrinsic strain softening character of the
polymeric material. Recently, new insights
were obtained concerning the supposed
intrinsic strain softening character of poly-
meric materials, and it was demonstrated
that necking is caused by a mechanical (and,
to a lesser extent, thermal) runaway of
(initially) small instabilities due to the
strong nonlinear strain rate dependence of
the yield stress (Govaert and Tervoort,
1993). Shear yielding occurs preferentially
in relatively densely entangled (or cross-
linked) polymers (see Sec. 12.3.3) and is
favored when the conditions that tend to
promote crazing are suppressed (e.g., the
application of hydrostatic pressure). Fig-
ure 12-6 shows an optical micrograph of a
polycarbonate sample viewed between
crossed polars and uniaxially deformed just
past the yield point at room temperature.
At an angle of approximately 45 C
(direction of maximum shear stress), sharp
shear bands are visible. Various types of
shear bands are listed in the literature termed
microshear bands or diffuse zones. Accord-
ing to Bowden (1970) the differences in the
shear band structure mainly arise from their
differences in growth speed.
588 12 Deformation and Toughness of Polymers
Figure 12-6. Microshear bands in a polycarbonate
sample that has been uniaxially deformed just past
yield at room temperature, viewed between crossed
polars (load direction: horizontal).
12.3.3 Crazing Versus Shear Yielding
Henkee and Kramer (1984) demonstrat-
ed a transition from crazing to shear yield-
ing in polystyrene (PS, a typical craze-
deforming polymer) at room temperature as
a result of electron beam irradiation of the
material. The electron beam irradiation
induces crosslinking (at very high irradia-
tion doses because PS is relatively inert to
electron beam irradiation) of the polysty-
rene resulting in an increased network den-
sity (i.e., the total of physical entanglements
and chemical crosslinks). A more detailed
physical explanation for this network den-
sity dependent transition in the deformation
mechanism, occurring at a network density
of 9xlO25 chains nT3, has been proposed by
Kramer and Berger (1990). They ascribed
this transition to the fact that an increasing
network density results in a higher surface
tension, which hampers the void formation
process of crazing.
Wu (1990) proposed that polymers that
tend to deform by crazing possess network
densities lower than 9xlO25 chains m~3 and
polymers that deform by shear yielding have
network densities above the value of 9x1025
chains m~3. This classification arises from
a comparison of the craze initiation stress
with the shear band initiation stress for a
large number of amorphous glassy poly-
mers. At a network density of approximate-
ly 9xlO25 chains m~3 the craze initiation
stress roughly equals the shear band initia-
tion stress; below this network density the
craze initiation stress is lower than the yield
stress and crazing prevails.
The experimental observations of a
crazing-shear yielding transition depending
on the entanglement density of the amor-
phous glass are also, at least qualitatively,
confirmed by calculations performed by
Termonia and Walsh (1989). They modeled
the deformation behavior and mechanical
properties of polymeric glasses by taking
into account the role of the interactive forc-
es between macromolecular chains as well
as chain slippage through entanglements.
The network structure can deform elastical-
ly (0-2% elongation) and plastically. Plas-
tic deformation occurs via stretching or slip-
page (disentanglement) of the entanglement
strands, depending on the strain rate and the
local stress state. Via a two-dimensional
Monte Carlo simulation, the minimum ener-
gy state is retained after each increment in
the strain. These calculations clearly dem-
onstrate a transition from a crazing to a
shearing mode of deformation with increas-
ing network density. This transition is visu-
alized if the network structure is observed
after a certain deformation. If crazing pre-
vails 'holes' can be observed in the molec-
ular network. These holes are either the
result of disentanglement, or are due to
chain breakage. At higher network densities
shear yielding is observed, as indicated by
the absence of holes in the network struc-
ture, and homogeneous deformation is
observed instead. It has to be noted that
these model calculations have to be inter-
preted only qualitatively, since the thickness
of the calculated fibrils differs consider-
ably from the experimentally determined
values.
 12.4 Natural Draw Ratio Versus Local Strain 589

The applicability of the network density

classification proposed for the transition
from crazing to shear deformation accord-
ing to Wu (1990) is very limited since the
transition is highly influenced by the testing
conditions applied. For instance, straining
of a typical shear-deforming polymer like
polycarbonate at elevated temperatures
(instead of room temperature) results in a
transition from shear yielding to crazing.
This is explained by Donald (1985) in terms
of disentanglement crazing; high tempera-
tures enhance the disentanglement process
during deformation, resulting in a less
densely entangled network structure which
tends to deform by crazing.

12.4 Natural Draw Ratio Versus

Local Strain
Kramer and co-workers compared the
theoretical extension ratio of the molecular
network of a large group of amorphous poly-
mers [Amax; see Eq. (12-7) or (12-9)] with
the local extension ratio in a craze or shear
deformation zone (Donald and Kramer,
1982 a, b, c; Henkee and Kramer, 1984)
using the technique introduced by Lauter-
wasser and Kramer (1979). The extension Figure 12-7. (a) Craze fibril extension ratio Acraze
ratios in a craze fibril or within a shear de- versus the maximum extension ratio of an ideal entan-
formation zone can be determined from glement network, Amax (assuming no chain slippage
or scission); and (b) extension ratio in a deformation
optical densitometry of transmission elec-
zone, ADZ, versus Amax [reproduced with permission
tron micrographs of these structures. Fig- from Donald and Kramer (1982 a, b, c) and Henkee
ure 12-7 summarizes some of the results of and Kramer (1984)].
their studies: the craze fibril extension ratio,
Acraze, and the extension ratio in a shear def-
ormation zone, ADZ, are plotted versus the Independent of the type of network struc-
natural draw ratio (which is a polymer net- ture (entanglements or crosslinks), a clear
work parameter). In Figs. 12-7 a and 12-7b correlation can be observed between the
the data presented were obtained from value of Amax, on one hand, and the value of
measurements on entangled thermoplastic Acraze and ADZ, on the other. For the shear-
polymers. Similar results are published by deforming polymers, roughly 60% of the
Henkee and Kramer (1984) on chemically theoretical draw ratio is measured inside a
crosslinked polymers. deformation zone. In the case of craze-
590 12 Deformation and Toughness of Polymers
deforming polymers a one-to-one correla-
tion seems plausible, however, additional
experiments revealed a large destruction of
the original entanglement network during
craze formation (Henkee and Kramer,
1986). Hence the one-to-one correlation is
somewhat misleading for the crazing case,
since the actual (local) network structure
possessed a higher value of Amax after craze
formation (Amax after). Consequently, rough-
ly the same discrepancy between the natu-
ral draw ratio (after craze formation) and
the value of Acraze (/Lcraze/AmaX5 after = 0.6), as
found between the natural draw ratio and
ADZ, results.
12.5 Toughness Improvement
in Practice
To improve the macroscopic toughness of
amorphous glassy polymers, several
approaches have been proposed in the liter-
ature. In principle, two possible methods
exist to increase the macroscopic toughness:
(i) the addition of a plasticizer and (ii) the
initiation of multiple deformation mecha-
nisms in a large volume of the material,
induced by the presence of a low modulus
dispersed phase. Both methods will be
reviewed briefly.
12.5.1 Plasticization
The addition of a plasticizer is a relative-
ly simple technique to improve the macro-
scopic toughness of an amorphous polymer
(Kinloch and Young, 1985). The plasticizer
lowers the yield stress of the polymer and
can, consequently, increase the elongation
at break of the polymer. The disadvantage
of this approach is the (undesired) decrease
in the modulus, glass transition temperature,
and yield strength of the polymeric materi-
al. Recently, the concept of controlled local
plasticization was introduced by Argon and
co-workers (Gebizlioglu et al., 1990; Argon
et al., 1990). This method is based on the
principle of increased solubility under the
influence of high, negative pressures. Such
high negative pressures are supposed to
occur for instance in the active zone of a
widening craze. Hence only local plasticiza-
tion occurs in the region of the deformation
mechanism. Therefore the disadvantages of
the addition of a 'traditional' plasticizer
would be minimized to only a minor
decrease of the Young's modulus and ten-
sile strength. Recently, however, it has been
shown for the model system polysty-
rene/polyisobutylene (PS/PIB) (Janssen,
1993), where the solubility of the PIB can
be increased in a controlled manner (by a
decrease of the molecular weight as a con-
sequence of electron beam irradiation), that
a substantial change in solubility did not
result in any change of the mechanical prop-
erties of the blend. Therefore the applicabil-
ity and practical relevance of the mechanism
proposed by Argon or the impact toughen-
ing of polymeric systems must be ques-
tioned seriously.
12.5.2 Rubber Modification
The most frequently applied method to
improve the toughness of polymeric
systems is in general the addition of dis-
persed rubbery particles. The function of
these particles is to generate numerous
stress concentrations throughout the poly-
meric matrix (Bucknall, 1977; Coumans
et al., 1980). As a result, multiple deforma-
tion mechanisms are initiated in the matrix
and multiple crazing or multiple shear de-
formation is induced. The rubbery phase
only marginally contributes to the tough-
ness of the overall composite (Newman and
Strella, 1965).
 12.5 Toughness Improvement in Practice
12.5.2.1 Multiple Crazing
The influence of various parameters (e.g.,
the rubber phase volume fraction, rubber
particle size, and degree of adhesion
between the rubbery particles and the
matrix) have been given a lot of considera-
tion since the introduction of the first com-
mercial type of high impact polystyrene
(HIPS) in 1948 (Bucknall, 1977, 1990;
Hobbs, 1986; Keskkula et al., 1986; Cigna
etal., 1992). The elongation to break of
polystyrene can be increased by optimizing
the variables mentioned above, up to a value
of about 30%. Even if the testing conditions
become more severe (i.e., high strain rates,
notched impact testing at low temperatures),
the toughening effect of the dispersed rub-
bery particles remains (Bucknall, 1977,
1990).
Although an enormous amount of papers
can be found in the literature dealing with
the rubber-toughening of craze-deforming
polymers, only a few systematic studies are
reported on the influence of the rubber phase
volume fraction and particle size on the
rubber-toughening efficiency (Cigna et al.,
1976, 1986, 1992; Bucknall etal., 1986,
1987). Bucknall etal. (1986) studied the
influence of the rubber phase volume frac-
tion on the notched Charpy impact strength
of polystyrene by diluting a standard HIPS
sample with pure PS. A sharp decrease in
the impact strength was observed below a
certain rubber phase volume fraction, which
was explained in terms of an altered local
stress state of the matrix phase. The same
authors investigated the influence of parti-
cle size on the notched Charpy impact
strength of rubber-modified polystyrene,
and the toughening efficiency of the rubbery
particles was found to decrease below a
diameter of 1 |im (Bucknall et al., 1987).
The explanation for this observation is given
by Donald and Kramer (1982 d, e) in a sep-
591
arate paper, where the detailed mechanisms
of craze initiation, growth, and breakdown
around rubbery particles in thin films of
HIPS and acrylonitrile-butadiene-styrene
copolymer (ABS) were studied using trans-
mission electron microscopy. They demon-
strated that crazes are rarely initiated in
polystyrene by particles having a size below
1 |im, and it was suggested that the stress
concentration induced by the rubbery parti-
cles must act over a certain critical distance
in order to initiate crazes, since the distance
over which the stress concentration of a rub-
bery particle acts is directly proportional to
its particle size. This critical size, below
which the toughening efficiency decreases,
depends on the type of polymeric matrix, as
clearly reported in review papers by Wu
(1990). The observation of a minimum
particle size to initiate crazes automatical-
ly explains the occurrence of an optimum
particle size for a given concentration
of rubbery particles, since this optimum
particle size is equal to the minimum par-
ticle size below which crazes cannot be
generated. So-called optimum particle
sizes are reported in the literature varing
from 2.5 |im for polystyrene down to
0.25 |Lim for poly(methylmethacrylate) (Wu,
1990).
The influence of adhesion between the
rubbery phase and the matrix on the Izod
impact strength of rubber-toughened poly-
styrene has been reported by Van Gisber-
gen and co-workers (Van Gisbergen, 1991;
Van Gisbergen etal., 1990, 1991). It was
shown that the impact properties of poly-
styrene/ethylene-propylene-diene mono-
mer (EPDM) blends can be improved sig-
nificantly with electron beam irradiation
when a suitable compatibilizer is used (in
their experiments a styrene-butadiene
diblock copolymer). Differences in mor-
phology and crosslinking of the dispersed
phase could be eliminated as explanations
592 12 Deformation and Toughness of Polymers
for the observed phenomenon due to the
experimental setup used. Hence a change in
the interfacial adhesion is the most plausible
explanation.
Only recently, the precise function of the
dispersed elastomer present in craze-
deforming matrices was clarified by Bubeck
et al. (1991), who performed real-time,
small-angle X-ray scattering measurements
on rubber-modified, craze-deforming ther-
moplastics. These experiments unambigu-
ously demonstrate the occurrence of two
distinct events during the loading of rubber-
modified, craze-deforming thermoplastics.
The first step of plastic deformation is the
internal cavitation of the rubbery particles
leading to microvoids within the dispersed
spheres. Subsequently, crazes are initiated
at the equator of the rubbery particles, while
the microvoids within the rubbery phase
are prevented from coalescence to form
larger voids (which could lead to prema-
ture crack initiation) as a result of a moder-
ate degree of crosslinking of the rubbery
phase.
12.5.2.2 Multiple Shear Deformation
The influence of dispersed rubbery parti-
cles on the macroscopic toughness of shear-
deforming thermoplastic polymers has been
studied extensively by Wu (1985, 1988) and
Borggreve (1988) for the semi-crystalline
nylon-6/EPDM rubber model system. For
shear-deforming polymers it has been dem-
onstrated that, independent of the rubber
phase volume fraction and particle size, the
maximum degree of toughness can be
obtained on a macroscopic level if the poly-
meric material is made locally thin below
the critical matrix ligament thickness (DIc).
The value of the critical matrix ligament
thickness is related to the testing tempera-
ture (Borggreve, 1988). In Fig. 12-8 the
1.00
0.00
-50 -30 -10 10 30 50 70 90
Temperature (C)
Figure 12-8. Critical matrix ligament thickness Dlc
versus temperature for nylon-6/rubber blends [repro-
duced with permission from Borggreve (1988)].
value of Dlc is shown as a function of the
testing temperature for nylon-6.
Above a temperature of 50 C, a steep
increase in the critical thickness is observed
due to temperature approaching the glass
transition temperature of nylon-6 (60 C).
Below this temperature the value of Dlc
increases only moderately with increasing
temperature, independent of the glass tran-
sition temperature of the nylon-6 matrix or
the dispersed EPDM rubber phase (Borg-
greve, 1988). The physical explanation of
this critical thickness, below which the
polymer reveals a maximum degree of duc-
tility, is not fully understood. Several expla-
nations have been proposed by Margolina
and Wu (1988) and Sjoerdsma (1989) based
on the percolation of yielding ligaments,
however, no convincing experimental ver-
ification was given for any of the explana-
tions proposed.
An important feature of these rubber-
modified, shear-deforming thermoplastic
polymers has been demonstrated by Borg-
greve et al. (1989 a, b), who have shown a
pronounced influence of the mechanical
properties of the dispersed elastomeric
 12.6 The Concept of a Critical Thickness
phase on the brittle-to-tough transition of
nylon-6 blends. Chou et al. (1988 a, b) have
demonstrated for the system of polypropy-
lene (PP) blended with ethylene-propylene
rubber (EPR, the dispersed phase) that a
brittle-to-ductile transition can be realized
not only by a change in the testing temper-
ature, but also by a change in the strain
rate.
Thermosetting polymers also suffer from
brittle fracture, especially under relatively
severe testing conditions. Due to the high
network density (i.e., crosslink density),
thermosetting polymers deform by shear
deformation, although very recently, Sue
and co-workers reported the observation of
crazes in a moderately crosslinked 1,2-
dihydrobenzocyclobutene-maleimide resin
(Sue et al., 1995). The high network density
of these materials limits their intrinsic
toughness through their low natural draw
ratio [see Eq. (12-9)]. Therefore rubber
modification in these systems can only
result in a marginal toughness improve-
ment. An excellent review on toughening
mechanisms occurring in (rubber-modified)
epoxides has been published by Garg and
Mai (1988).
Several systematic studies on the influ-
ence of crosslink density on the toughen-
ability of chemically crosslinked polymers
are reported in the literature, where the
influence of the dispersed toughening agent
has been studied as well (Yee and Pearson,
1986; Pearson and Yee, 1986, 1989) Com-
pared to thermoplastic polymeric systems,
the toughening concepts do not differ much
for thermosetting polymers with respect
to the addition of a dispersed phase of
lower modulus. However, alternative tough-
ening concepts are also applied, including
crack-tip bifurcation and crack-tip bridg-
ing (Pearson and Yee, 1990). These alterna-
tive mechanisms result in only a marginal
toughness improvement.
593
12.6 The Concept
of a Critical Thickness
The original experiments performed by
Kramer and Berger in the 1980s (Kramer
and Berger, 1990) resulted in considerable
progress in the understanding of toughness
from a molecular point of view. However,
comparison of the local strain level within
a deformation area with the theoretical
strain to break on stretching the molecular
network structure to its full extension was,
up to now, of no relevance to the macroscop-
ic toughness of polymeric systems. Illustra-
tive in this context is the paradox between
the theoretical draw ratio of the entangle-
ment network of polystyrene (300%) and
the macroscopic elongation to break of only
3%, i.e., the two orders of magnitude differ-
ence. On a microscopic scale, the theoreti-
cal draw ratio can be approached (inside
crazes or shear bands), therefore, it can be
expected that a transition from brittle to duc-
tile deformation occurs upon changing the
sample dimensions (from 'macroscopic' to
'microscopic'). Some early hints of these
effects came from experiments that showed
that the craze structure in thin polystyrene
films changed to a perforated sheet structure
much closer to that of a deformation zone
below film thicknesses of 150 nm (Donald
etal., 1981).
Experiments performed by Wu( 1985,1988)
and Borggreve (1988) on the nylon-6/rub-
ber system clearly revealed an influence of
the (local) dimension of the polymeric mate-
rial (ligament thickness between rubbery
particles) on the brittle-to-ductile transition
of the blends. The physical explanation of
this transition as well as the more general
validity of this dimension-induced brittle-
to-tough transition was not given by the
authors.
The critical dimension below which
amorphous glassy polymers macroscopical-
594 12 Deformation and Toughness of Polymers

ly deform up to the theoretical strain to break adhering rubbery particles, i.e., the equiva-
has been studied thoroughly for amorphous lent of holes.
glassy polymers by van der Sanden and co-
workers (van der Sanden et al., 1993 a, b, c;
1994 a, b; van der Sanden and Meijer, 12.7.1 Multilayered Tapes
1993 a, b; 1994 a, b). This concept of a crit-
PS and PE were coextruded using a Mul-
ical thickness will be discussed extensively
tiflux static mixer (Sluijters, 1965; Schilo
in Sees. 12.7 and 12.8 with an emphasis on
and Ostertag, 1972) into thin laminated
polymer processing.
tapes possessing a total thickness of approx.
For thermoplastic polymers with different
0.3 mm, a width of 10 mm, and infinite
entanglement densities [polystyrene; poly-
length, and containing a varying number of
styrene-poly(2,6-dimethyl-1,4-phenylene
layers (from 8 up to 1024). PS and PE were
ether) (PS-PPE) blends], the local dimen-
used in five different proportions, i.e.,
sions are decreased in one (films) or two
PS/PE: 100/0, 75/25, 50/50, 25/75, and
directions (ligaments between nonadhering
0/100. The principle of the static mixer is
rubbery particles) by control of the micro-
outlined in Fig. 12-9. Starting with parallel
structure. Below a critical (local) size, the
layers of both polymers (stage A, Fig.
sample macroscopically demonstrates the
12-9), the layers are split up and compressed
maximum degree of ductility, comparable
vertically in opposite directions (stage B,
with the theoretical strain to break. The
Fig. 12-9). Subsequently, an extension in
occurrence, and network density depen-
the horizontal direction results in double the
dence, of the critical dimension is modeled
number of layers (stage C, Fig. 12-9). If the
in terms of an energy based criterion (see
number of elements is increased, so too is
Sec. 12.8).

12.7 The Critical Thickness

of Polystyrene
In this section the concept of a critical
thickness below which brittle samples
become ductile will be outlined taking data
from van der Sanden and co-workers (van
er Sanden, et al., 1993 a, b, c, 1994 a, b; van
der Sanden and Meijer, 1993 a, b, 1994 a, b),
as published in the early 1990s. PS is taken
as the model system. Tapes consisting of
alternating layers of polystyrene and poly-
ethylene (PE) were prepared in order to
investigate the influence of the PS layer
thickness on the tensile deformation pro-
cess. The concept of a minimum thickness
Figure 12-9. Principle of the AKZO Multiflux static
is also transferred to a standard (3-mm mixer. One element is shown. In the text, 1 is referred
thick) PS system in which the critical thick- to as the vertical direction, 2 the horizontal direction,
ness is achieved locally by introducing non- and 3 the direction of flow.
 12.7 The Critical Thickness of Polystyrene
Figure 12-10. SEM micrographs of (a) a PS/PE
50/50 w/w tape with 3 mixing elements, (b) PS/PE
25/75 tapes with 6 mixing elements, and (c) 9 mixing
elements.
the total number of layers (to the power of
2). [For further experimental details the
reader is referred to van der Sanden et al.
(1993 a)].
Figure 12-10 a is an SEM (scanning elec-
tron microscope) micrograph of an alternat-
ing PS/PE 50/50 w/w tape (three mixing ele-
ments), possessing both PS and PE layers of
10-|Lim thickness. It is clear from this micro-
graph that the adhesion between the PS and
PE layers is poor, due to the fact that PE
crystallizes (causing shrinkage) during
595
cooling from the melt to room temperature.
Consequently, PE serves as a useful, mini-
mally adhesive layer for forming the thin,
stratified PS structures.
Figure 12-10 b represents the minimum
PS layer thickness attainable with this stat-
ic mixing equipment, i.e., 0.8 |um (PS/PE:
25/75 w/w; six mixing elements). Upon fur-
ther increasing the number of elements, the
tapes contain discontinuities due to rupture
of the layers (Fig. 12-10c: PS/PE: 25/75
w/w; nine mixing elements), probably, due
to flow instabilities caused by the large dif-
ferences in viscosity. For a matched
(PS/PMMA) system, the minimum achiev-
able thickness of still continuous layers
proved to be 40 nm (van der Sanden et al.,
1994 a).
12.7.2 Mechanical Properties
of Polystyrene (PS) Tapes
Figure 12-11 shows the stress-strain
curves of pure PS and PE tapes with a total
tape thickness of about 0.3 mm. Curve A
represents the typical stress-strain curve of
PS with a breaking stress of 40 MPa and a
strain at break of 1.5 %. PE, on the other hand
(Fig. 12-11, curve B), is a very ductile poly-
mer with a strain at break of about 225%
under the same testing conditions.
In Fig. 12-12, a stress-strain curve of a
multilayered tape (PS/PE 25/75 w/w, six
mixing elements) is shown (for dumbbell-
shaped samples pulled parallel to the direc-
tion of coextrusion). The sharp decrease in
the stress at 33% strain is the result of rup-
ture of the PS layers. After passing their
strong decrease in stress the measurement is
stopped, with the PE layers unbroken, as
indicated by the constant level of stress after
passing 33% strain. If we assume that the
stress-strain behavior of PE is not influ-
enced by a change in the absolute thickness
(Pan et al., 1990) we can (corresponding to
596 12 Deformation and Toughness of Polymers
50
30
B 225 %
Figure 12-11. Stress-strain curves of the reference
materials: (A) PS; (B) PE.
Figure 12-12. Stress-strain trace of a PS/PE 25/75
w/w multilayered tape (6 mixing elements; strain rate
0.25 mhT1).
the volume fraction of PE present in the total
composite) subtract the stress-strain curve
of PE from the stress-strain curve of the
multilayered composite. The stress-strain
trace of the thin PS component results. In
Fig. 12-13, these traces are shown for four
different tapes with different PS/PE compo-
sitions and numbers of layers.
10 20 30
Strain (
Figure 12-13. Stress-strain curves for pure PS tapes
with varying PS layer thicknesses: (A) 35 |um, (B)
4.5 um, (C) 1.5 pm, (D) 0.8 |im.
Curve A corresponds to a PS layer thick-
ness of 35 \im (PS/PE: 50/50 w/w) and
resembles the ordinary stress-strain behav-
ior of PS, as observed in Fig. 12-11, curve
A. If the layer thickness of PS is decreased
to 4.5 jam (PS/PE: 25/75 w/w), the maxi-
mum stress is raised to 70 MPa and the strain
at break is increased to a value of 5%
(Fig. 12-13, curve B). Further decreasing
the PS layer thickness results in a shift of
the strain at break to a value of more than
30% (Fig. 12-13, curve D, the thickness of
the PS layers is 0.8 |im; PS/PE: 25/75 w/w).
In Fig. 12-14 the strain at break of PS is plot-
ted as a function of the absolute PS layer
thickness, as obtained from the data for three
different PS/PE ratios.
As can be inferred from this figure, the
critical thickness for PS is below 1 |im for
the given testing conditions. However, due
to limitations in the minimum continuous
PS layer thickness that could be achieved,
the exact value of the critical PS layer thick-
ness cannot be determined. In fact, due to
the presence of some adhesion between the
alternating PS and PE layers, multiple
cracking is observed here. For the less crit-

50
40
r 30
2 20
10
10"7 106 10"5 10" 4
Thickness (m)
Figure 12-14. Strain at break of PS tapes as a func-
tion of PS layer thickness.
ical, more entangled system of PS-PPE
(40-60), the critical thickness shifts to
higher absolute values and the transitions
from brittle to multiple cracking and from
multiple crazing to shearing can be observed
[see van der Sanden et al. (1994 a) for fur-
ther details].
Kramer and co-workers (Donald et al.,
1981; Chan et al., 1981) also noticed a
change in the craze structure if the thickness
of a PS film (free surface, exposed to air)
was below 0.15 |Lim. Clearly, there is close
correspondence with the critical thickness
of PS reported here.
Another size effect in multilayered
structures has been observed by Ma et al.
(1990). Their explanation for the strong
increase in strain at break of multilayered
composites upon decreasing the layer thick-
ness, based on polycarbonate (PC) and
styrene-acrylonitrile copolymer (SAN),
was related to the micromechanics of these
multilayered structures. In the PC/SAN
12.7 The Critical Thickness of Polystyrene 597
system analyzed by Ma and co-workers a
considerable level of adhesion is present
between the two constituents of the compos-
ite, while in the case of the PS/PE system
the level of adhesion is negligible (Wu,
1982). Hence the size effects observed in the
nonadhesive PS/PE multilayered structures
are probably not induced by complex micro-
mechanics that strongly depend on the pre-
cise level of adhesion.
As in the (multiple) necking of tensile
bars (Ward, 1971), in this PS/PE multilay-
ered system, where adhesion is small, the
prerequisite of an increase in the drawabil-
ity below a certain minimum thickness is
more straightforward. The process of defor-
10 3
mation can only be sustained if the stress in
the oriented parts is below the breaking
stress, while the stress in the undeformed
connected matrix surpasses the yield stress.
This principle can be generally applied to
polymer systems that are characterized by
the fact that the initiation of deformation
always starts locally. By lowering the PS
layer thickness (<1 jiim), these conditions
are apparently approximated, resulting in a
continuation of the process of deformation.
12.7.3 Rubber-Modified Polystyrene
The principle of a critical thickness, as
approximated for thin layers of PS (<1 \im),
should also exist in a standard PS sample if
the local thickness inside the sample is
below the critical value. In order to test this
hypothesis, holes were introduced to create
multiple thin PS ligaments inside the mate-
rial. The holes were generated by the intro-
duction of rubbery particles, which should
not be attached to the PS matrix. For this
purpose, core-shell rubbers were used pos-
sessing a PMMA shell (type-I): the PMMA
does not adhere to the PS matrix (Wu, 1982)
and, as a consequence of thermal shrink-
age, the rubbery domains easily become
598 12 Deformation and Toughness of Polymers
detached from the PS matrix upon, or even
before, mechanical deformation. In Fig.
12-15 SEM micrographs of both types of
core-shell, rubber-modified PS samples are
shown, containing different weight frac-
tions of rubber (40, 50, and 60 wt.%). The
samples are (at liquid nitrogen temperature)
cut from injection-molded tensile bars par-
allel to the direction of extrusion. In all
cases, discrete rubbery particles are
observed (size: 0.1-0.3 |Ltm) without any
significant agglomeration.
In Fig. 12-16 the stress-strain curves of
PS containing various amounts of type-I
core-shell rubber are shown (40, 50, and
60 wt.%; strain rate 0.05 mm"1). Lower
weight fractions of rubber are omitted for
the sake of simplicity (these samples are all
brittle, possessing a strain at break not
exceeding 10%). Curve A corresponds to a
blend containing 40 wt.% core-shell rubber.
The strain to break is rather low taking the
high weight fraction of rubber into account.
Increasing the rubber weight fraction to
Figure 12-15. SEM micro-
graphs of core-shell,
rubber-modified PS: (a)
40 wt.% type I; (b) 50 wt.%
type-I; (c) 60 wt.% type-I;
(d) 60 wt.% type-II.
50 wt.% results in an increase in the strain
to break to 25%, comparable with the strain
to break of commercially available high
impact polystyrene containing a rubber
weight fraction of only about 25%, but with
a different microstructure. However, upon
adding 60 wt.% core-shell rubber a sharp
increase in the strain to break is observed,
clearly related to the critical ligament thick-
ness below which a sharp increase in duc-
tility is obtained.
Clearly, local deformation can be initiat-
ed at stress concentrations near defects
(holes) and more or less controlled by the
introduction of a second, low modulus
phase; however, deformation, i.e., stretch-
ing of the entanglement network, can only
be sustained if the sample as a whole fol-
lows this deformation process. If the aver-
age distance between the rubber particles is
calculated (Wu, 1988) (Dx) (due to the high
rubber volume fraction, a body-centered
cubic lattice is assumed), it can be stated that
the critical interparticle distance (Dlc) for PS
 12.7 The Critical Thickness of Polystyrene
50
40 -
~~-
30 - A
B
C 200 %
.
Vj D
Strain (%)
30
Figure 12-16. Stress-strain curves of type-I, core-
shell, rubber-modified PS [(A) 40 wt.%; (B) 50 wt.%;
(C) 60 wt.% rubber] and type-II core-shell, rubber-
modified PS [(D) 60 wt.% rubber].
is less than 0.05 |um. The PS modified with
50 wt.% rubber contains ligaments of a
thickness of about 0.06 |Lim, which is clear-
ly above the critical thickness, while the
60 wt.% rubber-modified sample contains
matrix ligaments of a thickness of about
0.04 (im, which is obviously just below the
critical ligament thickness.
To check the importance of the absence
of adhesion in obtaining locally thin PS lig-
aments that can easily be stretched to a mac-
roscopic strain of 200%, core-shell rubbers
having a polystyrene shell were also used
(type-II; 'perfect' adhesion to the PS
matrix). Even if 60 wt.% of the adhering
core-shell rubber is present in the PS matrix,
a strain at break of only about 6% is meas-
ured (Fig. 12-16, curve D).
To gain more insight into the type of de-
formation mechanism for blends containing
polystyrene and the nonadhering (type-I)
core-shell rubber, tensile tests were per-
formed with simultaneous volume measure-
ments. Dilatometry allows measurement of
the volume change (AV/Vo) of the specimen
during longitudinal straining. Crazing is
599
10
Longitudinal strain (%)
Figure 12-17. Volume-strain curves of type-I, core-
shell, rubber-modified PS: (A) 40 wt.%; (B) 50 wt.%;
(C) 60 wt.% rubber (strain rate: 0.05 min"1).
accompanied by an increase in volume (void
formation) of the specimen during longitu-
dinal elongation (Kinloch and Young,
1985). In the case of shearing, longitudinal
straining will not result in an increase in the
volume-strain. For rubber-modified mate-
rials it is not always clear whether a volume
increase during straining is the consequence
of dilatation of the rubbery particles or the
result of the crazing mechanism initiated at
the rubbery particles.
Figure 12-17 shows the results of some
dilatometric measurements for PS blends
containing 40 wt.% (curve A), 50 wt.%
(curve B), and 60 wt.% (curve C) type-I
core-shell rubber (the volume-strain curves
for the blends containing 10, 20, and
30 wt.% rubber are omitted for the sake of
simplicity).
For the blend containing 40 wt.% core-
shell rubber, the (AV7V0) curve increases
slightly in the region of elastic behavior
(0-1.5% longitudinal strain). At a longitu-
dinal strain of about 2.5% the slope of the
curve increases sharply. This may result
from either of two processes: (1) the core-
600 12 Deformation and Toughness of Polymers
shell rubber becomes more detached from
the PS matrix; or (2) the crazing mechanism
is operative in this material (Kinloch
and Young, 1985). The slope of the
volume-strain curve goes asymptomatical-
ly to unity, indicating an equilibrium
between the increase in volume-strain (void
content) and the increase in elongational
strain. If the rubber concentration is
increased to 50 wt.%, almost the same
behavior is observed for the volume-strain
curve, except that in this case the slope of
the curve is less than unity, after passing the
elastic region. This implies that the increase
in void content is lower than the increase in
longitudinal elongation. This can only be
explained by a contribution of shear defor-
mation to the total deformation behavior of
the sample (Kinloch and Young, 1985),
since it is known that the mechanism of
shear, deformation occurs without an
increase in the sample volume. Finally,
curve C clearly confirms this statement: in
this case the slope of the (AV/V0) curve
decreases to zero and remains at zero until
a maximum strain of 200% is reached, indi-
cating that under these conditions the sam-
ple deforms purely by shear deformation.
Hence a transition from crazing to shear de-
formation occurs if the interparticle distance
is decreased from 0.06 |im(50 wt.% rubber)
to 0.04 |Lim (60 wt.% rubber), which corre-
lates well with the sharp increase in the
strain to break shown in Fig. 12-16.
12.7.4 Local Thickness
It was shown that brittle polymers
become ductile below a critical thickness,
as demonstrated for isotropic tapes of poly-
styrene. The onset of a sharp increase in the
strain to break of polystyrene was found if
the thickness was reduced below 1 |Lim. The
exact value of the critical thickness could
not be determined using layered structures,
because the minimum continuous PS layer
thickness that could be achieved was
restricted to 0.8 |im. The true yield stress of
PS was found to be about 70 MPa.
For rubber-modified polystyrene, the
influence of the local ligament thickness
on the mechanical response was discussed,
and the exact value of the critical surface-
to-surface interparticle distance (i.e., liga-
ment thickness) was determined to be
0.05 |im. Below this critical value the mate-
rial demonstrates a remarkably ductile
behavior.
12.8 Critical Thickness
and Network Density
In Sec. 12-7 (van der Sanden et al.,
1993 a) it was shown that the macroscopic
deformation and toughness of amorphous
polymers, which are prone to catastrophic
strain localizations, can be controlled by
changing the microstructure. The concept of
a material-specific critical thickness, either
in the form of thin sheets in stratified struc-
tures (with a nonadhering polymer acting as
a spacer) or as ligaments separated by holes,
was verified for polystyrene (PS). For PS,
with ligaments of a (local) thickness of
0.05 \xm, the maximum macroscopic strain
at break was found to be 200%, about 60%
of the theoretical maximum strain at break
(320%). Kramer and co-workers (Kramer
and Berger, 1990; Donald and Kramer,
1982) observed the same deviation between
the (maximum) natural draw ratio (Amax) of
a shear-deforming polymer and the local
strain level inside a plane-stress deforma-
tion zone (ADZ). Their explanation for the
discrepancy between the expected and the
experimentally determined value is asso-
ciated with the rather naive character of the
model (Kramer and Berger, 1990; Donald
and Kramer, 1982), which is based on the
 12.8 Critical Thickness and Network Density
maximum extension of only a single entan-
glement strand.
In order to transfer the maximum strains
from the distinct localizations in crazes and
shear bands to the macroscopic level, the
stress in the deformed regions should not
surpass the breaking stress, while the stress
in the connected, undeformed material
should be higher than the yield stress. Thus
a dependence of the critical thickness on the
maximum extension ratio and thus on the
network or entanglement density is to be
expected. This aspect of the deformation
behavior of polymers will be discussed in
this section, combined with the influence of
the entanglement density on the final mac-
roscopic strain to break.
The system polystyrene-poly(2,6-
dimethyl-l,4-phenylene ether) (PS-PPE)
was chosen as a model system (van der San-
den, 1993 b), because for this miscible pair
of amorphous polymers (Fried et al., 1982;
MacKnight et al., 1978) the entanglement
density can be varied by adjusting the rela-
tive volume fractions of both constituents
(Prest and Porter, 1972). The results for mul-
tilayered tapes of PS-PPE/PE [thin films
of PS-PPE alternating with polyethylene
(PE)] as well as for nonadhering core-shell,
rubber-modified materials (thin matrix lig-
aments) will be discussed [for a detailed
analysis of multilayered PS-PPE/PE tapes
the reader is referred to van der Sanden et al.
(1994 a)]. The competition between crazing
and shear deformation was studied via dila-
tometry and, finally, a simple model has
been proposed to explain the relationship
between the critical thickness and the entan-
glement density.
12.8.1 Entanglement Density
PS and PPE were compounded in various
weight fractions (PS-PPE 80-20, 60-40,
40-60, and 20-80) in order to obtain
601
Table 12-1. Glass transition temperatures for neat
PS-PPE blends.
Blend composition Glass transition temperature
80-20 105
60-40 123
40-60 144
20-80 174
blends with various entanglement densities.
Table 12-1 shows the glass transition tem-
perature (Tg) values of PS-PPE blends after
extrusion and injection molding, as revealed
by DSC (differential scanning calorimetry).
For all blend compositions only a single Tg
value is observed, clearly confirming the
miscibility of PS and PPE on a molecular
scale (Fried et al., 1982; MacKnight et al.,
1978).
The storage shear modulus (GO of neat
PS-PPE blends was determined in the melt
as a function of the angular frequency (&))
(10~ 2 -10 2 rad s"1) for at least five different
temperatures over a range of 50 C (for fur-
ther experimental details the reader is
referred to van der Sanden et al. (1993 b).
Shifting of the G versus co curves to a re-
ference temperature of approximately 40 C
above the glass transition temperature
resulted in a master curve. The rubber pla-
teau modulus GN0 is equal to the storage
modulus G' at the frequency where tan 8 is
at its minimum in the plateau zone of the
master curve (Wu, 1987 a, b). Applying the
classical concept of rubber elasticity theo-
ry, the molecular weight between entangle-
ment nodes, Me, can be calculated (Ferry,
1980)as
M^pRTI G NO (12-10)
where p is the density, R the gas constant,
and T the reference temperature.
The master curves of the PS-PPE 100 - 0,
80-20, and 60-40 blends obtained from
602 12 Deformation and Toughness of Polymers
10 6
5
CD 10
y.yy -
10 4
A: PS-PPE 100-0
B: PS-PPE 80-20
C: PS-PPE 60-40
10 3
10 10" 2 101 10 10 1 10 2
Reduced angular frequency (rad s 1 )
Figure 12-18. Master curves of PS-PPE blends [(A)
100-0, (B) 80-20, and (C) 60-40] as obtained from
dynamic mechanical thermal analysis (the reference
temperatures are respectively 130, 145, and 160 C).
dynamic mechanical thermal analysis are
shown in Fig. 12-18. The master curves for
the PS-PPE 40-60 and 20-80 blends are
omitted because these samples showed void
formation during measurement at the
required high temperatures, indicating ther-
mal degradation of the samples. The tem-
peratures to which the master curves are
shifted (7g + 40 C) are respectively 130,
145, and 160 Cforthe PS-PPE 1 0 0 - 0 , 8 0 -
20, and 60-40 blends.
It is clear from Fig. 12-18 that an increase
of the PPE content in the PS-PPE blends
results in a shift of the G' curve to higher
values. The rubber plateau modulus is deter-
mined at the minimim of tan 8 in the plateau
region and is used to calculate the molecu-
lar weight between entanglement nodes
using Eq. (12-10). The entanglement den-
sity (ve) can be calculated using (Kramer
andBerger, 1990)
v
e=~~ (12-11)
where NA is Avogadro's number.
In Fig. 12-19 the value of the entangle-
ment density is plotted versus the PS-PPE
10 3 0 20 40
PPE concentration (wt%)
Figure 12-19. Entanglement density versus PPE
content in PS-PPE blends. The solid curve is accord-
ing to Prest and Porter (1972).
composition (filled squares). Prest and Port-
er (1972) have determined the entanglement
density for several PS-PPE blends as well.
They experimentally derived an equation to
describe the entanglement molecular weight
as a function of the blend composition
(12-12)
where % is the weight fraction of PPE in
the blend and Me (PS) is the entangle-
ment molecular weight of polystyrene
(Onogi et al., 1970), Me(PS)= 19.1 kg
mol"1. Although Prest and Porter derived
this equation for a limited range of blend
compositions (0 < % < 0.4), it is assumed to
be valid up to ^=0.8.
Values of ve for the various PS-PPE com-
positions are calculated by combining
Eqs. (12-11) and (12-12). The results of
these calculations are also shown in Fig.
12-19 (solid curve). As can be inferred from
this figure, the entanglement density as
obtained from our rheological measure-
ments corresponds well with the values
obtained from the data of Prest and Porter.
The entanglement density varies linearly
 12.8 Critical Thickness and Network Density 603

between the values of pure PS (3.2xlO25

chains m"3) and of pure PPE (13.2xlO25
chains m ).

12.8.2 Multilayered Polystyrene-

Poly(2,6-Dimethyl-1,4-Phenylene Ether)/
Polyethylene (PS-PPE/PE) Tapes
Multilayered PS-PPE/PE samples were
prepared using a Multiflux static mixer
(Sluijters, 1965; Schilo and Ostertag, 1972).
The principle of this mixer was described in
Sec. 12.7.1; however, in this study an
improved version of the previously intro-
duced Multiflux mixer was used. Thin lam-
inated tapes consisting of alternating layers
of PS-PPE and PE were prepared with a var-
ying number of layers: from 128 (6 mixing
elements) up to 4096 (11 mixing elements).
PS-PPE and PE were applied in three dif-
ferent proportions: 75/25, 50/50, and 25/75
w/w.
In Fig. 12-20 SEM micrographs are
shown of various microtomed multilayered
PS-PPE/PE tapes. The continuity of the
layers is clear for Figs. 12-20 a and 12-20c
and only a small variation in the layer thick-
ness can be observed. For the PS-PPE/PE
25/75 w/w l tape (PS-PPE 80-20; 1 mixing Figure 12-20. SEM micrographs of multilayered
elements, Fig. 12-20b), however, the layer PS-PPE/PE tapes, (a) PS-PPE/PE 75/25 (PS-PPE
continuity is clearly absent. Obviously, the 80-20), 6 mixing elements, (b) PS-PPE/PE 25/75
PS-PPE composition (read: viscosity ratio (PS-PPE 80-20), 11 mixing elements, and (c)
PS-PPE/PE 25/75 (PS-PPE 60-40), 11 mixing ele-
of PS-PPE/PE) has a large influence on the ments.
maximum number of mixing elements pos-
sible to use in the Multiflux mixer before
layer discontinuity occurs (compare
Figs. 12-20b and 12-20c). (For pure PS, static mixer did not exceed 6; see Sec.
tapes consisting of continuous layers could 12.7.1).
only be obtained if the number of mixing For an extended discussion of the defor-
elements in the previously used Multiflux mation behavior and mechanical properties
of PS-PPE/PE tapes, the reader is referred
to van der Sanden et al. (1994 a). Here, only
1
The blend composition is indicated with a two num- a few results for the multilayered systems
ber code: 'weight fraction PS present in the matrix' - will be presented in order to compare these
'weight fraction PPE present in the matrix'. with data obtained from core-shell, rubber-
604 12 Deformation and Toughness of Polymers
uu
75
50
PS-PPE 60-40 \
25
10" 2
10" 1
PS-PPE Layer thickness (|jm)
Figure 12-21. Strain at break of PS-PPE/PE tapes as
a function of PS-PPE layer thickness (strain rate
0.25 min"1).
modified PS-PPE blends, in Fig. 12-21 the
strain the break of stratified tapes is plotted
versus the PS-PPE layer thickness for
PS-PPE 60-40 and 40-60 blends.
As can be inferred from Fig. 12-21
(PS-PPE 60-40), the strain to break
increases with decreasing layer thickness.
The experimentally achievable maximum
strain at break (about 70%) is observed for
the thinnest PS-PPE layers (PS-PPE/PE
25/75, 11 mixing elements). A further
decrease in the layer thickness, by increas-
ing the number of mixing elements, results
in a discontinuous layer structure.
For PS-PPE 40-60 (Fig. 12-21), the
thickness below which an increase in the
strain at break is observed is located at
a higher level (-0.25 |im) compared to
PS-PPE 60-40 (-0.06 |nm). Thus a pro-
nounced influence of the entanglement den-
sity is found. For the PS-PPE 40 - 60 blend,
the maximum level of strain at break attain-
able in the ductile region can be estimated
as 70%.
In contrast to pure PS (see Sec. 12.7),
which only showed the onset of an increase
in the strain at break with stratified struc-
tures, the PS-PPE 40-60 blend seems to
+ PS-PPE/PE 25/75
reach its maximum macroscopic strain, and
A PS-PPE/PE 50/50
thus the true critical thickness is found. It is
O PS-PPE/PE 75/25
therefore even more interesting to compare
these data with the more practical 'holey'
structures obtained by adding nonadhering
OL PS-PPE 40-60 core-shell rubbers.
\
12.8.3 Rubber-Modified PS-PPE Blends
Strain-to-break data obtained from slow
10 speed (0.05 min"1) tensile tests of various
rubber-modified PS-PPE blends are shown
in Fig. 12-22. The data for PS (Fig. 12-22,
curve A) are taken as a reference (see
Sec. 12.7.3). If 20 wt.% PPE is added to PS,
the strain to break as a function of the rub-
ber concentration (Fig. 12-22, curve B)
shows, analogous to PS, a steep increase
with increasing rubber weight fraction.
However, in this case the transition occurs
at a lower rubber concentration (50 wt.%),
i.e., a higher ligament thickness compared
to PS. The maximum value of the strain to
break in the 'tough region' is about 100%
and considerably lower than the value for
250
200
150
100
Rubber concentration (wt%)
Figure 12-22. Strain at break of rubber-modified
PS-PPE blends versus rubber concentration with the
matrix composition as the parameter (PS-PPE): (A)
100-0, (B) 80-20, (C) 60-40, (D) 40-60, and (E)
20-80 (strain rate 0.05 min"1).
 12.8 Critical Thickness and Network Density
core-shell, rubber-modified blends having a
pure PS matrix (strain at break of approxi-
mately 200%).
Curves C and D in Fig. 12-22 clearly con-
firm this trend. With an increasing PPE con-
tent in the matrix, two phenomena are
observed: (i) the critical ligament thickness
is positioned at a lower rubber concentra-
tion and (ii) the maxium value of the strain
to break in the ductile region decreases. (For
curves C and D the levels of the strain to
break are equal in the tough region).
Notice that the strain to break in the duc-
tile region of the core-shell, rubber-modified
PS-PPE 60 - 40 and 40 - 60 blends coincides
with the maximum strain to break observed
for the corresponding PS-PPE/PE tapes. For
the PS-PPE 20-80 blend, all the samples
show a macroscopic strain to break of about
65%, independent of the rubber weight frac-
tion (Fig. 12-22, curve E). Clearly, no brittle-
to-ductile transition is found in the given test
range. As shown in van der Sanden and Meij-
er (1994 a), PS-PPE 20 - 80 blends can dem-
onstrate a brittle-to-ductile transition under
more extreme testing conditions (tensile
speed: 1 m s"1; notched).
12.8.4 Theoretical Considerations
12.8.4.1 Macroscopic Strain
The maximum extension ratio of an
entanglement network can be calculated
using the classical theory of rubber elastic-
ity (Kramer, 1983).InFig. 12-23 the experi-
mentally determined, maximum macro-
scopic strain to break (Amacr) of the various
multilayered and rubber-modified PS-PPE
blends is shown as a function of the theoret-
ical maximum extension ratio (Amax) of the
entanglement network of the PS-PPE
phase.
As can be inferred from Fig. 12-23, the
experimentally determined values correlate
605
Figure 12-23. Maximum macroscopic draw ratio
(Amax) versus the natural draw ratio (Amax) for strati-
fied and core-shell, rubber-modified PS-PPE blends.
well with the results of Kramer and co-
workers on strain levels determined locally
inside a deformation zone (Kramer and
Berger, 1990; Donald and Kramer, 1982f)
(ADZ = 0.6 Amax). The reason for the discrep-
ancy between the theoretical value, Amax,
and XDZ (or Amacr) must be related to the non-
ideal character of the entanglement network
and the assumption of taking one single
entanglement strand in order to estimate the
theoretical extension ratio of a three-
dimensional entanglement network, as
already discussed in the introduction of Sec.
12.8.
The macroscopic strain-to-break data of
Fig. 12-23 can be presented as a function of
the entanglement density (see Fig. 12-24) to
yield the overall picture of deformation and
toughness of amorphous polymers. The
open circles correspond to data obtained
from multilayered and rubber-modified
PS-PPE blends, and the filled circles corre-
spond to data obtained from a thermoset
epoxide system possessing varying cross-
link densities (van der Sanden and Meijer,
1993 a). This latter model system is beyond
the scope of this chapter, and therefore the
606 12 Deformation and Toughness of Polymers
25 50
25 3
Network density (x1 0 chains/m )
Figure 12-24. Draw ratio versus network density
(entanglement and/or crosslink density). For details,
see text.
reader is referred to van der Sanden and
Meijer (1993 a) for further details.
12.8.4.2 Critical Microscopic Thickness
The rubber weight fraction at which a
sharp increase is observed in the strain to
break for rubber-modified PS-PPE blends
(Fig. 12-22) corresponds to a certain aver-
age surface-to-surface interparticle dis-
tance, Dj (i.e., ligament thickness), which
can be calculated from the rubber particle
size and volume fraction (assuming a body-
centered-cubic lattice) (Wu, 1985, 1988;
Borggreve, 1987). It can be inferred from
Fig. 12-22 that the critical ligament thick-
ness increases with increasing PPE content
present in the matrix (analogous to multi-
layered PS-PPE/PE tapes; see Fig. 12-21).
In order to derive a simple first-order
model describing the phenomenon of the
thickness-dependent brittle-to-ductile tran-
sition, the conditions have to be investigat-
ed that allow for a continuation of local de-
formation without fatal fracture. A lattice
of holes, which is a schematic representa-
tion of nonadhering rubbery particles in a
PS-PPE matrix, creates thin ligaments of
polymeric material, i.e., potential deforma-
tion initiation places. The smallest size of a
fracture surface is the stretched fibril origi-
nating from the matrix ligament between
two neighboring particles. Brittle fracture
can only occur if the stored elastic energy
per matrix ligament is larger than the ener-
gy required to create brittle fracture of this
fibril. The stored elastic energy per ligament
can be considered to be correlated with the
75 volume of matrix material that is relieved
from elastic stress if a brittle fracture were
to occur in the connecting fibril. Although
only detailed micromechanical analysis in a
substantial volume around a matrix filament
could give conclusive answers on the elas-
tic energy stored in the volume that is
released after rupture of the fibril, a rough
first approximation could be the matrix vol-
ume between two holes; see the shaded area
in Fig. 12-25 a (direction 1 is the direction
of the applies stress). This volume can be
estimated to be a sphere, having a diameter
of dx (= h). The maximum average stress in
this volume is estimated as the yield stress,
cry, since higher stresses would result in duc-
tile plastic deformation of the ligament. The
available elastic energy, t/av, per ligament
is therefore
tfav=f(4)3^- (12-13)
where E{ is the Young's modulus of the
PS-PPE blend.
The energy required to create a brittle
fracture, /re, can be estimated from
(12-14)
where F is the surface energy of the poly-
meric matrix material. The size of a possible
fracture surface (diameter d2\ Fig. 12-25 b)
is proportional to the original cross-
sectional area of the matrix ligament divid-
 12.8 Critical Thickness and Network Density
brittle-to-ductile transition (kx is a constant)
b
\ II
1
2 J
Figure 12-25. Schematic view of a matrix ligament
between two holes, representing nonadhering rubbery
particles: (a) before plastic deformation and (b) dur-
ing plastic deformation. The shaded area represents
the elastically deformed volume that is relieved of
elastic stress once the fibril breaks.
ed by Amax, since this is the most critical con-
dition, analogous to the use of the yield
stress in Eq. (12-13).
The surface energy is given by (Kramer
and Berger, 1990)
r = y + -vcdU (12-15)
/ 4 e In Fig. 12-26 the calculated value of A c
where / i s the van der Waals surface ener-
gy, d is the root mean square end-to-end dis-
tance between junction points in the net-
work, and U is the polymer backbone bond
energy. (The influence of the moderate
degree of molecular orientation on the value
of the surface energy is neglected.) Accord-
ing to Kramer and Berger, 1990), ve d scales
roughly as v^72 (the polymer backbone bond
energy is roughly equal for all amorphous
polymers).
Combining Eqs. (12-13), (12-14), and
(12-15) results in an energy criterion for the
607
d\ = Ac = (12-16)
If the value of Dl is larger than Dlc (the
critical interparticle distance), brittle frac-
ture of the ligament is possible (f/av > Ure)
and will therefore occur. If, on the other
hand, Dl < >Ic, brittle fracture cannot occur
([/ av < Ure) and complete deformation of the
ligament will take place, eventually leading
to a fully ductile macroscopic fracture
behavior.
Taking for PS, 7=40 mJ m~2, k} =
7.13xlO 15 J chain"172 m"172 (Kramer and
Berger, 1990), Ex = 3.28xlO9 Pa (Kambour,
1983), Amax = 4.2, and <7y = 82.8 MPa (Kam-
bour, 1983) results in D lc = 0.055 |Lim
[Eq. (12-16)], which is surprisingly close to
the experimentally determined value
(0.05 |Lim; see Sec. 12.7) given the simplic-
ity of the model and the assumptions made
of the volume of matrix material released
after rupture of the fibril.
Extending the model by introducing the
ve dependence of Amax [Amax = 2 v ~1/2; the
constant &2 = 2.36xl0 1 3 chains 172 m-3/2
(Kramer and Berger, 1990)] results in
= Ac = (12-17)
is plotted as a function of the entanglement
density for several PS-PPE blends. The full
curve is drawn according to Eq. (12-17),
taking for the yield stress a constant value
of 70 MPa; the broken curve is also drawn
according to Eq. (12-17), but taking for
the yield stress data published by
Kambour (1983). The Young's modulus of
the PS-PPE phase is assumed to be inde-
pendent of the entanglement density
( 1 = 3.28xl0 9 Pa). In Fig. 12-26 the
experimentally determined values of Dlc
for various core-shell, rubber-modified
608 12 Deformation and Toughness of Polymers
E non of a brittle-to-ductile transition [for a
3 0.20
/ ' cjy after
''DeGennes (1991)
0.10
o referred to van der Sanden and Meijer
3 6 9 12
25 3
Network density (x10 chains/m )
Figure 12-26. Critical material thickness (DIc) ver-
sus the matrix entanglement density (ve) for the vari-
ous PS-PPE blends. The curves are according to the
model. For details, see text.
PS-PPE blends are given as well (filled
squares). The value of Dlc for the PS-PPE
20-80 blend is taken from van der Sanden
and Meijer (1994 a) (high speed tensile
tests). Not only is the slope representing the
entanglement density dependence of the
critical thickness predicted well by both
curves, but the absolute values of the criti-
cal thickness are also surprisingly correct
taking into account the simplicity of the
model and the serious assumptions that have
been made.
In Fig. 12-26 two data points are also
shown as obtained from multilayered
PS-PPE blends (open squares). As already
discussed, these data compare well with
those obtained from core-shell, rubber-
modified PS-PPE blends but, surprisingly,
they are also close to the predicted values.
In the stratified structures, the estimation of
the volume of matrix material containing
elastic energy to create a brittle fracture is
much more complicated and, moreover,
requires a number of assumptions to be made
on the development of the deforming parts.
Although the model presented needs
refinements in, for instance, the estimation
of the released volume containing stored
elastic energy, the results are promising
towards an understanding of the phenome-
more detailed discussion of the critical
thickness observed for relatively densely
crosslinked thermosets, the reader is
(1994 a)]. Moreover, the influence of test-
ing temperature and testing speed can be
incorporated relatively easily via the tem-
perature and strain rate dependence of the
yield stress and Young's modulus of the
matrix (van der Sanden and Meijer, 1994 a).
12.9 Concluding Remarks
As demonstrated by Kramer and co-
workers (see Sec. 12-4), a systematic inves-
tigation on a wide variety of different types
of polymers can result in a clear understand-
ing of the strain to break (i.e., toughness) of
amorphous glassy polymers from a molec-
ular point of view, at least on a microscop-
ic scale such as the craze extension ratio and
the draw ratio in a shear deformation zone.
The network density is the key parameter in
these investigations, since with a decreas-
ing network (entanglement and/or cross-
link) density both the theoretical and the
experimental microscopic draw ratio
increase strongly. Intriguing in this context
is that routes towards other ultimate prop-
erties like stiffness and strength, at least for
flexible semi-crystalline polymers like
polyethylene, also depend fully on the
drawability of the network. Analogously, in
the search for the ultimate toughness, the
maximum attainable draw ratio can be cho-
sen as a discriminating parameter since
toughness can be roughly defined as the
product of deformation stress and strain to
break. The first parameter is relatively con-
stant within the class of amorphous glassy

polymers, while the latter shows some
apparent contradictions, since on a macro-
scopic scale the experimental strain to break
is in most cases more than two decades
lower than the maximum strain of the
molecular network. Striking in this context
is the theoretical draw ratio of polystyrene
(PS), which equals 320% and is experimen-
tally verified by Kramer and co-workers on
a microscopic scale to be 300% (see
Sec. 12.4), while macroscopically the strain
to break of polystyrene roughly equals only
1-3%.
In the research discussed in this chapter,
these discrepancies were investigated and a
universal approach for the macroscopic
toughness of amorphous polymeric systems
was aimed at using a systematic experimen-
tal approach covering the complete class of
polymeric networks. This approach has
resulted in the possibility to estimate the
ultimate toughness of polymeric systems
and a theory that is capable of defining
directions for further research in the devel-
opment of controlled toughness.
While the large microscopic draw ratio is
found on the scale of local deformation
mechanisms such as craze fibrils or shear
deformation zones, the low macroscopic
draw ratio is operative on a scale of a few
millimeters. Hence a decrease of the mac-
roscopic sample dimensions should eventu-
ally result in an increase of the macroscop-
ic strain to break. In Sec. 12-7 of this chap-
ter, the macroscopic dimensions of PS were
decreased in one (thin films) or two dimen-
sions (ligaments). Both approaches finally
resulted in a sharp increase of the macro-
scopic strain to break at a certain critical
thickness of less than 1 |im. Below this crit-
ical size, either given by the film thickness
or by the average distance between the
added nonadhering rubbery particles, the
macroscopic draw ratio reaches values com-
parable with the theoretical strain to break
12.9 Concluding Remarks 609
(see Fig. 12-24, network density of 3xlO25
chains m~3).
In Sec. 12-8 of this chapter, the network
density dependence of the critical thickness
and the maximum macroscopic toughness
(strain to break) were investigated for the
class of thermoplastic polymers (see
Figs. 12-24 and 12-26).
The macroscopic draw ratios below the
material-specific critical thickness clearly
fit the curve given by 60% of the theoreti-
cal draw ratio (see Fig. 12-24). Obviously,
the maximum macroscopic toughness is
influenced by the existence of a distribution
in the network densities (any other network
arguments would only lead to higher pre-
dicted values)2.
Similar to the maximum macroscopic
draw ratio, the critical thickness is depen-
dent on the network density of the polymer.
With increasing network density, the criti-
cal thickness below which the maximum
degree of macroscopic ductility is observed
increases (see Fig. 12-26).
The physical explanation for the occur-
rence and network density dependence of
the critical dimension was given in
Sec. 12.8 and originates from an energy
based criterion for brittle fracture assuming
that deformation will always be initiated
locally. The stored elastic energy within a
matrix ligament is compared with the
required fracture surface energy to generate
a brittle fracture of this ligament. If the
stored elastic energy equals, or is higher
than, the fracture surface energy required,
brittle fracture will occur locally and extend
2
For a given network density, the maximum draw
ratio is independent of the type of network, as physi-
cal entanglements and chemical crosslinks both act as
'nodes of enhanced friction' on the time scale of a de-
formation process (typically a few seconds or less),
and no chain slippage and/or disentanglement can
occur at the testing temperatures applied (van der San-
den and Meijer, 1993 a).
610 12 Deformation and Toughness of Polymers
throughout the complete sample; if the
stored elastic energy is lower than the frac-
ture surface energy, macroscopic ductile
fracture behavior occurs. The results of the
most simplified calculations concerning
this fracture criterion were shown in
Fig. 12-26. Given the simplicity of the
model, a surprisingly good correlation is
observed between the predicted values and
the experimental data. Extrapolation of the
predicted curve to network densities of
200x1025 chains m~3 (typical for standard
crosslinked thermosetting polymers)
reveals that the critical thickness of these
samples is of the order of a few microme-
ters [see van der Sanden and Meijer
(1994 a)]. Hence the addition of only a few
percent of rubber to these systems results in
their maximum macroscopic toughness.
However, the absolute toughness of this
class of materials is of course limited.
These experiments clearly suggest a pos-
itive influence of a decreased cavitation
stress of the elastomeric filler and the ben-
eficial absence of adhesion between the
elastomer and the matrix in obtaining the
ultimate toughness. This in clear contrast
with earlier findings (see Sec. 12.5) if only
an intermediate toughness is pursued, e.g.,
via the introduction of a multiple crazing
mechanism, where improved adhesion can
influence the macroscopic toughness in a
favorable manner. The optimal particle sizes
reported for craze-deforming materials (see
Sec. 12.5) are not relevant with respect to
the ultimate toughness of amorphous poly-
mers, since in principle no limitations exist
for a minimum hole size in the ultimate
toughening concepts presented here.
Based on the above understanding of ulti-
mate macroscopic toughness, the elegance
of developing sub-micrometer, or even
nano-sized, polymeric structures emerges.
One of the most brittle of all amorphous
polymers, i.e., polystyrene, manifests itself
as a very ductile polymer below a local
thickness of 0.05 |im (see Figs. 12-24 and
12-26). This offers a challenging perspec-
tive in developing macroscopically tough
polystyrene by adding holes in order to
create the required (local) critical thickness.
Generally, foams are materials with low
stiffness and strength, which are not very
tough. This is due to the too large cell diam-
eters used. In Fig. 12-27 the foam density of
polymers is plotted versus the cell diameter
for different values of the (critical) intercel-
lular distance.
Traditional PS foams possess typical
cell diameters of 50 |im, gas volume frac-
tions of 95 vol.%, consequent densities of
0.05 g cm"3 (50 kg m~3), and therefore wall
thicknesses of a few micrometers or larger.
Consequently, they do not show any ductile
macroscopic properties, as the critical thick-
ness for PS is 0.05 |Lim (see Fig. 12-27).
Only the development of PS foam with cell
diameters smaller than 0.1 |im can result in
extremely ductile foam-like structures with
a volume fraction of gas-filled cells <30%,
which would shear without a considerable
loss of stiffness. Logically, a lower limit
exists in the cell size that can be applied,
1.00
0.80 -
3 0.60 -
0.40 -
0.20 -
0.00
0.01 0.1 1 10 100
Cell diameter (|jm)
Figure 12-27. Foam density as a function of the cell
diameter for different values of the critical intercellu-
lar distance.

since, finally, on a molecular scale density
fluctuations also exist, while most amor-
phous glassy polymers do not reveal a mac-
roscopic ductile fracture behavior as a con-
sequence of these (locally) thin ligaments.
The curve corresponding to a wall thickness
of 0.5 |Lim (Fig. 12-27) is valid for the typi-
cal critical thickness of polycarbonate at
low temperatures under notched high speed
impact conditions, while the 5-|im curve
corresponds to relatively densely cross-
linked thermosets.
In order to experimentally verify the
toughness of these sub-micrometer foams,
e.g., PS or PMMA, such foams must be pro-
duced. The practical production of such
foams is an important challenge for polymer
processing in the future3.
12.10 Acknowledgements
The author is grateful to Profs. Han Meij-
er, Piet Lemstra, and Ed Kramer and Ir.
Bernd Jansen for their contributions to this
work.
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13 Photopolymerization and Ultraviolet Curing
of Multifunctional Monomers
Christian Decker

Laboratoire de Photochimie Generate, URA - CNRS 431, ENSCMu,

Universite de Haute Alsace, Mulhouse, France

List of Symbols and Abbreviations 617

13.1 Introduction 619
13.2 Basic Principle of Photoinitiated Curing 620
13.3 Different Types of Photoinitiator 620
13.3.1 Radical Formation by Photocleavage 621
13.3.2 Radical Generation by Hydrogen Abstraction 622
13.3.3 Cationic Photoinitiators 623
13.4 Different Types of Photocurable System 624
13.4.1 Photoinitiated Radical Polymerization 625
13.4.1.1 Unsaturated Polyester Resins 625
13.4.1.2 Thiol-ene Systems 625
13.4.1.3 Acrylate and Methacrylate Monomers 626
13.4.2 Photoinitiated Cationic Polymerization 627
13.4.2.1 Epoxides 627
13.4.2.2 Vinyl Ethers 628
13.4.2.3 Hybrid Systems 628
13.5 Processing of Ultraviolet-Curable Systems 629
13.5.1 Coating Applications 629
13.5.2 Ultraviolet Oven 630
13.5.3 Cure Test 631
13.6 Kinetic Study of Photoinitiated Curing 632
13.6.1 Methods of Curing Analysis 632
13.6.2 Real-Time Infrared Spectroscopy 632
13.7 Novel Acrylate Monomers 634
13.7.1 Reactivity 634
13.7.2 Kinetic Parameters 636
13.7.2.1 Quantum Yield 636
13.7.2.2 Kinetic Chain Length 636
13.7.2.3 Propagation and Termination Rate Constants 637
13.7.2.4 Rate of Chain Growth 637
13.7.3 Properties of Ultraviolet-Cured Polymers 638
13.8 Vinyl Ether Monomers 638
13.8.1 Photoinitiated Cationic Polymerization of Vinyl Ethers 638
13.8.2 Photoinduced Curing of the Acrylate/Vinyl Ether System 639
Materials Science and Technology
Copyright WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
616 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers

13.8.2.1 Cationic Photoinitiator 639

13.8.2.2 Radical Photoinitiator 640
13.8.3 Photoinduced Curing of the Maleate/Vinyl Ether System 641
13.9 Ultraviolet Curing of Acrylic Monomers in a Polymer Matrix 643
13.9.1 Poly(methylmethacrylate) (PMMA) 643
13.9.2 Poly(vinylchloride) (PVC) 644
13.9.3 Polyurethane (PUR) 644
13.9.4 Natural Rubber 645
13.10 Industrial Applications of Ultraviolet Curing 646
13.10.1 Graphic Arts 646
13.10.1.1 Printing Plates 646
13.10.1.2 Ultraviolet-Curable Printing Inks 647
13.10.1.3 Overprint Varnishes (OPVs) 648
13.10.2 Coatings 648
13.10.2.1 Wood Finishing 648
13.10.2.2 Plastic Coatings 649
13.10.2.3 Metal Coatings 650
13.10.3 Adhesives 650
13.10.3.1 Laminated Adhesives 650
13.10.3.2 Pressure-Sensitive Adhesives (PSAs) 651
13.10.4 Electronics 651
13.10.5 Stereolithography 652
13.10.6 Dental Composite Materials 653
13.11 Conclusions 654
13.12 Acknowledgements 655
13.13 References 655
 List of Symbols and Abbreviations 617

List of Symbols and Abbreviations

light absorbance
initial acrylate double bond concentration
Planck's constant
absorbed light intensity
incident light intensity
propagation rate constant
K termination rate constant
kcl kinetic chain length
I sample length
[MJ monomer concentration
[M], monomer concentration at end of irradiation, after given time t
rate of initiation
rate of polymerization
rate of polymerization at end of irradiation, after given time t
s photosensitivity
t time
glass transition temperature
x degree of conversion
X, Y coordinates

contrast
photoinitiator absorptivity
A wavelength
v frequency
quantum yield of formation of the initiating species
polymerization quantum yield

CW continuous wave
DSC differential scanning calorimetry
EDGA ethyldiethyleneglycol monoacrylate
HDDA hexanedioldiacrylate
IPN interpenetrating network
IR infrared
LDI laser direct imaging
MA maleate
NMR nuclear magnetic resonance
OPV overprint varnish
PC polycarbonate
PCB printed circuit board
PI photoinitiator
PMMA poly(methylmethacrylate)
PSA pressure-sensitive adhesive
PUR polyurethane
618 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers

PVC poly(vinyl chloride)

QUV accelerated weathering device
RH hydrogen donor substrate
RTIR real time infrared
TMPTA trimethylolpropane triacrylate
UV ultraviolet
VE vinyl ether

13.1 Introduction
One of the most efficient methods to
rapidly generate strongly crosslinked poly-
mers consists of exposing multifunctional
monomers to ultraviolet (UV) radiation in
the presence of a photoinitiator. A liquid
resin can thus be transformed within a frac-
tion of a second into a solid polymer, total-
ly insoluble in the organic solvents and very
resistant to heat and mechanical treatments.
The term radiation curing is often used to
designate such crosslinking polymerization
induced by UV or visible light, lasers or
electron beams. The subject has been exten-
sively investigated and thoroughly surveyed
in some excellent textbooks and com-
prehensive review articles (Roffrey, 1982;
Pappas, 1985, 1992; Decker, 1987, 1989,
1993 a; Hoyle and Kinstle, 1990; Oldring,
1991 a; Fouassier and Rabek, 1993).
Because of its distinct advantages, i.e., an
ultrafast polymerization performed at ambi-
ent temperature in the absence of any sol-
vent, this advanced technology has experi-
enced a steady growth during the last
decade. It has found an increasing number
of applications in various industrial sectors,
mainly for the hardening of thin specimens,
owing to the limited penetration of UV light
into organic compounds. The most impor-
tant end uses are to be found in the coating
industry for the surface protection of all
kinds of materials (metals, plastics, glass,
paper, wood, fabrics, etc.) by fast drying
varnishes, paints, or printing inks, as well
as in the manufacture of radiation-curable
adhesives and composite materials. Another
unique feature of photocuring is that the
polymerization reaction only occurs in the
illuminated areas, thus allowing high reso-
lution relief images to be generated by light-
induced insolubilization of photoresists.
Such photopolymers are now commonly
used to produce printing plates, optical
13.1 Introduction 619
disks, microcircuits, and 3-D recording
plates for holographic devices. Photocuring
technology has recently achieved a predom-
inant position in some specific sectors, such
as for the coating of optical fibers and in
laser stereolithography.
Most of the research efforts devoted to
photocuring have been focused on the
design of high performance formulations,
which would polymerize both fast and
extensively to give polymer networks show-
ing outstanding physical and chemical prop-
erties. Great progress has been achieved in
recent years with the development of ever
more efficient photoinitiators (Dietliker,
1991) and highly reactive new monomers
(Tu, 1985; Watt, 1985) and oligomers
(Oldring, 1991b; Martin, 1985) for both
clear and pigmented resins. A large choice
of commercially available products makes
it possible to select the proper formula-
tions to meet the cure speed and product
properties required for particular applica-
tions.
In this article, the basic principle of the
photoinitiated polymerization of multifunc-
tional monomers will be outlined first,
together with a short review of the various
systems most widely used in today's radia-
tion curing applications. The performance
of some newly developed monomers will
then be discussed with respect to both the
kinetics and mechanism of such ultrafast
polymerization reactions, along with the
properties of the polymer network thus
formed. Special emphasis will be given to
the UV curing of multiacrylate resins, which
are among the most widely used photo-
polymers in radiation-curing applications,
because of their high reactivity which
allows a quasi-instant formation of densely
crosslinked networks by a chain process.
620 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers
13.2 Basic Principle
of Photoinitiated Curing
Photocuring is typically a process that
transforms a multifunctional monomer into
a crosslinked macromolecule by a chain
reaction initiated by reactive species gener-
ated by UV irradiation. Since most of the
monomers do not produce initiating species
with a sufficiently high yield upon UV expo-
sure, it is necessary to introduce a photosen-
sitive initiator which will make the polymer-
ization start upon illumination. The overall
process can be represented schematically as
in Scheme 13-1.
UV-curable formulations are usually
made of three basic components:
1. A photoinitiator, which effectively ab-
sorbs the incident light and readily gen-
erates reactive radicals or ions.
2. A functionalized oligomer, which by
polymerizing will constitute the back-
bone of the tridimensional polymer net-
work formed.
3. A mono- or multifunctional monomer,
which acts as a reactive diluent and will
thus be incorporated into the network.
The photoinitiator plays a key role in that
it governs both the rate of initiation and the
penetration of the incident light into the
sample, and therefore it governs the depth
of cure. The rate of polymerization depends
Photoinitiator
Reactive species
(radicals or ions)
UV radiation
Multifunctional
monomer
initially on the reactivity of the functional
group, its concentration, and the viscosity of
the resin. The chemical structure and func-
tionality of both the monomer and the oligo-
mer are also important, for they will deter-
mine the final degree of polymerization as
well as the physical and chemical character-
istics of the UV-cured polymer. The various
types of photoinitiator and of monomer
systems currently employed in UV-curing
applications will now be briefly described.
13.3 Different Types
of Photoinitiator
An efficient photoinitiator has to have
high absorption in the emission range of the
light source, usually a medium pressure
mercury lamp (248 < A<578 nm). The excit-
ed states thus formed must have a short life-
time (a few nanoseconds), to avoid quench-
ing by oxygen or monomer, and generate
initiating species with the highest possible
quantum yield. The various deactivation
pathways of the excited initiator molecule
are represented schematically in Fig. 13-1.
The rate of initiation (rt) is directly relat-
ed to the light absorbance (A) of the photo-
initiator, to the quantum yield of formation
of the initiating species (0{) and to the inci-
dent light intensity (70)
-A)] (13-1)
- Crosslinked polymer
Scheme 13-1.
 13.3 Different Types of Photoinitiator 621

Light
absorption

QUENCHING
(O2, monomer)

PHOTOINITIATOR GROUND STATE

Figure 13-1. Various deactivation pathways of the excited photoinitiator molecule. * represents an excited state.

A unique advantage of photoinitiation, 13.3.1 Radical Formation

compared to thermal polymerization, is that
very high values of rx can be attained sim-
ply by adjusting the light intensity, which
can be varied over a large range, even dur-
ing the polymerization. Moreover, the depth
of cure can be finely controlled through the
photoinitiator concentration, [PI], which
directly affects the light absorbance
= e/x[PI] (13-2)
where / is the sample thickness and the
photoinitiator absorptivity.
A large variety of photoinitiators have
been developed during the past 20 years in
order to obtain photocurable resins that can
be hardened within a fraction of a second
under intense illumination. Their photolysis
mechanism and performance under UV or
visible exposure have been studied exten-
sively (Crivello, 1981; Hageman, 1985;
Pappas, 1987; Fouassier, 1985) and are
reviewed in an excellent textbook (Dietli-
ker, 1991). The various photoinitiators used
in UV-curing applications can be classified
into three major categories, depending on
the way the initiating species are generated.
by Photocleavage
This class includes aromatic carbonyl
compounds that are known to undergo a
homolytic C-C bond scission upon UV
exposure, with the formation of two radical
fragments
hv
x
c- + c x (1)
o
The benzoyl radical was shown to be the
major initiating species, while the other
fragment may, in some cases, also contrib-
ute to the initiation (Hageman, 1985). The
most efficient photoinitiators belong to this
class, such as the benzoin ether derivatives,
benzilketals, hydroxyalkylphenones, a-
amino ketones, and acylphosphine oxides.
The last two compounds proved to be par-
ticularly efficient for the photocuring of pig-
mented systems (Desobry et al., 1990; Jaco-
622 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers

bi et al., 1985). Photoinitiators containing 13.3.2 Radical Generation

one of these chromophores and an acrylate by Hydrogen Abstraction
double bond, as well as polymeric photo-
Some aromatic ketones, like benzophe-
initiators, have been shown to substantially
none, thioxanthone, or camphorquinone, do
reduce the amount of photoinitiator that can
not undergo fragmentation when they are
be extracted from UV-cured coatings with
promoted to their excited states by UV irra-
no significant loss in initiation efficiency
diation, but tend to abstract a hydrogen atom
(Li Bassi, 1987; Koehler and Ohngemach,
from an H-donor molecule via an exciplex,
1989).
to generate a ketyl radical and the donor rad-
ical

hv
O)-Ho>r RH

O
OH (2)
Initiation of the polymerization occurs through the H-donor radical, while the inactive
ketyl radical disappears by a radical coupling process. Tertiary amines are mainly employed
as co-initiators, because of the high reactivity of the a-amino alkyl radical towards the
monomer double bond
hv
Ar2C = N-CH2- Ar 2 C-OH+ > N - C H -

CH2=CH- (3)

N-CH-CH2-CH-

The use of tertiary amines has the additional advantage of helping overcome the inhibi-
tion effect of oxygen on radical-induced polymerizations (Decker and Jenkins, 1985). The
oxygen dissolved in the monomer is rapidly consumed by a-chain peroxidation process,
which generates hydroperoxide groups, which are still able to initiate detrimental thermal
and photochemical degradation reactions
RH
:N-CH- :N-CH-
i I (4)
O-O* OOH

The role of amines in UV radiation cur-

ing has recently been reviewed (Davidson,
1993). Beside their beneficial effect in
accelerating surface cure, amines tend to
impart some yellowing to UV-cured prod-
ucts and to decrease their hardness, due to
an efficient chain transfer process. It should
be mentioned that the benzophenone plus
amine photoinitiator system has sometimes
been erroneously considered as a synergis-
tic combination. Actually, both components
need to be present to produce initiating rad-
icals upon UV exposure, as benzophenone
alone is not capable of initiating the poly-
merization in the absence of an H donor
molecule.
 13.3 Different Types of Photoinitiator 623

13.3.3 Cationic Photoinitiators Different types of these powerful proto-

nic acids can thus be formed with a large
Bronsted acids are readily generated by
yield, and they have been used to initiate the
the photolysis of diaryliodonium (Crivello
cationic polymerization of vinyl ethers and
and Lam, 1978 a) or triarylsulfonium (Cri-
heterocyclic monomers. Although the rate
vello and Lee, 1989) salts in the presence of
of polymerization of cyclo-aliphatic epox-
an H donor molecule
ides was found to be lower than for radical
Arl +Ar*+R'+HBF 4 curable acrylates (Decker and Moussa,
(5) 1992), cationic initiators are increasingly
being employed in UV-curing applications,
Ar3S+PF6 + RH Ar2S + Ar* + R' + HPF6 especially when the speed of cure is not the
(6) prime criterion. The two most remarkable

RADICAL PHOTOINITIATORS

Benzoin derivatives

Benzil ketals

Hydroxyalkylphenone

Acylphosphine oxides

Benzophenone derivatives

Thioxanthone derivatives

CATIONIC PHOTOINITIATORS

Diaryliodonium salts R R AsF 6 '

Figure 13-2. Different types of

Triarylsulfonium salts
photoinitiators used in UV radiation
curing.
624 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers

features of cationic-initiated polymeriza-
tion are its lack of sensitivity towards atmos-
pheric oxygen and the effective post-
polymerization which continues to proceed
in the dark after UV exposure (Decker and
Moussa, 1990 a). The formulas of some typ-
ical cationic and radical photoinitiators are
given in Fig. 13-2.
13.4 Different Types
of Photocurable System
A great number of multifunctional mono-
mers and oligomers have been developed
over the years for use in photocurable for-
mulations, and they produce highly cross-
linked polymers. It should be noticed that
once the initiating radicals or ions have been
generated by photolysis, the following steps
(chain propagation and termination) will
essentially be the same as in a conven-
tional polymerization, except for the much
larger rate of initiation provided by UV irra-
diation. Figure 13-3 shows the formulas of
some typical multifunctional monomers and
oligomers used in the different kinds of UV-
curable formulations, which will now be
briefly reviewed.

RADICAL-TYPE MONOMERS

Polyester / Styrene

- pil -OUI C* .AAAAA

-CH=CH2

Thiol / ene

C(R SH)4 + CH2= CHR1CH = CH2

Acrylates

CH 2 -CH 3 TMPTA

CH2 = C H - C - O - R - O - C - C H = CH2
o o
with R : polyester, polyether, polyurethane, polysiloxane

CATIONIC - TYPE MONOMERS

Epoxides

Vinyl ethers

C H 2 = C H - O - f CH 2 CH 2 O-jhCH=CH 2 DVE - 3

CH2 = C H - O - R - O - C H = C H 2

with R : polyester, polyether, polyurethane Figure 13-3. Different types of UV-

curable system.
 13.4 Different Types of Photocurable System 625

13.4.1 Photoinitiated Radical multifunctional monomers are involved

Polymerization
There are three main classes of UV-
curable resins that polymerize by a radical
mechanism, as discussed in the following
three sections.
13.4.1.1 Unsaturated Polyester Resins
Photopolymerizable resins consisting of
an unsaturated polyester dissolved in sty-
rene were among the first to be used in large
scale UV-curing applications (Chandler,
1970; Laus, 1976). Here the radical-
initiated crosslinking occurs by direct addi-
tion copolymerization of the vinyl monomer
with the unsaturations (usually maleic or
fumaric structures) located on the polyester
backbone
(Morgan et al., 1977). A great number of ki-
netic and mechanistic studies have been de-
voted to this subject, which has recently been
reviewed in a comprehensive monography
(Jacobine, 1993). With a hydrogen abstrac-
tion type photoinitiator, the chain reaction
can be formally represented as follows
Ar2C = O + R S H ^ A r 2 C - O H + RS' (8)
RS* +CH 2 =CH-R'>RS-CH 2 -CH-R'
(9)
RS-CH 2 -CH-R' + RSH >
RS-CH 2 -CH 2 -R' + RS* (10)
The thiol-ene polymerization proceeds by
a step growth addition mechanism, which is
propagated by a free-radical, chain transfer

C CH = CH C CH = Crosslinked (7)
polymer

The relatively slow cure, together with

volatility problems and the reduced number
of monomers available, has limited the
development of this system, which is main-
ly used in the wood finishing industry.
13.4.1.2 Thiol-ene Systems
The photoinduced addition of a thiol (RSH)
to an olefinic double bond can be used as a
network-forming reaction, provided that
reaction involving the thiyl radical (RS*)
(Lenz, 1967). As with all step-growth
processes, it requires stoichiometric con-
ditions in order to achieve a fast and
complete polymerization. With multifunc-
tional monomers, such as tetrafunctional
thiols [C(RSH)4] combined with a diene
(CH 2 =CH-R'-CH = CH2), a three-dimen-
sional network is formed, in which the con-
necting chains are made of an alternating
copolymer

I I
S S
I I
R R
I
-R'-CH2-CH2-S-R-C-R-S-CH2-CH2-R'-CH2-CH2-S-R-C-R-S- (11)
R R
I I
S S
I I
626 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers

The crosslink density of the polymer net-
work, as well as its properties, depends on
the functionality, the length, and the chem-
ical nature of the polyene (R') and thiol pre-
polymer (R) chains, and can thus be tailored
as desired. Because peroxy radicals formed
by the O2 scavenging of alkyl radicals
are also capable of abstracting hydrogen
atom from the thiol, UV-curable thiol-ene
systems are much less sensitive to air inhi-
bition than conventional radical-induced
polymerizations
(12)
With the development of new types of
prepolymers, such as vinyl-functionalized
silicones (Jacobine and Nakos, 1992), there
has been a marked increase in interest in
thiol-ene photopolymerization, which is
now used in a large number of applications
(coatings, adhesives, sealants, printing
plates, and microcircuits).
13.4.1.3 Acrylate and Methacrylate
Monomers
The light-induced polymerization of mul-
tiacrylate monomers and oligomers has been
studied extensively, particularly its kinetic
and mechanistic aspects (Blanding, et al.,
1978; Collins and Costanza, 1979; Tryson
andSchultz, 1979; Tu, 1983; Decker, 1983 a,
1993 b; Kloosterboer et al., 1984; Klooster-
boer and Lippits, 1984; Ahn et al., 1986;
Decker and Moussa, 1987a, 1989, 1990b;
Kloosterboer, 1988; Nakamura et al., 1990;
Bowman and Peppas, 1991; Anseth et al.,
1995 a, b; Decker and Elzaouk, 1995 a). The
great commercial success of these UV-
curable resins stems from their high reactiv-
ity, and from the possibility of creating a
large variety of crosslinked polymers with
tailormade properties. The polymerization
of a diacrylate monomer initiated by photo-
generated benzoyl radicals can be schemat-
ically represented as shown in Scheme
13-2.

Initiation

C CH 2 CH C O
O O

+ monomer

Propagation

-?- O
- CH
2 "- CH -- C H 2 -- CH -- CH2 -- CH
C=O
1
1
C =o

C =o c =o
1 1
CH C H 2 - - C H -- C H 2 - CH C H 2 - CH -- CH
\

Termination

P
n + Pm '" P ]
n
. j
^ Occlusion Scheme 13-2.
 13.4 Different Types of Photocurable System
After a fast start, the polymerization pro-
gressively slows down, due to severe mobil-
ity restrictions of the reactive sites caused by
gelation and ultimately vitrification, which
leads to premature chain termination. Thus
a certain amount of residual unsaturation and
trapped radicals remain in the UV-cured
polymer network (Kloosterboer et al., 1984;
Decker and Moussa, 1987 a). Multifunction-
al methacrylate monomers undergo a simi-
lar crosslinking polymerization, but at a
slower pace than the acrylate derivatives,
because of a less efficient propagation reac-
tion (lower value of kp). Although these
radical-induced reactions are strongly in-
CH 2 CH 2
+ monomer)
x-o
CH9-R CH-R
hibited by oxygen, a fast and extensive
curing is achieved in the presence of air, even
for thin films, because of the very high initi-
ation rates provided by intense illumination.
Different types of chemical structure can
be used for the prepolymer backbone, e.g.,
polyurethanes, polyesters, polyethers, and
polysiloxanes. As a general rule, low mod-
ulus elastomers are obtained with aliphatic
chains, whereas hard and glassy polymers
are formed when the crosslinked segments
contain aromatic structures. In addition, the
acrylate monomer introduced to reduce the
viscosity also affects the physical and
mechanical properties of the UV-cured poly-
mer, as well as the overall extent of cure.
Viscoelastic measurements suggest that
the UY-cured polyurethane-acrylate net-
work consists of rigid acrylate clusters
which are bonded together by the flexible
urethane chain. As the quantity of monomer
added to reduce the viscosity can be as large
as that of the functionalized oligomer, these
clusters may represent more than half of the
total polymer network formed.
627
13.4.2 Photoinitiated Cationic
Polymerization
Light-induced cationic polymerization is
one of the most efficient methods to rapid-
ly cure monomers that are inactive toward
radical species, in particular vinyl ethers and
heterocyclic monomers such as epoxides,
lactones, and cyclic ethers.
13.4.2.1 Epoxides
In the presence of a photogenerated pro-
tonic acid, the ring-opening polymerization
of epoxides proceeds through the oxonium
ion
X-O-CH2-CH- < ' (13)
k
If difunctional epoxides or epoxy-
substituted polymers are used as the starting
material, crosslinking readily occurs to gen-
erate a tridimensional polymer network (Cri-
velloandLam, 1978 b; Crivello, 1978,1984;
Pappas et al., 1984; Watt, 1985; Decker and
Moussa, 1994; Bayer and Lehner, 1990). By
contrast to radical-initiated polymerization,
the chain carrier species is not interacting, so
that the living polymerization will continue
to develop after the UV exposure and thus
provide a beneficial post-cure effect which
can be enhanced further by a thermal treat-
ment. Termination still occurs, either by
chain transfer to give an inactive species, or
by reaction of the propagating species with
nucleophilic impurities, in particular traces
of water. Another advantage of cationic poly-
merization is that the oxonium ion and the
carbocation are inactive toward the oxygen
molecule, thus allowing even thin coatings to
be cured rapidly in the presence of air.
The actual rate of polymerization of
difunctional epoxides is still one order of
magnitude lower than that of diacrylate
628 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers
monomers, most probably because of a
lower propagation rate constant (Decker
and Moussa, 1992). In this respect the
remarkable performance of some novel
cyclo-aliphatic epoxy-silicones should be
mentioned, which were shown to polymer-
ize cationically as fast and as extensively as
acrylate monomers to give polymers with
excellent physical and chemical properties
(Davidson, 1993; Crivello and Lee, 1990).
13.4.2.2 Vinyl Ethers
Vinyl ethers are amongst the most reac-
tive monomers that polymerize cationical-
ly, and they are increasingly used in photo-
curable resins. The reaction kinetics have
been thoroughly investigated (Crivello
etal., 1983; Dougherty and Vara, 1990;
Lapin and Snyder, 1990; Sauerbrunn et al.,
1990; Decker and Decker, 1994), and the
subject has recently been covered in a com-
prehensive review (Lapin, 1992). Divinyl
ethers, as well as vinyl ether terminated
polyesters, polyurethane, polyesters, and
polysiloxanes, were shown to undergo fast
and extensive polymerization when
exposed to UV radiation in the presence of
an onium salt. The high reactivity of these
monomers is due to the electron rich C = C
bond and to the stabilization by resonance
of the carbocation
(14)
O
R - C H 2 - C H - O ~ - <H> R 2
The functional group attached to the vinyl
ether has a strong effect on the rate of poly-
merization, a fact that was explained on the
basis of differences in the nucleophilicity of
this group. Monomers containing aromatic
structures generally cure faster than their
aliphatic homologs, because of the delocal-
ization of the nonbonding electrons by the
phenyl ring (Lapin, 1989).
13.4.2.3 Hybrid Systems
Polymer networks with well-defined
characteristics can be obtained by the pho-
toinitiated polymerization of a mixture of
multifunctional monomers. By taking two
monomers that polymerize by different
mechanisms, e.g., radically for the acrylate
and cationically for the vinyl ether, two
interpenetrating polymer networks (IPNs)
with contrasting properties have been pro-
duced within a few seconds under intense
illumination (Crivello et al., 1983; Decker
and Decker, 1994). The IPN formed com-
bines the main features of the two networks,
on the one hand, the elastomeric vinyl ether
polymer, and on the other hand, the glassy
acrylate polymer. Kinetic studies have
shown that the two monomers can polymer-
ize either simultaneously or one after the
other, depending on their respective reactiv-
ities (Decker and Decker, 1994).
Different types of UV-curable hybrid
system have been developed in recent years,
in particular vinyl ether/unsaturated ester
(Noren et al., 1990; Schouten et al., 1992),
vinyl ether/acrylate (Dougherty and Vara,
1990; Sauerbrunn et al., 1990; Snyder and
Green, 1992), and epoxide/acrylate (Per-
kins, 1981; Ravijst, 1990) [for a review see
(Peters, 1993)]. The major advantages of
these hybrid systems lie in their superior
combinations of properties, which were
achieved by adjusting the proportion of the
two components, thus allowing improve-
ment of the solvent resistance, the adhesion,
and the abrasion and scratching resistance
of the UV-cured product.
A reliable evaluation of the respective
reactivity of the different types of UV-
curable system can be made by comparing
their polymerization profiles, as shown on
Fig. 13-4. These conversion versus time
curves were recorded by means of real-time
infrared spectroscopy operating under the
 13.5 Processing of Ultraviolet-Curable Systems
Conversion (%)
100
0 1 2 solvent-free formulations must be carefully
Exposure time (s)
Figure 13-4. Polymerization profiles of different
types of UV-curable system recorded by real-time
infrared spectroscopy: 1: acrylate, 2: vinyl ether, 3:
polyester/styrene, 4: methacrylate, 5: cycloepoxide.
same experimental conditions with respect
to light intensity and wavelength, photoini-
tiator concentration, film thickness, and the
presence of air. Acrylate monomers appear
to be the most reactive ones, a feature which,
together with the good properties of the
polymer formed, explain the great success
of those compounds in UV-curing applica-
tions.
13.5 Processing of Ultraviolet-
Curable Systems
Because of its distinct advantages, UV-
curing technology is increasingly employed
in an ever-growing number of applications,
mainly in the coating industry, graphic arts,
and microelectronics. A typical industrial
line UV processor is made of two parts: the
coating machine, where the UV-curable
resin is applied onto the substrate, and the
UV oven, where the liquid resin is dried
within a fraction of a second on passing
under a powerful lamp. The precise condi-
629
tions under which each of these two process-
es are conducted will depend on the consid-
ered application.
13.5.1 Coating Applications
Different types of application machines
have been developed in order to deposit a
uniform film of controlled thickness, which
can vary from a few micrometers for UV
inks or printing plates up to 100 |Lim for pro-
tective coatings. The viscosity of these
adjusted for the coating machine used by
adjusting the proportion of diluting
monomer.
Roller coater: Thin layers of a fluid resin
can be applied on rigid or flexible sub-
strates by means of two rollers, which
rotate either in the same direction as the
conveyor belt or in reverse. These rollers
are sometimes heated in order to reduce
the viscosity of the formulation without
adding too much reactive diluent. This
technique is restricted to flat surfaces and
is mainly employed for UV-curable print-
ing inks and finishing varnishes.
Curtain coater: The resin is deposited by
simply flowing laminarly onto a substrate
that moves horizontally. The thickness of
the film is controlled by the width of the
curtain and by the belt speed. This process
is used to apply relatively thick layers
(>50 |um) on substrates of variable thick-
ness and has found its main applications
in wood finishing.
Spraying: A uniform film can also be
applied by means of a spray gun. It is nec-
essary to use a highly fluid resin, a require-
ment which can again be achieved by
warming up the formulation and using a
heated spray head. This technique is well
suited for the surface treatment of three-
dimensional objects and is widely em-
ployed in furniture finishing.
630 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers

13.5.2 Ultraviolet Oven today's UV-curing lines are equipped with

The coated specimen is placed on a con-
veyor and passes into the UV oven where it
is exposed to intense UV radiation. The belt
speed can be varied over a large range,
depending on the application considered.
This is typically a few meters per minute for
wood coatings and rises up to several hun-
dred meters per minute for overprint var-
nishes or printing inks. Figure 13-5 shows
schematically the set-up of an industrial line
UV processor.
As atmospheric oxygen has a strong inhi-
bition effect on the radical-induced poly-
merization of acrylates, especially when it
is carried out as thin films, performing the
UV irradiation under oxygen-free condi-
tions will be highly beneficial. This can be
achieved by flushing the oven chamber con-
tinuously with a nitrogen flow. Because of
its high cost, nitrogen blanketting is restrict-
ed to specific applications where very high
cure speeds are required, such as for the
coating of optical fibers (up to 10 m/s).
UV lamp: The light source plays a key role
in every UV-curing reaction, because only
the photons that are absorbed by the sam-
ple are likely to produce the initiating spe-
cies. It is therefore important to achieve
the best overlap between the absorption
spectrum of the photoinitiator and the
emission spectrum of the lamp. Most of
medium pressure mercury lamps which
can emit intense UV radiation over a long
period of time (>2000 h). Figure 13-6
shows a typical emission spectrum of such
a lamp ("H" bulb), together with the
absorption spectrum of a benzilketal pho-
toinitiator. It can be seen that part of the
emission occurs in the visible range, and
even in the near infrared, thus leading to
heating of the curing chamber. An effi-
cient air-cooling device is therefore nec-
essary to prevent an excessive tempera-
ture rise in the UV oven, as well as to evac-
uate the ozone formed by photolysis of
atmospheric oxygen.
The addition of metal halides to the
mercury vapor leads to a shift of the spec-
tral output towards the visible region. By
converting shortwave UV radiation into
longwave radiation, which is not so
strongly absorbed by the sample, such
doped lamps allow a greater penetration
of light and for a more complete deep-
through cure to be achieved in thick spec-
imens. They also proved most useful for
the photocuring of pigmented systems
(inks, paints), which have a narrow trans-
mission window in the near UV range
(350-400 nm). In addition, this type of
lamp ("D" or "V" bulbs) generates much
less ozone, because it emits hardly any
radiation below 230 nm, where oxygen

UV - OVEN

APPLICATOR

Resin

Coated
plate^
Plate

1m-
3 Figure 13-5. Schematic representation of
an industrial processor for the UV curing of
organic coatings.
 13.5 Processing of Ultraviolet-Curable Systems
Relative intensity
100
80-
200 300 400 500
Wavelength (nm)
Figure 13-6. Emission spectrum of a medium pres-
sure mercury lamp and the absorption spectrum of a
benzilketal photoinitiator (a).
absorbs. A combination of the two types
of lamp is often mounted on the same line
in order to achieve successively a fast sur-
face cure by means of the mercury lamp
and a deep-through cure by means of the
doped lamp.
The power output of the lamps is usually
expressed in watts per linear centimeter. Its
value is typically of the order of 8 0 -
120 W/cm, but it can rise up to 240 W/cm
with some of the newly developed, high-
powered lamps. A 1-m wide UV curing line
will thus require an electrical power supply
of 24 kW per lamp.
Reflector: In order to convey the greatest
part of the light emitted isotropically by
the UV source towards the sample, it is
necessary to use reflectors. These are gen-
erally made of polished aluminum, which
has a high reflectance in the UV and vis-
ible range. Their shape will depend on the
desired irradiation conditions, either a
short and very intense exposure, or a long-
er exposure at medium intensity. A para-
631
bolic reflector provides a relatively wide,
parallel beam (10-20 cm). This is well
suited for curing three-dimensional
objects or for coating heat-sensitive sub-
strates. An elliptical reflector will give the
highest light intensity, which is reached at
the focal point. Such reflectors lead to the
fastest and most extensive curing, mainly
because of the sharp rise of temperature
that occurs during the very short exposure.
It should be emphasized that whichever
reflector is used the total amount of radi-
ation received by the specimen will be the
600 same, i.e., the product light intensity x the
exposure time essentially remains con-
stant. At a line speed of lOm/min, the
energy received by the sample is of the
order of 500 mJ cm"2 for each pass under
the lamp.
13.5.3 Cure Test
Various empirical tests are currently used
to get a rough estimate of the degree of cur-
ing of the coating emerging from the UV-
processing line. The simplest one consists
of touching the sample surface to evaluate
its degree of tackiness. The tack-free test
can also be carried out by spreading talc
powder onto the cured sample and seeing
whether all the particles can be removed
upon blowing. This widely used on-line test
only gives information about the surface
cure. The deep-through cure is best evalu-
ated by the scratching test, which involves
scratching the film with the edge of a fin-
gernail under pressure or with a drawing
pencil of different hardness ranging from
soft (2B) to extremely hard (9H). Other
methods are based on the evaluation of the
coating properties, such as by pendulum
hardness, dynamic modulus analysis, abra-
sion resistance, tape adhesion, or solvent-
rub resistance. Although quite useful from
a practical point of view, these methods pro-
632 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers
vide no quantitative data about the actual
extent of cure. A number of analytical tech-
niques have been employed to more accu-
rately determine the degree of polymeriza-
tion of UV-cured polymers, i.e., the amount
of functional groups which have reacted
upon UV exposure. The performances and
limitations of these techniques have been
discussed and compared in a recent review
article (Decker, 1992 a), and will be present-
ed briefly in the next section.
13.6 Kinetic Study
of Photoinitiated Curing
One of the common features of all UV-
curable systems is the rapidity at which the
polymerization takes place under intense
illumination, usually less than one second.
Therefore it is difficult to accurately follow
the kinetics of such ultrafast reactions,
which is a prerequisite for a better under-
standing and control of the curing process.
Moreover, evaluation of the kinetic param-
eters (rate of polymerization, kinetic chain
length, propagation and termination rate
constants) is essential in order to compare
the reactivity of different photosensitive
resins and assess the performance of novel
photoinitiators and monomers.
13.6.1 Methods of Curing Analysis
Two types of analytical method are cur-
rently used to study the kinetics of radiation
curing:
1) Those based on discrete measurements of
the chemical modifications induced after
a short exposure to UV light (IR or NMR
spectroscopy, gravimetry).
2) Those based on the continuous monitor-
ing in real time of some physical modifi-
cations induced by light, e.g., the heat
evolved, the shrinkage, and changes of
the refractive index or the viscosity.
The first methods provide quantitative
and reliable information on the extent of
cure but, besides being time-consuming
techniques, they do not allow the separation
of the post-polymerization reaction, which
occurs during the lapse of time between the
end of the exposure and the measurement.
For this reason, real-time analysis is carried
out more often, in particular differential
scanning calorimetry (DSC), which is by far
the most widely used technique for photo-
curing kinetic studies [for a comprehensive
review, see Hoyle (1992)]. Its major disad-
vantage lies in the slow response (typically
2 s for a full scale response of the heat flow),
so that it is not possible to monitor polymer-
ization reactions that occur within less than
10 s correctly by DSC. This constraint
requires the use of low intensity radiation
(typically below 10 mW cm"2) and, as a con-
sequence, operation in oxygen-free media,
since oxygen inhibition then becomes more
important, especially in thin films.
13.6.2 Real-Time Infrared Spectroscopy
A novel technique based on IR spectros-
copy has been developed in order to over-
come these limitations. Real time infrared
(RTIR) spectroscopy combines the advan-
tages of the two types of method as it allows
the kinetics of ultrafast photopolymeriza-
tions to be monitored continuously and
quantitatively (Decker and Moussa, 1988).
The sample is placed in an IR spectropho-
tometer chamber and exposed simultane-
ously to the UV beam, which induces poly-
merization, and to the IR analyzing beam,
which monitors the decrease of the IR absor-
bance of the monomer reactive group.
Because of the short response time of the IR
detector (30 ms), this technique permits
 13.6 Kinetic Study of Photoinitiated Curing
Conversion (%)
100
0.5 1 1.5
Exposure time (s)
photochemical reactions that occur within a
few tenths of a second to be monitored and
thus allows operation at the high light inten-
sities found in industrial applications (up to
1 W cnT2).
Figure 13-7 shows some typical conver-
sion versus time curves recorded by RTIR
spectroscopy for an acrylate monomer
exposed to intense UV radiation in the pres-
ence of different types of photoinitiator. The
typical S shape of these curves results from
a combination of two factors:
1) The initial induction period due to the
inhibition effect of oxygen on this
radical-induced reaction.
2) The slowing down of the polymerization
above 30% conversion, due to gelation
with its related mobility restrictions.
The actual rate of polymerization (Rp) can
be determined at any stage of the reaction
simply from the slope of the RTIR profile.
Its maximum value, usually reached
between 10 and 30% conversion, is a reli-
able parameter for comparing the monomer
reactivity or the photoinitiator efficiency.
Another advantage of RTIR spectroscopy is
that it allows a precise evaluation of the
amount of unreacted monomer that remains
in the UV-cured polymer. Knowing this
633
Figure 13-7. Influence of the photoinitiator
(1%) on the polymerization of a polyure-
thane acrylate: 1: benzophenone + amine,
2: benzoin derivative, 3: hydroxyalkyl-
phenone, 4: benzilketal, 5: acyl phosphine
oxide. Light intensity: 80 mW cm"2.
quantity is important, as it is likely to affect
the long-term properties of the final product.
RTIR spectroscopy has proved well suit-
ed for studying the influence of physical and
chemical parameters on the polymeriza-
tion kinetics of different types of mono-
mer (acrylates, vinyliques, epoxides, vinyl
ethers) exposed to UV, visible, or laser radi-
ation (Decker, 1991, 1995; Decker and
Moussa, 1990c, d). Figure 13-8 shows, for
example, the influence of the light intensity
on the UV curing of an acrylate formulation.
This technique can be used for both clear
Conversion (%) mW cnrr2
100
Exposure time (s)
Figure 13-8. Influence of the light intensity on the
polymerization of a polyurethane acrylate. Photoini-
tiator: benzil diketal (3%).
634 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers
and pigmented systems over the range of
thickness typical of coating applications
(1-100 |Lim). RTIR spectroscopy is the most
versatile technique currently available for
following in real time the dynamics of ultra-
fast curing reactions. Quantitative evalua-
tion, speed of analysis, and sensitivity are
among its main advantages; these cannot be
matched by any alternative method of kinet-
ic investigation (Decker, 1992 a).
13.7 Novel Acrylate Monomers
The monomer used to lower the viscosity
of UV-curable resins plays a key role by act-
ing on both the polymerization rate and on
the overall extent of cure, as well as on the
properties of the crosslinked polymer formed.
Increasing the monomer functionality was
found to accelerate the curing reaction, but
also to reduce the final degree of conver-
sion, because of early gelation of the irradi-
ated sample and related mobility restrictions
of the reactive sites. In addition, the great-
er crosslink density leads to glassy polymer
materials that are harder, but also less flex-
ible than monofunctional-type systems.
13.7.1 Reactivity
One of the main goals in UV-curing chem-
istry is to create new monomers that under-
go fast and extensive polymerization to give
polymers with the desired physico-chemical
characteristics. Very promising results have
been obtained by introducing a carbamate
or oxazolidone group in the structural unit
of a monoacrylate (Decker and Moussa,
1990 e; Moussa and Decker, 1993 a)
C H 2 = CH C O C H 2 C H 2 NH C O CH
O CH
Acticiyl CL-960 (SNPE)
CH = CH C O CH 9 CHO N CH O
II II
O C CH2
O O
Acticiyl CL-959 (SNPE) (16)
In the presence of a radical-type photo-
initiator, light-induced polymerization was
found to occur faster than with typical
monoacrylates, and even diacrylate mono-
mers, as shown by the RTIR profiles record-
ed (Fig. 13-9). With a formulation contain-
ing a polyurethane-diacrylate as the oligo-
mer, close to 100% conversion was reached
within a few seconds, thus leading to a cured
polymer containing a very low amount of
unreacted double bonds.
A striking feature observed with these
monomers bearing a single acrylate func-
tion is that they become totally insoluble
upon UV exposure, very much as a difunc-
tional monomer would. An efficient chain
transfer reaction involving the labile hydro-
gens introduced by the carbamate or oxazol-
idone group was considered to be respon-
sible for such a crosslinking process, as well
as for the enhanced reactivity (Decker and
Elzaouk, 1995 a; Moussa and Decker,
1993). UV-curing experiments performed
with benzophenone as the photoinitiator
have confirmed the H donor character of
these novel monomers. The polymerization
developed rapidly and extensively upon
irradiation, in marked contrast to the case
with conventional mono- or diacrylate mono-
mers like hexanedioldiacrylate (HDDA), as
shown by Fig. 13-10.
The reactivity of the UV-curable resin also
depends on the functionality and chemical
CH.
I (15) (15)

Conversion (%)
1001
50-
1 2
Exposure time (s)
Conversion (%)
100
Ebecryl 80
/ A c t i c r y l CL-960
50-
y/ 1
Exposure time (s)
Figure 13-10. UV curing of various acrylate mono-
HDDA
mers in the presence of benzophenone (5%).
structure of the acrylated oligomer used to
create the three-dimensional network, as
well as on its viscosity, which affects the
propagation and termination rate constants.
Aromatic systems usually undergo a faster
but less complete polymerization than their
aliphatic homologs, because of the forma-
tion of a stiff and glassy polymer material
(Fig. 13-11). In this respect, the remarkable
performance of a newly developed amino-
polyester acrylate (Ebecryl 80 from UCB)
should be mentioned; this was found to poly-
merize both fast and extensively, in particu-
13.7 Novel Acrylate Monomers 635
Figure 13-9. Influence of the monomer
used as reactive diluent on the light-
induced polymerization of a polyurethane
acrylate. Monomer/oligomer = 1. Photo-
initiator: benzil diketal (3%). Light inten-
sity: 120 mWcm" 2 .
lar in combination with the oxazolidone-
acrylate monomer (Fig. 13-11). Energy as
low as 0.1 mJ cm"2 proved to be sufficient
to completely insolubilize the photoresist
and obtain a sharp relief image after solvent
development (Decker, 1993 c). Here again,
the high reactivity of this compound seems
to be related to a strong hydrogen donor char-
acter of the molecule (Fig. 13-10), which
favors the chain transfer process and allows
the polymerization reaction to develop
extensively, even in the solid state.
Conversion (%)
1001
Ebecryl 80
0.5 1
Exposure time (s)
Figure 13-11. Light-induced polymerization of var-
ious acrylate functionalized oligomers, with an oxa-
zolidone-acrylate as the reactive diluent. Photoinitia-
tor: benzil diketal (1%).
636 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers
13.7.2 Kinetic P a r a m e t e r s
13.7.2.1 Q u a n t u m Yield
A n important quantity, w h i c h can b e
evaluated from the recorded profiles, is the
polymerization q u a n t u m yield, &p, w h i c h
expresses the p h o t o c h e m i c a l efficiency of
this chain reaction
<PP= (13-3)
number of monomer groups polymerized
number of photons absorbed
It can b e calculated simply by taking the
ratio of the a m o u n t of acrylate double b o n d s
p o l y m e r i z e d after a given exposure [Ao
(1 - x), w h e r e x is the degree of conversion]
to the a m o u n t of p h o t o n s absorbed during
the same time (Iaxt, w h e r e Ia is the absorbed
light intensity). This quantity was found to
drop above 3 0 % conversion as the reaction
was slowing d o w n (Decker, 1990). T h e
initial <Pp values obtained for the various
systems e x a m i n e d are reported in Table
13-1. T h e high reactivities of both the
oxazolidone-acrylate and the polyester-
acrylate oligomer appear clearly from this
quantitative c o m p a r i s o n . With the best per-
forming system, each p h o t o n absorbed is
Table 13-1. Polymerization quantum yield of UV-
curable acrylate resins irradiated in the presence of
aira.
Monomer Op (molecule/photon)
EDGAb HDDAC Acticryl
CL960
Polyurethane-acrylate 200 700 1700
Polyphenoxy-acrylate 230 800 2000
Polyester-acrylate 500 1700 4200
(Ebecryl 80)
Film thickness: 25 |Ltm, light intensity:
500 mW cm"2, monomer/oligomer = 1/1;
ethyldiethyleneglycol monoacrylate;
hexanedioldiacrylate.
capable of inducing the polymerization of
more than 4000 acrylate double bonds, even
in the presence of air. Besides providing an
accurate evaluation of Rp and &p, RTIR
analysis also permits the determination
of the amount of unreacted double bonds
that remain trapped in the UV-cured poly-
mer. For instance, in a rigid polyphenoxy-
acrylate, the unsaturation content was meas-
ured to be about 20% after prolonged irra-
diation, compared to nearly 0% for the elas-
tomeric polyurethane-acrylate.
13.7.2.2 Kinetic Chain Length
The polymerization of multifunctional
monomers generates a three-dimensional
polymer network with an infinite molecular
weight. Therefore it is not possible to eval-
uate the kinetic chain length (kcl) of cross-
linking polymerization from molecular
weight measurements, as is usually done.
One of the distinct advantages of photo-
chemical initiation is that it makes such an
evaluation possible from quantum yield
measurements, since
_ number of acrylates polymerized
number of initiating radicals
= (13
~0~ "4)
Taking an initiation quantum yield &v of
0.4 radical photon"1 for the initiator used
(Groenenboom et al., 1982), the kinetic
chain length was calculated to be 10000
acrylates polymerized per initiating radical
for the most reactive system irradiated in the
presence of air, and up to 50000 in an
oxygen-free medium. Such high kcl values
show how effectively the chain reaction
can propagate in these multifunctional
monomers, even at the high initiation rates
provided by intense illumination.

13.7.2.3 Propagation and Termination
Rate Constants
Individual rate constants of propagation
(kp) and termination (kt) can be evaluated
from the RTIR polymerization profile
recorded during and after the UV exposure
(Fig. 13-10). The ratio kp/k?5 was calculat-
ed from rate measurements under steady-
state irradiation conditions using the follow-
ing equation
(13-5)
Under the nonsteady conditions prevail-
ing after the UV exposure, where initiating
radicals are no longer produced (dark poly-
merization), the rate equation becomes
(Tryson and Shultz, 1979)
[M],
(13-6)
(Rp\
where [M]j and (RF)l represent the monomer
concentration and the rate of polymerization
at the end of the irradiation and the onset of
the dark reaction (7 = 0), and [M]t and (RF)t
Conversion (%
100
DARK
Time (s)
Figure 13-12. Post-polymerization in the dark of a
polyure thane acrylate resin after a 100 ms UV expo-
sure in the absence of oxygen. Photoinitiator: triaryl-
sulfonium salt (2%).
13.7 Novel Acrylate Monomers 637
represent the monomer concentration and
the rate of polymerization, after a given time
/. The linear time dependence of the
left-hand term (Fig. 13-12) allows the ratio
kt/kp to be determined from the slope of
the straight line. For the multiacrylate
monomers studied, the kp value was as high
as 6xlO3 L mol"1 s"1, while the kt value was
only2xl0 4 molL"1 s"1, which is four orders
of magnitude lower than in the polymeriza-
tion of methyl acrylate. A low value of kv
together with a high value of kp, are the main
reasons why such multiacrylate monomers
polymerize so fast upon intense illumina-
tion (Decker and Moussa, 1990f; Decker
et al., 1996).
13.7.2.4 Rate of Chain Growth
An interesting observation was made by
studying the influence of the light intensity
on the polymerization rate of multiacrylate
monomers (Decker and Moussa, 1990 b). As
the light intensity was increased above a cer-
tain value (200 mW cm"2), exactly the same
RTIR curves were recorded. This saturation
effect has been attributed to the fact that
when polymerization occurs very fast the
diffusion of the monomer becomes the
rate-limiting factor, rather than the rate of
production of initiating radicals, which is
then extremely high. The RTIR profile
therefore provides a good estimate of the
actual rate at which the polymer chains are
growing.
Similar curing experiments have been per-
formed by using a pulsed nitrogen laser as
the light source. Here the duration of the UV
emission is only 10~8 s, which is about the
time it takes to generate the initiating radi-
cals. Thus the polymerization itself will only
occur in the dark, so that the curve recorded
by RTIR spectroscopy will accurately reflect
the chain growth process. Its rate will depend
primarily on the propagation rate constant,
638 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers
the number of initiating radicals generated
by the laser flash, and the monomer concen-
tration: Rv = kv [R'][M]. The fact that the
same polymerization profile was obtained
upon pulsed laser irradiation and upon con-
tinuous exposure to high intensity light is a
point in favor of a monomer diffusion con-
trolled reaction under these extreme irradia-
tion conditions (Decker, 1993 c).
13.7.3 Properties of Ultraviolet-Cured
Polymers
The UV-cured polymers based on the
novel acrylate monomers were found to be
completely insoluble in the organic sol-
vents, which makes these very reactive pho-
toresists well suited for imaging applica-
tions. Because of their high crosslink den-
sity, these materials also exhibit a good
resistance to moisture, strong acids, and
weathering (Decker et al., 1991), as well as
to thermal treatment. Accelerated aging
tests conducted at 110 C in the presence of
air have shown that the IR spectra of these
polymers remain essentially unchanged
after 1000 h (Decker and Moussa, 1987 b).
The mechanical properties of these UV-
cured polymers depend primarily on the
chemical structure, functionality, and con-
centration of the various constituents of the
resin, as well as on the irradiation conditions
and on the extent of cure. The crosslinked
polymers containing aliphatic polyurethane
chains show a strong elastomeric character
with a low Tg (<0C) and a good impact
resistance, and they are therefore ideally
suited for the surface protection of flexible
supports. By contrast, UV-cured coatings
containing polyphenoxy chains are hard and
stiff and are more appropriate for the treat-
ment of rigid substrates requiring a good
resistance to scratching.
A quite remarkable feature was observed
with the novel acrylate monomers contain-
ing a carbamate or oxazolidone group when
they were introduced in a UV-curable
polyphenoxy-acrylate formulation. These
highly reactive diluents have the distinct
advantage of imparting both hardness and
elasticity to the crosslinked polymer. Such
photocured films proved to be almost as
hard as glass but, nevertheless, highly flex-
ible, with elongation at break values above
50% (Decker and Moussa, 1990 e).
13.8 Vinyl Ether Monomers
13.8.1 Photoinitiated Cationic
Polymerization of Vinyl Ethers
Vinyl ethers (VE) are known to undergo
an easy polymerization in the presence of
protonic acids (Lapin, 1992). SuchBronsted
or Lewis acids can readily be generated by
the photolysis of diaryliodonium or triaryl-
sulfonium salts
P3 S + *2 RH
0S OS OS 0 + 2 0+4R* +2HPF6 (17)
+
+ C H 2 = C H - O - R >
CH3-CH-O-R (18)
-> Polymer
+ monomer
Figure 13-13 shows the conversion ver-
sus time profile of the divinyl ether of tri-
ethyleneglycol (RapiCure DVE-3 from ISP)
exposed to UV radiation (50 mW cm"2) in
the presence of a sulfonium salt (2 wt.%).
After a short induction period, the polymer-
ization developed rapidly until total con-
sumption of the monomer, so that the cross-
linked polymer contained no residual unsat-
uration. This is due to the elastomeric char-
acter of the polymer formed (low Tg), which
provides sufficient molecular mobility to
the reactive species for completing the chain
process.

Conversion (%)
100
Time (s)
Figure 13-13. Photoinitiated cationic polymeriza-
tion of a vinyl ether monomer. Photoinitiator: triaryl-
sulfonium salt (2%).
When compared to the radical-induced
polymerization of acrylate systems, the
cationic polymerization of vinyl ethers
presents two distinct advantages:
1) It is insensitive to oxygen inhibition
because of the lack of reactivity of the
propagating carbocation toward the O2
molecule.
2) The carbocation species do not react
among themselves, so that, in the absence
of nucleophilic species, the polymeriza-
tion will continue to proceed after the UV
exposure when initiating species are no
longer being created, as shown by
Fig. 13-13.
Vinyl ethers are mainly used in UV-curing
applications, either as reactive diluents to
speed up the polymerization of epoxy-
functionalized oligomers (Crivello et al.,
1983), or to perform the crosslinking of
vinyl ether terminated polymers (Minoda
et al., 1987).
13.8 Vinyl Ether Monomers 639
13.8.2 Photoinduced Curing
of the Acrylate/Vinyl Ether System
13.8.2.1 Cationic Photoinitiator
The photolysis of onium salts generates
both protonic acids and free radicals by
hydrogen abstraction from a donor mole-
cule. Therefore it is possible with a single
photoinitiator to induce the polymerization
of both cationic and radical-type monomers.
Figure 13-14 shows the cure profiles of a 1/1
mixture of DVE-3 and trimethylolpropane
triacrylate (TMPTA) irradiated in the pres-
ence of a sulfonium salt. RTIR spectrosco-
py is unique in that it allows the polymer-
ization of each individual monomer to be
monitored in real time simply by selecting
the proper IR absorbance wavelength
(1415 cm"1 for acrylates and 1628 cm"1 for
vinyl ethers).
The triacrylate monomer was found to
polymerize first and to reach a remarkably
high 90% conversion within a few seconds
as a result of the plasticizing effect of the
vinyl ether monomer. By contrast, the pres-
ence of TMPTA reduces both the polymer-
ization rate and the cure extent of the vinyl
Conversion (%)
1001
1415 cm-1
Acrylate
1628 cm"1
2 3
Exposure time (s)
Figure 13-14. Light-induced polymerization of a
vinyl ether/acrylate hybrid. DVE-3/TMPTA= 1. Pho-
toinitiator: triarylsulfonium salt (2%).
640 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers
ether, because of chain mobility restrictions
100i
brought about by the formation of the stiff
acrylate network. In such a hybrid system,
copolymerization is not likely to occur to a
great extent as vinyl ether and acrylate
monomers polymerize by different mecha-
nisms with the formation of two interpene-
trating polymer networks with well con-
trasted characteristics: on one hand, a hard
and glassy acrylate polymer, on the other
hand, a highly flexible and elastomeric vinyl
ether polymer. Some vinyl ether units might
still be included in the acrylate network, as
the acrylate radicals compete with the VE
carbocations to react with the vinyl ether
double bonds (see below).
13.8.2.2 Radical Photoinitiator
Vinyl ether monomers have the particu-
larity of undergoing a fast radical-induced
copolymerization when they are exposed to
UV radiation together with an acrylate
monomer (Crivello et al., 1983; Dougherty
and Vara, 1990). While inactive toward the
electron-rich vinyl ether double bond, vinyl
ether radicals are capable of reacting with
the electron-poor acrylate double bond.
When a TMPTA/DVE-3 mixture was
irradiated in the presence of an acyl phos-
phine oxide photoinitiator, the two mono-
mers were found to polymerize simultane-
ously (Fig. 13-15), with TMPTA polymer-
izing twice as fast as DVE-3. A great differ-
ence was observed between the two
monomers with respect to the overall cure
extent: nearly all the triacrylate had poly-
merized after 3 s of exposure (97% conver-
sion), whereas the vinyl ether polymeriza-
tion stopped after 2 s at only 50% conver-
sion. The cure limitation of the vinyl ether
must be due to the fact that essentially all of
the acrylate functions have already poly-
merized or are no longer accessible to the
VE radicals after 2 s of irradiation.
Conversion (%)
Acrylate
DVE-3 + TMPTA
Vinyl ether
1 2 3
Exposure time (s)
Figure 13-15. Light-induced radical polymerization
of a vinyl ether/acrylate hybrid. DVE-3/TMPTA= 1.
Photoinitiator: acylphosphine oxide (3%).
A direct consequence of the faster poly-
merization of the acrylate functions is that
the UV-cured copolymer contains a larger
amount of polymerized acrylate units than
of polymerized vinyl ether units. The com-
position of the monomer mixture was found
to have a strong influence on both the
respective rates of polymerization and the
composition of the crosslinked copolymer
(Decker and Decker, 1994). Based on these
data, acrylate radicals were shown to be
twice as reactive toward the acrylate double
bond as toward the vinyl ether double bond.
All the kinetic results obtained point to a
copolymerization mechanism involving a
cross-propagation of the vinyl ether and
acrylate radicals, together with a homopoly-
merization of the acrylate moiety, to give a
copolymer with isolated VE units according
to Scheme 13-3.
For a 1/1 monomer feed composition, the
copolymer will contain three times more
acrylate than vinyl ether units, with the fol-
lowing type of sequence for the growing
polymer chain
-A-VE-A-A-A-VE-A-A-VE-A-
A-A-A-VE-A- (19)

13.8.3 Photoinduced Curing of the
Maleate/Vinyl Ether System
Vinyl ethers can also copolymerize by a
radical mechanism with unsaturated esters,
e.g., maleates or fumarates, with the forma-
tion of an alternating copolymer (Noren
et al., 1990; Schouten et al., 1992). While
no significant homopolymerization could
be seen when DVE-3 or the dimaleate of
diethyleneglycol (DMA-2) was exposed
alone to UV light in the presence of an a-
hydroxy-alkylphenone photoinitiator, a fast
copolymerization developed in an equimo-
lecular mixture. Whatever the initial com-
position, the two monomers were found to
disappear at exactly the same rate to give a
highly crosslinked alternate copolymer con-
taining equal amounts of vinyl ether and
maleate units (Fig. 13-16).
The rate of polymerization reaches its
maximum value for a DVE/DMA feed ratio
of 1, as shown by Fig. 13-17. Also, for an
equimolar composition, the total amount of
unreacted double bonds is the lowest. For
ratios different from unity, the monomer in
excess will remain unpolymerized in the
cured polymer (Fig. 13-17).
By studying the influence of the monomer
concentration on the polymerization rate,
it was possible to determine whether the
chain reaction was proceeding by a cross-
propagation process or through a donor-
acceptor complex. The cross-propagation
mechanism will give a square root depen-
13.8 Vinyl Ether Monomers 641
A VE A*
Scheme 13-3.
dence of the polymerization rate on the
product of the monomer concentrations
(Decker and Decker, 1994)
VE* + MA VE - MA* (20)
MA* + VE MA - VE* (21)
0.5
_[ fr2 k2\ (13-7)
05
x(<2>i / a ) 05 x[MA]0055 x[VE]] 0 5
The second mechanism is based on the
homopolymerization of an MA-VE accep-
tor-donor complex, which leads to a linear
dependence of the polymerization rate on
the product of the monomer concentations
MA ^ (MA-VE) (22)
1
(13-8)
Photopolymerization experiments per-
formed at various compositions have shown
that Rp varies linearly with the product
[MA]x[VE] (Fig. 13-18). This result dem-
onstrates that the photoinitiated copolymer-
ization of DVE-3 with DMA-2 proceeds by
a mechanism where the propagating species
is a donor-acceptor complex. The fact that
polymerization was found to occur even in
the absence of added photoinitiator, by
direct excitation of the donor-acceptor com-
plex, provides further evidence in favor of
this mechanism (Decker and Decker, 1994).
642 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers

ChL DVE-3 CHO

CH-O-CH2-CH2-O-CH2-CH2-O-CH-CH^-O-CH
R-O-C-CH CH-C-O-R
II I DMA-2
O
CH C - O - C H CHO O-CH CH,OC-CH
2
I II k I
CH. CH
2
I I

R-O-C-CH CH-C-O-R
0 O Figure 13-16. Structure of the UV-
CH-C-O-R C-CH
0II I cured vinyl ether/maleate copoly-
U
Total residual Rp (mol I"1 s-1
Cure Rate (mol kg" 1 unsaturation (%) '
100
1.5

DVE-3 50/50 DMA-2 5 10

Monomer molar ratio [VE][MA] in mol2 V2

Figure 13-17. Light-induced radical polymerization
of a vinyl ether/maleate hybrid. Dependence of the
rate of polymerization () and the residual unsatura-
tion content (A) on the composition of the monomer
mixture. Photoinitiator: [a-hydroxyalkylphenone] = 2%.
Figure 13-18. Variation of the rate of polymerization
with the monomer concentrations product in the
photopolymerization of a vinyl ether/maleate hybrid.
DVE-3/DMA-2=l.

One of the distinct characteristics of mul- sional polymers or interpenetrating polymer

tifunctional vinyl ethers, besides their great networks, as well as statistical or alternate
reactivity, lies in their versatility, because copolymers (Table 13-2). Polymer materi-
they can generate by UV-curing tridimen- als with quite different properties have thus

Table 13-2. UV curing of vinyl-ether-based systems.

Monomer Co-monomer Polymer Mechanism

Divinyl ether tridimensional network cationic

Divinyl ether triacrylate interpenetrating polymer network cationic + radical
Divinyl ether triacrylate crosslinked copolymer radical
with isolated VE units
Divinyl ether dimaleate crosslinked alternate copolymer radical
 13.9 Ultraviolet Curing of Acrylic Monomers in a Polymer Matrix 643

been produced by acting on the formulation Conversion (%)

Sol fraction (%)
Hardness (s)
composition and on the selected photoini- 100
tiators and co-monomers.
-400

13.9 Ultraviolet Curing -300

of Acrylic Monomers
in a Polymer Matrix -200

When the light-induced polymerization -100

of a multifunctional monomer is carried out
in a polymer matrix, a semi-interpenetrating
polymer network will be formed. This type Exposure time (s)
of photopolymer has recently attracted the
Figure 13-19. Light-induced polymerization of a tri-
attention of polymer chemists, for it makes acrylate monomer (TMPTA) in a PMMA matrix.
it possible to rapidly create new organic Photoinitiator: [a-hydroxyalkylphenone] = 5%. Light
materials with tailor-made properties, intensity: 600 mW cm"2.
which cannot be achieved with a single
polymer alone (Moussa and Decker,
1993 b). The reaction kinetics have been ing process. After 2 s of exposure, the gel
studied quantitatively by IR spectroscopy fraction was 93%, which means that up to
for a triacrylate monomer (TMPTA) 86% of the PMMA has been incorporated
dispersed in various polymer binders: into the acrylate polymer network, probably
poly(methylmethacrylate), poly(vinylchlo- through a chain transfer reaction.
ride), polyurethane, and natural rubber.
w
I
+ C (PMMA)
13.9.1 Poly(methylmethacrylate)
(PMMA)
Conversion versus time curves show that
the polymerization of TMPTA, dispersed in (23)
PMMA in a 1/1 weight ratio, starts imme-
diately upon intense illumination (600 mW
cm"2), half of the aery late functions being TMPTA I
polymerized after only 0.1 s of exposure CH 9

(Fig. 13-19). Further irradiation leads to a I

slower increase of the degree of conversion,
which levels off at about 80% compared to
only 60% for the polymerization of TMPTA
in bulk. At the same time, the UV-cured
polymer becomes hard and insoluble in the
organic solvents. The fact that more than
50% (the original binder content) of the
cured material was found to be insoluble
provides strong evidence in favor of a graft-
CH C O
II
o
This process would also account for the
surprisingly high degree of cure reached in
such a glassy material, where molecular
mobility is likely to be very low.
A most remarkable feature is that it takes
an exposure as short as 0.1 s to transform
the elastomeric PMMA plasticized by the
644 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers
triacrylate monomer into a high modulus,
very hard material. Such an ultrafast photo-
forming process is likely to find applica-
tions in various industrial sectors. Com-
pared to thermoforming, UV-curing tech-
nology has the great advantage of allowing
molding to be performed at ambient temper-
ature in a very short time, by simple expo-
sure to UV light.
13.9.2 Poly(vinylchloride) (PVC)
Similar results have been obtained by
exposing TMPTA to UV radiation in a PVC
matrix, in the presence of a radical photoini-
tiator (3%) of an ce-hydroxyalkylphenone).
Here again, the high degree of conversion
(85%) and almost complete insolubilization
(95% gel fraction) observed after a few sec-
onds irradiation were explained on the basis
of an efficient chain transfer reaction in-
volving the labile hydrogens of the PVC
chain.
DSC experiments provide further evi-
dence indicating that a large fraction of the
PVC binder is chemically bonded to the
acrylate polymer network. The glass transi-
tion temperature of the TMPTA/PVC semi-
IPN was found to be located around 130 C,
which is 50 C above the Tg of virgin PVC,
but still below that of poly (TMPTA), which
rises above 150C for an extensively cured
polymer.
It should be mentioned that the light
intensity has a strong influence not only on
the cure speed, as expected from the rate
equation, but also on the final degree of con-
version, which rises from 50 to 85% when
Io is increased from 35 to 600 mW cm"2.
This enhancing effect was attributed to the
greater temperature reached in samples irra-
diated at high light intensities, because of
the large amount of heat evolved by the reac-
tion in such a short time (Kaczmarek and
Decker, 1994). This should favor the chain
propagation by increasing the molecular
mobility. Indeed, moderate heating at 70 C
for a few minutes was found to increase the
degree of conversion of the UV-cured sam-
ple from 60 to 75%, in good agreement with
previous observations (Decker and Moussa,
1987 c). Based on the heat of polymeriza-
tion (80 kJ per mole of acrylate polymer-
ized) and on the heat capacity of the system
(ca. 2 J/g/K), the temperature increase was
calculated to be of the order of 200 C, under
adiabatic conditions, for the highest light
intensity used in this study. Because most of
the heat evolved in the 25-|nm thick film is
rapidly dissipated by conduction, the actu-
al temperature is not likely to rise much
above 100 C.
13.9.3 Polyurethane (PUR)
Aliphatic polyurethanes (PURs) are
attractive polymers because of their great
elasticity, high impact resistance, and good
weatherability, but they prove vulnerable to
solvent attack and scratching. Polymerizing
in situ a multifunctional monomer is one of
the possible ways of improving the proper-
ties of such materials by creating a semi-
interpenetrating polymer network.
The rate of polymerization of TMPTA
was found to be substantially lower in a PUR
matrix than in PVC or PMMA. In addition,
80% of the binder remained soluble after
UV curing, thus indicating a poor grafting
efficiency. A substantial improvement in
reactivity has been achieved by replacing
TMPTA by an acrylate end-capped polyure-
thane chain (Actilane 23 from SNPE),
which showed good compatibility with the
PUR binder. The polymerization of the acry-
late group initially developed as fast as in
PVC or PMMA upon UV exposure, and
reached 100% conversion within less than
1 s (Moussa and Decker, 1993 b).
 13.9 Ultraviolet Curing of Acrylic Monomers in a Polymer Matrix
This highly reactive photopolymer
proved particularly well suited for adhe-
sives applications, because of its great elas-
ticity, good impact resistance, and excellent
adhesion on various supports. It was
employed to produce safety glasses by a
faster and cheaper process than the usual
thermal cure of polyvinylbutyrals under
high pressure (Decker and Moussa, 1995).
13.9.4 Natural Rubber
Another elastomer that can be readily
transformed into a semi-IPN by photocur-
ing is natural rubber, as shown by Fig. 13-
20. In this soft material, the light-induced
polymerization of hexanediol diacrylate
(HDDA) occurred even faster than in PVC
and PMMA, with the formation of a hard but
still flexible film. Rapid polymerization of
the isoprene groups of the rubber chain was
found to take place at the same time
(Fig. 13-20); this will therefore contribute
to the crosslinking of the binder. The fact
that the polymerization of the isoprene units
stops prematurely at 45% conversion, when
Conversion (%)
ACRYLATE
ISOPRENE
25
0.2 0.4 0.6 0.8 1.0
Exposure time (s)
Figure 13-20. Light-induced polymerization of a
diacrylate (HDDA) in a natural rubber matrix. Photo-
initiator: [acylphosphine oxide] = 5%. Light intensity:
600 mW cm' 2 .
645
most of the acrylate double bonds have poly-
merized, is a point in favor of a copolymer-
ization mechanism leading to a rubber-
acrylate network with isolated isoprene
units.
Similar results have been obtained
with an acrylate-functionalized rubber,
which generates by copolymerization with
TMPTA a tridimensional polymer network
in which the TMPTA chains are chemically
grafted onto the crosslinked rubber (Le
Xuan and Decker, 1993). Here again, the
isoprene double bonds were found to under-
go a fast polymerization as long as acrylate
double bonds were available.
A true IPN was formed when TMPTA was
irradiated in an epoxidized rubber matrix in
the presence of a cationic photoinitiator (tri-
arylsulfonium salt). Here the crosslinking
polymerization of the poorly reactive epoxy
group developed surprisingly fast and
extensively, as shown by Fig. 13-21. The
radical initiated polymerization of TMPTA
occurred at the same time, thus leading to
the independent formation of two inter-
penetrating polymer networks with well-
Conversion (%)
100
0.4 0.6
Exposure time (s)
Figure 13-21. Light-induced polymerization of a tri-
acrylate (TMPTA) in an epoxidized rubber matrix.
Photoinitiator: [triarylsulfonium] = 4%; () triaryl-
sulfonium (4%) + acylphosphine oxide (2%). Light
intensity: 600 mW cm"2.
646 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers
contrasted characteristics. The UV-cured
polymer combined the properties of the
elastomeric rubber network and of the hard
and glassy acrylate network, and proved
therefore to be very resistant to impact,
scratching, and abrasion, which makes this
material particularly well suited for coatings
applications.
A dual polymer network was generated
by polymerizing a functionalized rubber
bearing both epoxy and acrylate groups in
its main chain (Decker et al., 1994)
CH 3 CH3 (24)
3
V O OH
I
O = C CH = C H 2
The interesting feature is that here the two
IPNs, which are formed by different mech-
anisms (cationic and radical, respectively),
are tightly bound together through the rub-
ber chain, thus enhancing the network char-
acter of the crosslinked polymer.
13.10 Industrial Applications
of Ultraviolet Curing
UV-curing technology has found its
major openings in sectors where its distinct
advantages (fast cure, solvent-free formula-
tion, selective cure in illuminated areas)
have allowed it to outclass the other process-
ing techniques. It must be recognized that,
except in some specific areas, such as in
wood and plastic coatings, and overprint
varnishes, UV-radiation curing has not yet
achieved a real breakthrough and remains
marginal in terms of overall market share
(Dufour, 1993). Acrylate resins remain by
far the most widely used UV-curable
systems, with a total annual production of
approximately 60000 tonnes, compared to
less than 30000 tonnes for the unsaturated
polyesters in styrene (mainly for wood coat-
ings), while cationic-type resins represent
only a minor part (2000 tonnes). The appli-
cation fields in radiation curing can be
divided in four main areas: graphic arts,
coatings, adhesives, and electronics.
13.10.1 Graphic Arts
One of the most successful applications
of UV-curing technology is found in the
graphic arts, where this process has expand-
ed at a sustained pace during the last decade.
UV curing is used both in the pre-press part
of the operation to produce the printing
plate, as well as in the printing process itself
with the development of fast-drying, UV-
curable inks with low residual odours. It also
intervenes in the last step, when an overprint
varnish is to be applied in order to obtain
high quality glossy images.
13.10.1.1 Printing Plates
The printing process consists of the rapid
transfer through an ink of a given image
from a printing plate to a substrate (usually
paper), thus allowing a fast production of
prints. There are several processes current-
ly used in printing that involve the use of
UV curing: letterpress, gravure, flexogra-
phy, screen printing, and lithography [for a
detailed description, see Horton (1993)].
The different steps of the imaging process
are shown schematically on Fig. 13-22.
The printing plate is usually made of an
anodized aluminum sheet coated with a pho-
tosensitive layer, which is sometimes pro-
tected by a transparent film (laminate). The
thickness of the UV-curable layer can vary
from a few micrometers (for lithographic
plates) to a few millimeters (for flexolitho-
graphic plates). Imaging is achieved by
selective UV-exposure through a photo-
 13.10 Industrial Applications of Ultraviolet Curing
UV UV
EXPOSURE
DEVELOPMENT
PRINTING
mask, i.e., a silver negative obtained by a
traditional photographic process. Each plate
is uniformly exposed for about 30 s, usual-
ly under vacuum. Photocrosslinking only
occurs in the illuminated areas and leads to
insolubilization, with the formation of a
contrasted image, which needs a develop-
ment step in,order to be revealed. The solu-
ble, unexposed areas are easily washed
away by treatment with an aqueous-based
solvent. The relief image thus obtained will
serve repeatedly to transfer ink to the sub-
strate to be printed. The photocured coating
must be chemically inert towards the vari-
ous cleaning, development, and etching
solutions, as well as very resistant to abra-
sion in order to ensure a long service life in
the printing operation.
647
Photomask
Protective layer
Photosensitive layer
Support
Ink
Figure 13-22. Manufacturing prin-
ciples of a printing plate by photo-
lithography.
13.10.1.2 Ultraviolet-Curable Printing
Inks
Pigmented resins can be cured by UV
radiation provided that the proper photoini-
tiator be used, i.e., a compound that absorbs
in the transmission window of the pigment.
A number of such photoinitiators have been
developed for this specific application
(Dietliker, 1991) and proved to be very
effective for instantaneously curing acrylic
printing inks. Such UV inks present a
number of advantages over conventional
solvent-based inks:
Their high viscosity allows several colors
to be applied successively, wet on wet, and
it allows the drying to be carried out by a
single UV-exposure step.
Because they contain no solvent, radia-
tion-cured inks show no broadening of the
648 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers
dot, which leads to a better print defini-
tion and high gloss images.
The UV process is more economic in that
it requires less energy and achieves a high-
er productivity, with cure speeds up to 400
m/min for a few micrometer thick layers.
The whole process is performed at ambi-
ent temperature, without any solvent
emission, which makes it more friendly to
the environment.
The remarkable performances explain
why UV-curable inks are used increasingly
nowadays in the printing industry to achieve
high quality prints, not only on paper and
cardboard, but also on various kinds of plas-
tic and metal for decorative purposes.
13.10.1.3 Overprint Varnishes (OPVs)
For some specific applications, it is
necessary to further improve the surface
properties of the printed material, in partic-
ular its gloss, smoothness, abrasion and
scratch resistance, as well as its weathering
resistance for outdoor applications. This can
be achieved by applying a thin layer
(~5 |Lim) of a UV-curable varnish, which is
known to give high gloss and smooth sur-
faces.
Different types of polyurethane-acrylate
or epoxy-acrylate resins (or a combination
of the two) can be used in order to obtain a
top coat showing the desired properties to
effectively protect a printed substrate, espe-
cially with respect to the flexibility, hard-
ness, and abrasion resistance. The varnish is
usually applied by roller coaters, but also by
offset machines which offer the possibility
of printing and overprinting in line. UV-
cured OPVs have found a number of appli-
cations, in particular for the surface finish-
ing of postcards, book covers, metal cans,
and all kinds of packing materials.
13.10.2 Coatings
UV-curable varnishes are increasingly
used, not only as overprint clear coats, but
also as highly resistant coatings to protect
essentially any substrate: wood, plastic,
metal, glass, optical fibers, paper, leather,
fabrics, etc. In these applications the film
thickness is typically of the order of 20 -100
|Lim to ensure a long-lasting protection. The
coating can be applied onto the substrate
either by spraying or by a roll coater or a
curtain coater, depending on the desired film
thickness. The low viscosity of these resins
allows the coating to flow and level to form
a smooth finish. The coating is cured by
passing into a UV processor, up to 2 m wide,
consisting of a controllable, variable speed
conveyor belt and a battery of UV lamps, as
shown on Fig. 13-5. Some of the major
applications of UV curing in the coating
industry will be briefly reviewed next.
13.10.2.1 Wood Finishing
UV coatings have been used on wood sub-
strates for over 20 years, mainly as filters
and sealers for particle boards and other por-
ous substrates. With the development of
high molecular weight/low viscosity resins,
UV-curing technology is increasingly em-
ployed for finish and decorative purposes.
Currently, the most widely used resins are
unsaturated polyester-styrene, because of
their low cost, but they are being progres-
sively replaced by the more suitable acry-
late resins which offer a larger choice of end
properties of the cured film and are well suit-
ed for a specific application. When more
than one layer is applied, e. g., base coat and
top coat, sanding in between each layer is
often necessary to obtain a smooth surface
and achieve good interlayer adhesion. With
the development of efficient photoinitiators
absorbing in the near UV region, UV-curing
 13.10 Industrial Applications of Ultraviolet Curing
technology is not restricted to clear coats but
can now be applied to pigmented finishes,
thus allowing more emphasis to be given to
aesthetics and design than protection. The
fastest growing market of UV-cured lac-
quers is to be found in door finishing, par-
quet flooring, and furniture.
13.10.2.2 Plastic Coatings
A number of plastic materials are current-
ly protected by UV-cured, clear coats in
order to improve their surface properties and
aspect. The most widely treated substrate is
poly(vinyl chloride) (PVC), which is used
in floor covering, either as flexible rolls or
as rigid tiles. The resin formulation usually
contains a polyurethane-acrylate which
imparts good abrasion resistance, high
gloss, and durability to the cured polymer.
UV finishes are also applied on PVC wood
grain printed foils designed to be laminated
onto particle boards using conventional
methods (pressure and temperature).
UV-cured, clear coats are increasingly
used for the surface protection of organic
glasses, such as polycarbonates (PC) and
poly(methylmethacrylate) (PMMA), in
order to increase their hardness and wear
Gloss (%)
100 p ^
90-
80- PVC
70
Yellow
Index
i() PVC Coated PVC
J 1000 2000 3000
QUV Exposure time (hours)
649
and scratch resistance, as well as their
weathering resistance, without affecting
their optical properties. Good adhesion will
be achieved if some of the coating compo-
nents can diffuse into the plastic substrate
to form a transition layer. Today, UV-curing
finishing is used for a great variety of arti-
cles, such as lenses, mirrors, car headlamp
covers and reflectors, optical fibers, and
spectacle glasses.
By introducing a light-stabilizer in the
coating formulation, the light-fastness of
polymer materials known for their poor
resistance to weathering, e.g., polycarbo-
nates and PVC, can be substantially
improved. By filtering the most harmful
solar radiation out, the UV absorber effec-
tively retards the photooxidation of the sub-
strate, thus increasing the service life of the
coated material. This stabilizing effect is
clearly apparent on Fig. 13-23, which shows
the yellowing and loss of gloss of a clear
PVC plate exposed to accelerated QUV
aging. A five-fold increase in the light
stability was achieved by simply covering
the PVC plate with a 50-|im thick, UV-
cured, polyurethane-acrylate coating con-
taining 1.5% of a hydroxyphenyl triazine
stabilizer (Tinuvin 400 from CIBA)
Coated PVC
4000
Figure 13-23. Photostabilization of a clear
PVC plate using a UV-cured coating con-
taining a UV absorber.
650 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers
(Decker, 1993 d). Delamination of the coat-
ing upon weathering was prevented by the
addition of a radical scavenger which stabi-
lizes the polyurethane network as well as the
UV absorber, and greatly reduces the deg-
radation at the coating/substrate interface.
It should be mentioned that the introduc-
tion of a UV absorber slows down the cur-
ing reaction because it reduces the initiation
rate by competing with the photoinitiator in
scavenging the incident photons. This diffi-
culty can be overcome to a large extent by
using as a stabilizer a compound that is
transparent in the near UV and generates a
UV absorber in situ upon weathering (Deck-
er et al., 1995).
13.10.2.3 Metal Coatings
Although the energy savings provided by
the UV curing process are the greatest on
metal, this application sector has not yet
experienced great development. This is
partly due to the fact that good adhesion on
metals is quite difficult to obtain, mainly
because of the tension forces produced by
the shrinkage of the coating (Dufour, 1993).
Protective UV varnishes are applied on steel
pipes, to prevent corrosion, and on galva-
nized steel used in metallic furniture.
Another application of metal coatings is in
the manufacture of printed circuit boards,
where UV-curable photoresists are coated
onto a copper substrate before photo imag-
ing and subsequent etching of the unprotect-
ed areas (see Sec. 13.10.4).
13.10.3 Adhesives
Radiation curing has found two main
areas of application in the field of adhesives:
(i) to bond together two pieces of an assem-
bly (laminate), thus acting as a quick-setting
glue, and (ii) to produce pressure-sensitive
adhesives and release coatings (Woods,
1992).
13.10.3.1 Laminated Adhesives
An important limitation to the use of UV-
curable adhesives for bonding an assembly
is that one of the two parts must be trans-
parent to UV radiation. The process
involves the following three steps:
1) The adhesive is applied in the liquid state
to one of the parts to be bonded.
2) The two parts are assembled, taking care
to avoid the formation of air bubbles.
3) The assembly is exposed to UV light to
convert the adhesive from the liquid to
the solid state.
The two elements to be bonded can be
identical (homolaminates) or of a different
nature (heterolaminates), and consist either
of flexible films (polyester, polyvinyl ace-
tate, nylon, aluminum foil, paper) or of rigid
transparent plates (PMMA, PVC, PC, min-
eral glass).
UV-cured glass laminates show a great
potential as safety or acoustic glasses,
because they are produced by a process that
is faster, cheaper, and easier to work out than
the usual thermal cure carried out for hours
under high pressure. The photosensitive
system can be either a liquid resin to be
poured into a glass mold and UV cured at
ambient for less than one minute, or a plas-
ticized, photosensitive polymer film to be
squeezed between two glass plates under
moderate pressure and hardened by a short
UV exposure. In both cases, acrylate mono-
mers associated to an aliphatic polyurethane
were found to give the best performance in
terms of reactivity, adhesion, impact resis-
tance, transparency, and weathering resis-
tance (Moussa and Decker, 1993 b; Decker
and Moussa, 1995). Promising results have
been obtained with a three-component, UV-
cured laminate glass/polycarbonate/glass,
which combines the chemical inertness,
scratch resistance, and hardness of mineral
 13.10 Industrial Applications of Ultraviolet Curing
glass with a strong impact resistance due to
the polycarbonate core, which is sand-
wiched between two sheets of a UV-cured
polyurethane acrylate elastomer (Moussa
and Decker, 1992).
13.10.3.2 Pressure-Sensitive Adhesives
(PSAs)
The concept of radiation-curable PSA can
be simply described as a rapid photoinitiat-
ed crosslinking producing a viscoelastic
system where the properties of tack, peel
strength, and shear resistance are predeter-
mined (Ellerstein et al., 1993). It is this
tackiness that causes the adhesive to stick
instantly when it is pressed against a sub-
strate. Depending on the peel stength, PSA
tapes are considered as temporary
(<35 N/100 mm) or permanent (above this
value).
The photosensitive resin consists either of
a functionalized oligomer, usually with acry-
late groups, or of a reactive polymer which
will be applied as hot melt. There are basi-
cally two classes of reactive polymer used:
acrylic hot melts which may contain a tack-
ifying monomer, and thermoplastic rubbers,
predominantly block copolymers of styrene
with isoprene or butadiene (Huber, 1993).
The reasons for using radiation to produce
PSAs, rather than solvent-based adhesives,
remain essentially the same as for the other
UV-curable systems, and include pollution
control, economic gains, and enhanced per-
formance. Today, UV-curable PSAs are
increasingly utilized in the graphic arts,
electronics, and packaging to produce self-
adhesives foils, tapes, and labels.
13.10.4 Electronics
UV-curable systems have found several
applications in microelectronics where they
serve not only as photoresists in the imag-
651
ing step, but also as fast drying adhesives
and conformal coatings. In the manufacture
of printed circuit boards (PCBs), the photo-
lithographic process, which generates high
resolution relief images, is similar to that
presented in the graphic arts section
(Fig. 13-22), except that the printing step is
replaced by an etching step to transfer the
image into the copper substrate. Photocur-
able acrylate resins are currently used as
etch resists, solder masks, and marking inks.
The imaging performance of negative
working photoresists, i.e., systems that
undergo insolubilization upon exposure, are
quantified by two kinetics parameters: (i)
the photosensitivity (S), which corresponds
to the amount of energy required for total
insolubilization (usually expressed in mJ
cm"2), and (ii), the contrast (7), which is cal-
culated from the slope of the insolubiliza-
tion profile and reflects the sharpness of the
relief image. S values of a few millijoules
per square centimeter, together with a y>2,
are required in the manufacture of PCBs,
and are typically obtained with multifunc-
tional acrylate resins.
Conventional exposure tools, such as
contact printers, require the fabrication of
patterns on glass or film photomasks. Alter-
natively, a computer-controlled scanning
laser can be used to define a pattern direct-
ly on the photoresist. This maskless tech-
nology, laser direct imaging (LDI), offers a
means to produce boards with finer geome-
tries at higher yields (Chinnock, 1994). The
basic principle of LDI and its great poten-
tial in electronics have been discussed at
length in a recent review article on laser cur-
ing and imaging, and its manifold applica-
tions (Decker, 1994).
A schematic representation of the laser
writing device is shown in Fig. 13-24. The
modulated laser beam scans at high speed
the resist-coated board to produce the
desired pattern. Because the exposure time
652 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers

Rotating Polygon
Modulator Mirror

Lens

Correcting
mirrors

Transport
module

CW Laser

Figure 13-24. Laser scanner for direct

imaging of printed circuit boards.

is very short (10 7 s), the sensitivity of the 13.10.5 Stereolithography

photoresist must be extremely high (low
values of S). This can be achieved by using
multiacrylate resins which have been found
to polymerize quasi-instantly under UV
laser irradiation (Decker, 1983 b, c). With
some recently developed photoresists,
which show excellent performance (S =
0.1 mJ cm"2, 7=4), writing speeds up to
1000 m/s can be reached by means of an
argon ion laser tuned to its UV emission
(Decker and Elzaouk, 1995 b).
Laser direct imaging offers a number of
advantages, such as sharper and well-
defined lines, fewer defects, rapid prototyp-
ing, and greater flexibility in the manufac-
ture of PCBs. This advanced technology is
likely to become a valuable tool in the hands
of engineers to help overcome some of
today's limitations in the PCB industry, by
producing in a cost-effective way boards
with higher definition, more layers, and
smaller batch size.
One of the most remarkable features of
laser-induced curing is that it allows a liq-
uid resin to be transformed quasi-instantly
into a solid material; this phase change is
carried out selectively in the very areas that
are exposed to the laser beam (Decker,
1984). A new technology, stereolithogra-
phy, has taken advantage of this property to
create three-dimensional solid objects, by
scanning the surface of a UV-curable resin
with a laser to form a thin solid pattern, and
building up the model step-by-step by add-
ing one layer on top of another (Bernhard
et al., 1993). Complex 3D parts can thus be
obtained faster, with greater precision, and
more flexible processing than with conven-
tional modeling techniques. Figure 13-25
shows a schematic representation of the
laser stereolithography apparatus. Different
types of UV lasers can be used, the com-
monest being the argon ion laser (351 nm)
and the helium-cadmium laser (325 nm).
The photoreactive resin employed for
generating models by stereolithography
plays a key role in that it directly determines
 13.10 Industrial Applications of Ultraviolet Curing
LASER
/
/ \
OPTICS
COMPUTER CONTROL
. ,*- X - Y PLOTTER
USER INTERFACE
Laser beam
\
Object
ELEVATOR
Liquid
UV-curable
resin
both the laser writing speed and the mechan-
ical properties of the final object. Most of
today's commercial resins are based on mul-
tiacrylate systems, which were selected pri-
marily because of their high cure speed
under laser irradiation (Decker, 1984,1994)
and the tailor-made properties of the cured
polymer. In addition, there is substantial
experience with this type of compound,
which is most widely used in UV-curing
applications. These laser-curable resins are
essentially the same as those described in
Sec. 13.4. One of the practical problems
encountered with acrylate resins is that the
liquid-to-solid phase change is accompa-
nied by a relatively important shrinkage
(5 -10%). This will affect the ultimate accu-
racy of the 3D-object created. For this rea-
son, cationic UV-curable systems are
increasingly employed as laser-sensitive
resins for 3D imaging applications, because
of their low shrinkage (nearly 0%) and good
reactivity when associated to vinyl ethers.
Stereolithography has proved of great
interest in various industrial sectors (auto-
motive and aerospace industries, medical
engineering) for the prototyping of solid
653
Figure 13-25. Apparatus for creating 3D
objects by laser stereolithography.
objects, for it obviates the use of molds,
machine dies, and cutting tools. The success
of this advanced technology arises from the
fact that it allows the direct use of digital
design information to guide the formation
of a model that closely represents the orig-
inal design.
13.10.6 Dental Composite Materials
In the same way that pigment particles are
introduced in the formulations of UV-
curable printing inks or lacquers, it is pos-
sible to add some mineral charges such as
glass or silica particles to obtain an extreme-
ly hard and abrasion-resistant composite
material. This approach has found its major
opening in dentistry, where photocured den-
tal polymeric materials are increasingly
used as fast-hardening cements, sealants,
adhesives, and coatings (Linden, 1993).
Such one-pack resins present a number of
advantages over conventional systems:
- immediate readiness for use,
- extended working time,
- higher polymerization rate and short set-
ting time,
654 13 Photopolymerization and Ultraviolet Curing of Multifunctional Monomers
- better adhesion of the filler particle to the
resin matrix.
Photocurable dental pastes generally con-
tain methacrylate functionalized oligomers
(mainly bisphenol-A derivatives and poly-
urethanes) and a reactive acrylate monomer
to render the paste more malleable and
increase its reactivity. Because UV radiation
can cause skin cancer and damage to the
eyes, the curing has to be performed with
visible light, typically 470-nm radiation, so
the photoinitiator must absorb at this wave-
length. The most widely used photoinitiator
is camphorquinone which, in combination
with a tertiary amine, generates upon pho-
tolysis the initiating amine radical (see
Sec. 13.3.2).
The inert filler is the most important com-
ponent of the formulation as it can represent
up to 60% by volume of the total composi-
tion. It is usually made of small particles of
glass or silica, with a size ranging from 10
to 50 |Lim. To increase the polishability of
the cured cement, microfilled composites
have been developed by using as filler col-
loid silica with submicrometer particles
(0.05 |Lim). Some of the mechanical proper-
ties (hardness in particular) are, however,
inferior to those with larger particles, so that
the present trend is towards hybrid systems
containing both types of particle. Because
of the high filler content, the penetration of
light in these composite resins is limited,
and it is difficult to cure more than 3-mm
thick layers. Dental restoration by photocur-
able composites therefore has to be carried
out in a multiple step process, one layer on
top of another. Each layer is typically
exposed for 15 s to the blue light of a halo-
gen lamp.
As expected for this kind of application,
light-cured polymeric dental materials have
to pass a number of tests in order to evalu-
ate their biocompatibility (Linden, 1993).
The physical and aesthetic properties of
photocured dental resins are generally con-
sidered to be fully equal in quality to the
conventional ones. This feature, together
with the distinct characteristics of photoini-
tiation, accounts for the success of photo-
curing technology in dentistry and the large
variety of products which are now commer-
cially available (Linden, 1993). Light-cured
polymeric materials with ready-to-use sin-
gle paste are expected to experience a fast
growth in the near future, as they show the
great advantage of permitting complete con-
trol over the working time, together with a
relatively short setting time.
Other promising applications of photo-
and laser-induced polymerization include
the fast curing of composite membranes and
reinforced plastics (Bellobono and Righet-
to, 1993), the 3D imaging of holographic
recording media (Lougnot, 1993), and the
production of micrometer-size optical
guides by a laser-direct-write process
(Decker, 1992b).
13.11 Conclusions
Radiation curing has now become a field
of recognized importance in various indus-
trial sectors because of its unique advantag-
es regarding both process facility and prod-
uct quality. While this technology has found
its major openings in the coatings industry
and in microlithography, new applications
have appeared in microelectronics, holog-
raphy, and 3D-protoyping, as well as for the
production of fast-drying adhesives and
composite materials.
The high initiation rates that can be
reached under intense illumination allow
highly crosslinked polymeric materials to
be synthesized quasi-instantly by the UV
curing of multifunctional monomers. Such
ultrafast reactions are best monitored by

real-time infrared spectroscopy, a technique
that makes it possible to evaluate the impor-
tant kinetic parameters and assess the per-
formance of new monomers and photoini-
tiators under the same conditions as those
used in most industrial applications.
Significant progress has recently been
achieved with the development of different
types of highly reactive multifunctional
monomers and functionalized pre-
polymers. An important objective for future
research in this area is to further improve
not only the efficiency of these compounds
and photoinitiators, but the properties of
the UV-cured polymers as well. Thorough
mechanistical studies are also required for
a better understanding and control of the
various processes involved in such ultra-
fast crosslinking polymerization reactions.
Based on present achievements, the pros-
pects of radiation curing look rather bright.
They lie, above all, in the hands of the chem-
ist and his ability to create new materials
with tailor-made properties, but also in the
skill of the engineer to fully exploit the per-
formance and great potential of this
advanced technology.
13.12 Acknowledgements
The author thanks his co-workers at the
Polymer Photochemistry Laboratory: Drs. S.
Biry, D. Decker, B. Elzaouk, H. Kaczmarek,
H. Le Xuan, K. Moussa, and T. Nguyen.
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14 Conducting Polymers and Applications
Ladislav M. Wilson

Department of Chemistry, University of Cambridge, Cambridge, U.K.

List of Symbols and Abbreviations 661

14.1 Introduction 663
14.2 The Main Polymer Types and Structures 664
14.2.1 Structure, Doping, Conductivity, and Processing 667
14.2.2 Polymer Structure, Morphology, and Processability 670
14.3 Processing Insoluble Conducting Polymers (CPs) 670
14.3.1 Chemical Synthesis and Processing 671
14.3.2 Electrochemical Synthesis and In Situ Deposition 673
14.4 Processing Soluble Conducting Polymers for Films:
Soluble Polymers and Solubility Induced in Polyaniline by 'Soaps' . . 675
14.4.1 Soluble Polymers by Chemical Polymerization:
(3-Alkyl)Polypyrroles and Polythiophenes 676
14.4.2 Polyaniline and Substituted Poly anilines 678
14.4.3 Poly[2,5-alkoxy(phenylene-vinylene)]s and Soluble Poly(/?-phenylene)s . 678
14.5 Precursor Routes to 'Unprocessable' Polymers 679
14.5.1 Precursor Routes to Polyacetylene (PAC) Films 679
14.5.2 Precursor Routes to Poly(phenylene-vinylene) (PPV)
and Heterocycle-Vinylenes 680
14.5.3 Precursor Routes to Poly(/?-phenylene)s and Other Polymers
with p-Phenylene and Vinylene Units 681
14.6 Oriented Langmuir-Blodgett and Other Thin Films 683
14.7 Processing Fusible Polymers, Polymer Blends, and Latexes 685
14.8 Forming Polymers into Fibers 685
14.9 Post-Forming Treatment for Conductivity and Strength:
Polymer Doping and Stretch-Aligning 686
14.10 Other Conducting Polymers: Polymer Electrolytes 692
14.10.1 Filled Polymers 692
14.11 Applications 692
14.11.1 Photopolymerization and Photolithography 693
14.11.2 Conducting Polymer Film Devices in Electronics 694
14.11.2.1 Polymer Transistors 695
14.11.2.2 Light-Emitting Polymers 696
14.11.2.3 Electrochromic Devices 698
14.11.2.4 Polymer Battery Electrodes and 'Electrolytic' Capacitors 699
14.11.3 Antistatic Fabrics, Coatings, Filled Matrices, and Shielding 700
14.11.4 Chemical Detectors and Electrode Sensors 700
14.11.5 Copper Electroplating for Printed Circuits 701
Materials Science and Technology
Copyright WILEY-VCH Verlag GmbH & Co KGaA. All rights reserved.
660 14 Conducting Polymers and Applications

14.11.6 Nonlinear Optics and Photonics 701

14.11.7 Miscellaneous 701
14.12 References 702
 List of Symbols and Abbreviations 661

List of Symbols and Abbreviations

E Young's modulus
hv radiation energy
Mn number average molecular weight

a conductivity

ACN polyacene
COD cyclooctadiene
COT cyclooctatetraene
CP conducting polymer
CPA copolymer with perylene units
CSA camphor sulfonic acid
DC direct current
DMF dimethylformamide
DP degree of polymerization
EC electrochemical cell
ECD electrochromic device
EDTA ethylenediaminetetraacetic acid
FET field effect transistor
HT head-to-tail
IR infrared
ITO indium tin oxide
LB Langmuir-Blodgett
LCD liquid crystal display
LED light-emitting diode
LEP light-emitting polymer
LPPP "ladder" poly(/?-phenylene)
MEH-PPV poly[2-methoxy-5-(2-ethyl)hexyloxy]phenylene-vinylene
MIS metal-insulator-semiconductor
NLO nonlinear optical
NMP 7V-methylpyrrolidone
PAC polyacetylene
PANi polyaniline
PBD 1,4-poly(buta-1,3-diene)
PCB printed circuit board
PDAC polydiacetylene
PDMPV poly(2,5-dimethoxy)phenylene-vinylene
PEO poly(ethylene oxide)
PET poly(ethylene terephthalate)
PMMA poly(methylmethacrylate)
PP polypropylene
PPP poly(p-phenylene)
PPS poly-/?-phenylene sulfide
662 14 Conducting Polymers and Applications

PPV poly(phenylenevinylene)
PPy polypyridine
PTFE poly(tetrafluoroethylene)
PTH polythiophene
PVAcetate polyvinylacetate
PVAlcohol polyvinylalcohol
PVC polyvinylchloride
PVK poly(AT)vinyl carbazole
PYRo polypyrrole
ROMP ring-opening metathesis polymerization
S Siemens
SCE saturated calomel electrode
STM scanning tunneling microscopy
THF tetrahydrofuran
UHMW-PE ultrahigh molecular weight polyethylene
UV ultraviolet

14.1 Introduction
Traditional polymer materials or plastics
have become almost universally used in
so many applications that it is now difficult
to imagine a world without them. They
have been used for their many useful prop-
erties, e.g., ease of processing into desired
shapes, low cost, electrical insulation, flex-
ibility or toughness, and often chemical
inertness. However, the use of polymers
for their electrical conducting or electronic
semiconducting properties is relatively
new, and these new conducting polymers
(CPs) offer an exceptional combination of
useful properties and possibilities for a wide
range of general and also specialized appli-
cations (Dai et al., 1996;Dodabalapuret al.,
1995; Bakhshi, 1995). The possibility of
combining the useful properties of conven-
tional polymers, especially their ease of
processing and good mechanical proper-
ties, with the electrical conductivity of
metals have been the main goal and the driv-
ing force for the new field of 'synthetic
metals'.
The usefulness of a conducting or semi-
conducting polymer is clear, since this con-
ductivity is needed for electrical and elec-
tronic applications. There is a need for the
properties associated with plastics, e.g.,
their flexibility and their low weight com-
pared with metals. There are also process-
ing advantages that make conducting poly-
mers desirable compared to metals or inor-
ganic semiconductors, for example, in the
coating of large areas. There is now great
interest in using (semi)conducting polymers
in electronics, as it is possible to make tran-
sistors, light emitters, and batteries using
these polymer materials. Applications of
CPs can be in the high volume, 'low
technology' market as well as the low vol-
ume, high value electronics market, and CPs
are expected to be a billion dollar business
14.1 Introduction 663
by the end of the millenium. Therefore,
although the total production volume of CPs
might be low compared to that of conven-
tional polymers used in injection molding,
film blowing, or extrusion, they are at least
as important because of the total sales turn-
over of the final products, and while the pro-
cessing of CPs for low volume electronics
applications can be expensive compared to
the techniques used for conventional bulk
polymers, particularly if very high purity
and multi-step fabrication processes are
needed, this cost is not a problem if it can
be offset by the high value of the applica-
tion.
The processing of CPs covers a wide and
rapidly changing area, with many unique
processes distinct from conventional poly-
mer processing techniques, although they
are often applied as thin (or very thin) films
(Gardner et al., 1995;Saitoet al., 1994; Shi-
midzu et al., 1996). While conventional
nonconducting polymers are usually easily
fabricated, strong, flexible, and often inex-
pensive, many CPs were not normally so
easily synthesized or processed until quite
recently, because they have a conjugated
structure. In fact some of the conjugated
polymers used as CPs were originally
designed to be structural materials, with ten-
sile properties comparable to rigid engineer-
ing polymers, and they often have the asso-
ciated intractability and difficulties in pro-
cessing. For example, poly(phenyleneviny-
lene), PPV, has elastic moduli and tensile
strength comparable to Kevlar. Another pro-
cessing difficulty for some CPs (in the
doped conducting state) is their environ-
mental instability in normal ambient condi-
tions. However, much progress has been
made recently towards ease of processing
and higher stability, often with the develop-
ment of new types of polymers and the so-
called 'precursor' polymer routes or new
doping techniques.
664 14 Conducting Polymers and Applications
Research has also been directed towards
improving the conductivity of these materi-
als, either alone or in blends. Those that
are environmentally stable, such as polypyr-
role (PYRo), polyaniline (PANi), and poly-
thiophene (PTH) based materials have
found a wide range of uses and are commer-
cially available. As with conventional poly-
mers, the processing of CPs largely deter-
mines the properties of the final polymers
and is in turn itself determined by the prop-
erties required for particular applications.
For CPs the processing treatment is crucial
because it determines the conductivity of the
final polymer as well as the mechanical
properties.
Although the conducting properties of
some organic polymers were discovered in
the 1960s, research has accelerated over the
past 20 years. The impetus came in the
1970s with the discovery by Shirakawa and
Ikeda (1971) that poly acetylene (PAC)
could be made into free-standing films (Ito
et al., 1974), and that these could be made
highly conducting (Chiang et al., 1977;
Shirakawa et al., 1977) by doping. But the
environmental instability of PAC was a
drawback, and a boost came with the
synthesis of the more stable conducting
poly(p-phenylene) PPP, by Shacklette et al.
(1979) and their discovery that this polymer
could also be made conducting by doping
(Shacklette et al., 1980), along with others:
polypyrrole (PYRo) by Kanazawa et al.
(1979), poly-/?-phenylene sulfide (PPS) by
Chance et al. (1980) and Rabolt et al.
(1980), polythiophene (PTH) by Kaneto
et al. (1982), and the poly anilines (PANi) by
MacDiarmid et al. (1985). This opened up
the way for other conjugated and some non-
conjugated polymer materials. Intensive
research by both academic institutions and
industry in the 1980s and 1990s has already
led to important commercial applications
[see, e.g., Aldissi (1993b)].
14.2 The Main Polymer Types
and Structures
The structures of the main types of con-
jugated polymers are shown in Fig. 14-1,
together with some (initially) nonconjugat-
ed structures, e.g., polyaniline (PANi),
which are made conducting (and conjugat-
ed) by doping. Polyacetylene (PAC) has the
most simple conjugated structure, being a
chain of trans - C H - units with alternating
single and double carbon bonds and having
a band gap of 1.5 eV. Polydiacetylenes,
polytriacetylenes, and copolymers such
as poly(aromatic diacetylenes) have been
made by a copper-catalyzed coupling reac-
tion, and some of these are soluble (Kwock
et al., 1993). Other materials include poly-
pyrrole (PYRo), polythiophene (PTH),
with a band gap of 2.1 eV (M. Kobayashi
et al., 1984), poly(p-phenylene) (PPP),
poly(phenylenevinylene) (PPV), and poly-
(p-phenylene sulfide) (PPS). Soluble mod-
ifications of these polymers have been syn-
thesized, e.g., (3-alkyl)PTH, (2,5-dialkoxy)
PPP (Vahlenkamp and Wegner, 1994), and
2,5-dialkoxy)PPV, which are important pro-
cessable polymers. Further modifications of
the structure are possible, e. g., to give fused
dithiophene phenylenevinylenes, and the
phenyl-substituted PPV type polymers with
the phenyls on the vinylene units can be oxi-
datively cyclized with ferric chloride to give
the fully aromatic phenanthrene polymers,
which are organic solvent soluble. Phenyl-
substituted PPVs (with the phenyl substitu-
ents on the rings) have also been investigat-
ed, and can be drawn above their softening
points. Doping with iodine or SbF5 gave
conductivities of about 10~4 S/cm (Garay et
al., 1995).
Many of these more specialized polymers
with modifications to their chemical struc-
tures will not be discussed in detail as there
are an almost endless number of possible
 14.2 The Main Polymer Types and Structures 665

PAC variations and many are still at an experi-

mental stage. Polymers containing different
aromatic units, e.g., pyridine, pyrimidine,
quinones, and resorcinol ethers have been
PDAC synthesized (e.g., Maude et al., 1995).
Other recent materials, e.g., thiazole poly-
mers (Maruyama et al., 1995), poly(alkyl-
PYRo bithiazoles), and poly(isothianaphthene)
(Chen and Lee, 1995; Nanos et al., 1995),
having low band gaps, are conventionally
processable and conducting when doped.
PTH
Copolymers have also been investigated,
having combinations of different monomer
units in the polymer chains, for example,
(3-Alkyl)PTH copolymers based on phenylene and thio-
phene units (Czerwinski et al., 1988) or
phenylene and pyrrole (Reynolds et al.,
PPV 1994), and other polymers similar to PPV
but containing heterocyclic units together
with vinylene, such as poly(heteroarylene-
vinylene)s (Gandini and Mealares, 1994).
(2,5-Oxydialkyl)PPV Conducting polyalkyldioxy thiophenes
have been produced which are conductive-
ly very stable, the material containing units
that stabilize the positive charges on the
PPP conducting polymer (Heywang and Jonas,
1992).
Another class of polymers for which
(2,5-Dialkyl)PPP research is currently ongoing is the fused
ring 'ladder'-type polymers, which are
sometimes referred to as 'one-dimensional
graphite', for example, polyacene (as shown
PANi in Fig. 14-2), although the syntheses are
often difficult and the materials totally
intractable. However, some of these ladder
PPS polymers can be synthesized by Diels-Alder
condensation to give soluble precursor
polymers which are then converted to the
Figure 14-1. The structures of the main types of con-
ducting polymers: Polyacetylene (PAC), polydiacet- fully aromatic materials by dehydrogena-
ylene (PDAC), polypyrrole (PYRo), polythiophene tion (Schlicke et al., 1995); new soluble lad-
(PTH), poly(3-alkyl)thiophene [(3-alkyl)PTH], der polymers derived from the PPP struc-
polyphenylene-vinylene (PPV), poly(2,5-dialkyloxy)- ture (LPPP) have also been synthesized
phenylene-vinylene [(2,5-dialkyloxy)PPV], poly(/?-
phenylene) (PPP), poly(2,5-dialkyl)-/7-phenylene
(Scherf and Mullen, 1991), possessing a pla-
[(2,5-dialkyl)PPP], polyaniline (PANi), and poly-p- nar arrangement of the phenylene units
phenylene sulfide (PPS). along the polymer chain. An interesting
666 14 Conducting Polymers and Applications

H H H H H H
I I I
LPPP
Doped * AVV4#^A /V/
PAC c c xcd c d c c c
I I I I I I I
H H H H H H H
R1 = alkyl, R2 = aryl

Doped
PTH
ACN

Doped
PANi
H H H H

CPA ci- ci-

or
H
Figure 14-2. Ladder-type polymers :PPP-type ladder =\ I /=
N NI
polymer (LPPP), the "one-dimensional graphite" A /- if\\ ^ N
polyacene (ACN), and a copolymer with perylene
and
units (CPA).

(c)

example of a soluble polyacene has been
synthesized by a high temperature and pres-
sure solid-state polymerization from diphe-
nylacetylene (Kojima et al., 1995).
Polymers having electron donating and
withdrawing groups along the polymer
chain backbone have been found to have
extremely low band gaps, for example,
polymers with quinoid aromatic units and
thiophene units, and the polysquaraines and
polycroconaines with a band gap of 0.5 -0.7
eV (Havinga et al., 1992; Lambert and Fer-
raris, 1991). These can be water soluble and
the films have a conductivity of about
1 S/cm when doped.
The doped, conducting forms of polymers
represented in Fig. 14-1 are shown in
Fig. 14-3. Note that although the undoped
PANi (like the PPS) in the neutral state does
not have a conjugated polymeric structure,
when it is doped in the fully oxidized per-
nigraniline form it does have a fully conju-
gated structure (Fig. 14-3 c) and a partially
Figure 14-3. Schematic structures of doped conduct-
ing polymers. Iodine-doped PAC, p-doped PTH, and
p-doped PANi showing the ideal structural formulas
of the different forms: (a) emeraldine salt, (b) emeral-
dine base, and (c) pernigraniline.
conjugated structure (Fig. 14-3 b) when par-
tially oxidized. The materials shown are
only a representative group, as there is in
fact an almost endless number of possible
new variations of conjugated polymer struc-
tures (for example, those with different sub-
stituents on the polymer) and of combina-
tions of different monomers and comono-
mers to give copolymers.
An example of a different type of con-
ducting polymer showing low conductivity
is poly(AOvinyl carbazole (PVK), which is
not actually a conjugated polymer even
when doped, as shown in Fig. 14-4. This
material relies on electron hopping between
the carbazole units to give conduction.
 14.2 The Main Polymer Types and Structures
PVK
PBD
H
Figure 14-4. Structure of two nonconjugated (semi-
conducting polymers, poly(/V)vinyl carbazole (PVK)
and l,4-poly(buta-l,3-diene) (PBD).
PEO-LiX
Figure 14-5. Structure of an ion-conducting poly-
mer: solid polymer electrolyte poly(ethylene oxide)
(PEO) doped with a lithium salt (LiX).
Another material having a nonconjugat-
ed backbone is l,4-poly(buta-l,3-diene)
(PBD), also shown in Fig. 14-4. The all
trans form of this polymer turns dark and
becomes a semiconductor when doped with
iodine, having a conductivity of about
10~5 s/cm.
Filled conducting polymer materials are
of practical importance, but will not be dis-
cussed in detail here. Some polymeric solid
electrolytes are important in some CP appli-
cations, e.g., in secondary batteries, and are
shown schematically in Fig. 14-5, but will
not be discussed further here.
14.2.1 Structure, Doping, Conductivity,
and Processing
The nature of the chemical bonding in
conducting polymers is the key to their
conducting properties and their processing.
All the so-called intrinsically conducting
organic polymers have an extensive conju-
667
gated system of multiple bonds, either in
the doped or the undoped state, most often
containing alternating double and single
bonds along the polymer chains. This
conjugated system of covalent bonding
leads to small band gaps. Therefore the
polymers are often intrinsic semiconductors
(but sometimes still insulators) when pure
(or 'pristine'), and these materials do not
show high metal-like conduction until they
are doped by being oxidized (p-doped,
which is more common) or reduced (n-
doped).
The p-doped materials have positive
charges on the polymer chains (except mate-
rials such as the PANi base forms shown in
Fig. 14-3; compare with the charged PANi
salt form) and contain negative counter ions,
while the n-doped materials have negative
charges on the polymer chains and contain
positive counter ions. The intrinsic semicon-
ductor properties of the pure (undoped)
materials can be used in some semiconduc-
tor device applications. In the terminology
of semiconductors, the materials are in fact
extrinsic rather than intrinsic conductors
when doped, although the latter term is nor-
mally used. The doping can be done in a
variety of ways: chemical, electrochemical,
or by irradiation. In electronic devices such
as field effect transistors (FETs) there is the
possibility of charge injection, as in other
semiconductors. Chemical doping is per-
formed by treatment with oxidizing or reduc-
ing agents, or with acids (Han and Elsen-
baumer, 1989). Examples of dopants include
I2, AsF5, SbF5, (oxidizing), Na, Li (reduc-
ing), and HC1, camphor sulfonic acid (CSA)
(acid), which can be applied in the vapor
state, for example, by exposing the polymer
to the dopant in a vacuum chamber.
The effect of doping is shown schemati-
cally as follows
POL + nX (14-1)
agent
668 14 Conducting Polymers and Applications

where X = I2, Br2, AsF5, SbF5, etc., and silver and copper), conducting polymers can
X" = l3,15, SbF^, etc. have values anywhere between these
Reducing
extremes, as shown in Fig. 14-6. For exam-
POL + nM agent T (14-2) ple, PVK is conductive when doped with
SbF5, to about 1(T5 S/cm (Partridge, 1983),
+ + +
where M = Na, Li, etc., and M = Na , Li , polythiazole has conduction when n-doped
etc. with sodium of about 10~4 S/cm (Maruya-
ma et al., 1995), and the electron-accepting
POL + nHA - ^ U POL nH(n+) nA~ (14-3)
polyarylenes containing the 7T-deficient
where HA = HC1, etc., and POL = polymer. electron withdrawing imine nitrogens, such
Electrochemical doping can be per- as 2,5-polypridine (Kanbara and Yamamo-
formed in situ during synthesis of the poly- to, 1993) and 2,6-polyquinoxaline (Yama-
mer or after synthesis during further pro- moto et al., 1993), also show conduction
cessing of the polymer. Doping is accompa- when n-doped. All the CP materials inves-
nied by a drastic color change, often to a tigated so far have low to medium conduc-
dark color or black, together with a dramat- tivities when doped, e. g., PANi (Baughman
ic increase in the conductivity. While con- et al., 1988) and PPP (Mohammad et al.,
ventional plastics are insulating, with con- 1996), and up to several hundred or a little
ductivities between 10~14 and l(T 18 S/cm over a thousand Siemens per centimeter for
(the lower limit for Teflon and polystyrene) PTH, the exception being PAC, which has a
and metals have values in the range conductivity greater than a few thousand
104 S/cm to 106 (the higher value being for Siemens per centimeter up to about 105 S/cm

10 +06 1 0 + 0 6 -i Copper
Polyacetylene
Platinum
Poly(arylene-vinylene) - 1 0 + 0 4 10+04-
Polythiophene, polypyrrole Graphite
PQlyaniline 10 +02 10+02_
Synthetic
Polyfuran
<5 10+0 -
10-02. Germanium
8.
c
10- 0 4 -
Semicon- Silicon
ductors 10-06-
o
o 1 0 -08_ Polyethylene
O

10 - 1 2 -
Diamond

PTFE
S/cm 1 0 " 1 8 - Quartz
Figure 14-6. Conductivity chart showing the conductivities of conventional materials and the highest conduc-
tivity values for various polymers.
 14.2 The Main Polymer Types and Structures
when increased by stretch alignment (Naar-
man and Theophilou, 1987). The doped
films of PAC have a shiny metallic appear-
ance and the very highly conducting form is
called Naarman polyacetylene, in honour of
Naarman who first reported it. Iodine is
often used as a dopant and another possible
dopant for PAC is thionyl chloride, which
can produce a highly conducting state (Cal-
vertetal., 1988).
In conventional metallic materials, the
electrical conductivity depends on the elec-
tronic band structure and the available elec-
trons in the bands. With the bands either
totally full or empty there is no conduction,
but with partially filled bands and a band
gap that is comparable to the thermal exci-
tation energy conduction can occur. In these
polymers, however, conductivity is due to
the formation of solitons, polarons, and
bipolarons; the theoretical treatment of the
conduction mechanisms have been covered
in Vol. 4 of this Series. The conductivity of
these polymers is therefore produced by
doping (Rehwald and Kiess, 1992), and it
depends on the quantity and power of the
oxidizing or reducing dopant, which is con-
trolled by the processing conditions.
Defects in the molecular structure disrupt
the conduction paths along the polymer
chains, since it is the actual average conju-
gation path length along the polymer chains
that carries the charge. This average length
is the average distance between two defects
or the chain ends, and in defect-free poly-
mers has been equated with the persistence
length of the polymer chain. For example,
the conductivity of PAC decreases rapidly
when this conjugation length is reduced
from 100 A (10 nm) (the value for pristine
polymer) to 10 A; it decreased by eight
orders of magnitude (Roth et al., 1989), as
shown in Fig. 14-18 b. Work on the Ziegler
catalyzed polymerization to produce PAC
has produced high molecular weight poly-
669
mers with fewer defects (of the nonconju-
gated units) in the chains, which limit con-
ductivity. The conductivity can then be
increased further by increasing the order of
the polymer chain structure and packing,
i.e., increasing the planarity of the monomer
units in the chains and decreasing the num-
ber of conformational defects (Salaneck,
1989) in the chain packing by alignment of
the polymer molecule chains with each
other, which increases the average conjuga-
tion length along the molecules, giving an
essentially parallel orientation. Thus the
processing determines the conductivity of
the final polymer to a large extent. The con-
formational defects in CPs can give rise to
thermochromism [examples include polydi-
acetylene and the substituted (3-alkyl)PTH,
in solution and in the solid state], because
the conformation of the monomers along the
polymer chain is temperature-dependent
and causes a color change on changing the
degree of conjugation.
Interestingly, the conductivity of CPs
often increases with temperature, unlike for
metals, but for very highly doped PAC mate-
rials the conductivity is nearly temperature-
independent (Roth et al., 1989), as shown in
Fig. 14-22 b, and metallic-type conductivity
has been observed, for example, in PANi
[Holland et al. (1996), and see Sec. 14.9].
Conduction theory predicts that in a per-
fect single crystal of doped polyacetylene
the conductivity should be 2xlO7 S/cm,
which is higher than that of copper metal.
This shows the importance of oriented CP
materials and why the processing of CPs is
crucial. However, in practice the presently
observed maximum conductivity is a few
hundred times lower. Figure 14-6 shows the
maximum presently observed conductivity
of polymers on a scale from insulating
(quartz and PTFE) to conducting (copper).
The processing method is also important
in another way, as the nature of the contact
670 14 Conducting Polymers and Applications
interface of the metal or other conductor
[e.g., indium tin oxide (ITO)] with the CP
is critical in the performance of some devic-
es, e.g., transistors and light-emitting poly-
mer (LEP) devices; therefore the surface
treatment must be carefully controlled.
14.2.2 Polymer Structure, Morphology,
and Processability
The conjugated structure of CPs presents
difficulties when it comes to processing of the
materials, as mentioned when describing the
structures in Sec. 14.2.1. Because of the
extended conjugation and often also the rigid
aromatic repeat units in the polymers, flex-
ibility due to rotation about the axis of the
bonds along the polymer chain is restricted.
Thus the chains are rigid and stiff, and because
twisting and coiling in solution or in the melt
are prevented, they are insoluble, intractable,
infusible materials (or have such high 'melt-
ing points' that the material itself degrades),
and they are potentially highly crystalline.
The materials can also be chemically reac-
tive and very unstable in the doped state
under ambient conditions, for example,
PAC; undoped pristine PYRo is also not oxi-
datively stable (but it is more stable in the p-
doped state). It is an advantage to be able to
process the polymers in the doped state,
avoiding the need to dope the polymers after
they are formed. The processing techniques
and strategies that have been developed are
designed to circumvent these problems by
modifying the chemical structures of the
polymers, the polymerization processes, and
the processing routes to the final materials.
Over the last twenty years there has been a
search for improved materials; these have
now been produced and are coming to the
application stage. Major advances in the
chemical preparation of modified monomers
and polymerization techniques have led to
many of these advances in processing.
Some of the materials, for example, the
soluble polymers, can be processed by the
normal techniques used for conventional
polymers, while other processing methods
are more complex and are unique to CPs.
Among the main polymer types, PAC, PPP,
and PPV are usually prepared by the solu-
tion processing of a precursor polymer to
give films, and the precursor is then con-
verted to give the product. PANi, PYRo, and
PTH are usually electrochemically pro-
cessed to give films, while soluble, modi-
fied 'hairy rod' forms of PPP, PTH, and PPV,
e.g., (2,5-alkoxy)PPV, and other materials
have been synthesized, as well as the solu-
ble ladder polymer LPPR They are soluble
in common organic solvents such as
toluene; the LPPPs can be solution pro-
cessed (Leditzky and Leising, 1995) and
have been evaluated in LEP devices (Tasch
et al., 1996). The strategies used for pro-
cessing these and other polymers are dis-
cussed in the following sections.
Several of the CPs can be prepared as dis-
persions and applied as coatings (Aldissi,
1993 b). Many of them can be blended with
conventional thermoplastics such as poly-
ethylene or poly vinyl chloride to produce a
conducting material that is readily pro-
cessed by conventional methods, e.g., extru-
sion. These conventional processing meth-
ods are described elsewhere. To avoid rep-
etition, each of the processing techniques
will be discussed in turn with respect to the
relevant polymers.
14.3 Processing Insoluble
Conducting Polymers (CPs)
The problem of the processability of
insoluble and intractable polymers can be
circumvented in some cases by direct in situ
deposition of the CP, for example, by elec-
trochemical deposition of PYRo, PTH, and
 14.3 Processing Insoluble Conducting Polymers (CPs)
PANi to give films and coatings of the insol-
uble materials. The polymers can be formed
by photopolymerization and the films of the
materials crosslinked by irradiation, but
these processes will be discussed more
appropriately later (Sec. 14.11.1) in con-
nection with the applications of photoli-
thography. Films of insoluble polymers can
also be formed by chemical synthesis, for
example, the Ziegler catalyzed polymeriza-
tion or ring-opening metathesis polymeriza-
tion (ROMP) method for PAC.
14.3.1 Chemical Synthesis
and Processing
The original synthesis of PAC by Shira-
kawa and Ikeda [1971; also Ito et al. (1974)]
used solution polymerization with a Ziegler
catalyst to prepare the films. Materials with
improved conductivity can now be pro-
duced by this Ziegler catalyzed process
using high temperature aged catalysts
(Naarman and Theophilou, 1987; Basescu
et al., 1987), although the material has a
fibrillar, open morphology and is less com-
pact, with a lower density and conductivity
than the precursor route material discussed
in Sec. 14.5.1. Highly strechable PAC films
with a higher density and high mechanical
strength have been produced by changing
the Ziegler process (Akagiet al., 1989; Sue-
zaki et al., 1987) to a nonsolvent process.
A standard Ziegler type catalyst such as
Ti(OC4H9)4-AlEt3 in cumene solvent was
aged at room temperature for 1 h, then heat-
ed at 150 C for 5 h under an inert argon
atmosphere. The catalyst solution was then
transferred into the polymerization vessel
and the cumene removed under vacuum
pumping until the vapor pressure fell below
5 m Torr (667 mPa) to leave a coating of the
catalyst lining the vessel. Polymerization
was then carried out at -78 C by introduc-
ing acetylene at a pressure of 600 Tor
671
(80 kPa). The thickness of the PAC film
could be controlled by the initial thickness
of the catalyst layer coating and by the poly-
merization time. The films could be washed
with solvent in situ and were then handled
in an inert atmosphere, such as argon, to pre-
vent oxidative degradation by air.
Films of several micrometers to about 100
jLim thickness can be produced. The materi-
als as produced are initially cis-rich PAC
and can be converted to the predominantly
trans-PAC by heating at 150-160 C under
nitrogen or in a vacuum for 30 - 40 min, nor-
mally under stress to retain the sample
geometry. The differences between films
produced by the different processes have
been investigated (Shirakawa et al., 1991).
It was found that the most important factor
affecting the conductivity was the thickness
of the film, the conductivity increasing in
proportional with the inverse of the thick-
ness, i.e., the thinner the films, the higher
the conductivity, as shown in Fig. 14-7.
A different method for processing PAC
involves the ring-opening metathesis poly-
Film thickness (urn)
5.0 2.5
0 2 4 6 8 10
Reciprocal of film thickness (103 crrr 1 )
Figure 14-7. Relationship between the electrical
conductivity of iodine-doped, as-prepared films and
the reciprocal of the film thickness (Shirakawa et al.,
1991). Reprinted with permission from Elsevier
Science Ltd., Oxford, UK.
672 14 Conducting Polymers and Applications
merization (ROMP) of cyclooctatetraene
(COT); by having a side-chain substituent
on the COT monomer, a soluble substituted
form of PAC can be made as follows
(14-4)
X \=
This method does not use the acetylene
gas monomer or the extremely air and mois-
ture sensitive Ziegler type catalyst, instead
it uses a liquid monomer and a less sensitive
tungsten complex catalyst (Ginsberg et al.,
1990). The instability of doped and even
undoped PAC in normal atmospheric condi-
tions is still a great hinderance to the appli-
cations of this highly conducting material.
Both PANi and PYRo can be chemically
synthesized by oxidative polymerization,
usually using Fe m or Cu11 salts (Costello
et al., 1996), or persulfate (for PANi), and
PYRo can be polymerized directly onto fab-
ric fibers (Gregory et al., 1991), within pre-
formed polymer matrices (Pouzet et al.,
1993); it can even be grown within micro-
tubules via a template synthesis (Liang
et al., 1992).
PYRo, PTH, PPy (polypyridine), PPP, and
other materials such as polyquinoxalines can
be produced by the organometallic mediat-
ed coupling of dihaloaromatic monomers,
usually with nickel complexes to give prod-
ucts with low to reasonable molecular
weights (DP values, i.e., number of
monomers in the polymer chain, depend on
the type of polymer and are low for the insol-
uble conjugated materials, although they are
sometimes up to about 100). For example,
the 'Yamamoto coupling' reaction of the
dihaloaromatic monomer can be carried out
in dimethyl formamide (DMF) solution with
a nickel(cod)2 catalyst (cod= cycloocta-
diene) and bipyridyl ligand present. The
polymer product is then purified using
EDTA (ethylenediaminetetraacetic acid) to
ensure removal of any contaminating nickel
compounds (Yamamoto, 1995). These orga-
nometallic nickel complex mediated
coupling polymerizations give a much more
regular (and defect-free) product than the
oxidative chemical or electrochemical meth-
ods, because the coupling gives a well-
defined regio-regular bonding between the
monomer units. Coupling of e.g., alkyl chain
substituted bithiopene monomers can also
give stereoregular polymer structures.
PPP can be prepared by oxidative poly-
merization of benzene using copper com-
pounds, dehalogenation polymerization
with alkali metals or copper, and by the loss
of nitrogen from diazonium monomer com-
pounds. However, these methods do not give
highly regular structures or high molecular
weights (the DP is often only about 10) and
produce intractable polymer powders. High-
er molecular weight PPP is obtained by the
soluble precursor routes, and the organome-
tallic catalyzed coupling polymerizations
using the solubilizing side-chain substituted
monomers (described in Sec. 14.4.1). The
conductivity of pure pristine undoped PPP
is 10"9 to 10~13 S/cm, while the AsF5 doped
material normally has a conductivity of
about 10~2 up to about 500 S/cm, depending
on the synthesis method.
The PTH type polymers can be prepared
by direct oxidative chemical polymerization
(with an oxidizing agent such as ferric chlo-
ride) and by the electrochemical oxidative
polymerization described in Sec. 14.3.2.
Chemically synthesized polythiophene has
about 35% crystallinity, which can be
increased by post-synthetic thermal treat-
ment at 380 C for 30 min to about 56% (Mo
et al., 1985). These PTH type polymers are
quite stable in air in the doped state and so
are useful in normal applications, but the
problem with all these insoluble (or very
 14.3 Processing Insoluble Conducting Polymers (CPs)
low solubility) polymers is the difficulty of
processing them. Unless they are formed in
situ, for example, as a film that can be used
directly, the products are intractable pow-
ders which usually have low molecular
weights and cannot be used in applications.
14.3.2 Electrochemical Synthesis
and In Situ Deposition
Many objects, including those made from
insulating polymers, can be coated directly
with certain insoluble conducting polymers
(Tsumara et al., 1988). The polymer is
formed at an electrode surface and is elec-
trochemically doped as it is formed, so it is
produced in an electroactive and conductive
form. The conductivity of the product is
strongly dependent on the deposition con-
ditions. For example, solutions of aromatic
monomers, including bithiophene or bipyr-
role and terpyrrole, etc., can be oxidatively
polymerized at modest anode potentials to
produce conductive films. The polymeriza-
tion proceeds by electrophilic substitution
via a radical cation intermediate, retaining
the aromaticity and the conjugated struc-
ture. The growing polymer chains precipi-
tate onto the electrode surface when their
solubility limit is reached; this growth con-
tinues on the electrode surface to form a
film, which grows uniformly. If the poly-
merization is carried out in a solvent in
which the monomer adsorbs onto the elec-
trode surface, the film will be deposited uni-
formly from the beginning of the polymer-
ization. Films cannot be deposited if the oli-
gomers are soluble when stirring or if con-
vection occurs, nor from very dilute solu-
tions [see later for soluble polymers
(Sec. 14.4)]. Many of the films are produced
from commercially available reagents and
are stable in an ambient atmosphere, show-
ing little degradation in their electrical and
mechanical properties. Monomers used as
673
Table 14-1. Electrochemical peak potentials.
Compound Peak potential
(vs. SCE)
Pyrrole 1.2
Bipyrrole 0.55
Terpyrrole 0.26
Thiophene 2.07
Bithiophene 1.31
Terthiophene 1.05
Azulene 0.91
Pyrene 1.23
Carbazole 1.30
starting materials include (substituted)
derivatives of pyrrole, thiophene, aniline,
carbazole, azulene, pyrene, and tripheny-
lene, as well as the bipyrrole dimers, etc., as
shown in Table 14-1.
The electrochemical process for making
these films is versatile and provides a way
to vary the properties of the films. Polymer-
izations producing polyaromatic materials
have stoichiometries in the range 2-2.5
Faraday/mol of monomer. This is made up
of the charge for the stoichiometric forma-
tion of the polymer chain, almost 2.0 if the
chains are long, and an additional 0-0.5 for
the reversible oxidation of the polymer. This
value depends on the type of monomer, the
anion of the electrolyte, and the solvent, etc.
The degree of polymerization varies from
10-1000 monomers per chain. The films
have been investigated by a number of ana-
lytical techniques, and X-ray scattering
shows a mainly amorphous material with
some 20-50 A (2-5 nm) microcrystallites.
In the case of polypyrrole and polythio-
phene, scanning tunneling microscopy
(STM) has shown that the initial layer
[about 20 A (2 nm) thick] next to the elec-
trode is crystalline and the remaining outer
layer is amorphous (Yang et al., 1990), giv-
ing a bilayer morphology.
The realization of applications for each
polymer depends on the control and in par-
ticular the enhancement of the properties of
674 14 Conducting Polymers and Applications
the materials. Table 14-1 shows the oxida-
tion peak potentials for various starting
materials used to obtain CP films. These are
the normal potentials at which the electro-
polymerization is carried out, and it can be
seen that they are quite low, between about
1 and 2 V vs. SCE. In practice the potential
is kept at this value in an organic solvent to
avoid decomposition of the solvent, the
electrolyte, and the polymer. Reactions are
usually carried out in an organic solvent that
is aprotic and nonnucleophilic to avoid
unwanted reaction with the cationic inter-
mediates and the polymer product, although
electropolymerization of pyrrole and other
monomers in aqueous solution has been car-
ried out (Kupila and Kankare, 1995). Good
films of PANi are formed galvanostatically
(i. e., at a constant current) from 1 M aniline
in aqueous 2 M HC1, at a current density of
0.1 mA/cm2 (Kobayashi et al., 1984).
The surface of insulators can be electro-
chemically patterned with CPs (Zheng
et al., 1995), and multi-layers of different
CPs can be formed (Shimidzu et al., 1994)
by alternately electrochemically depositing
layers on a conducting (film-coated) sub-
strate; modified polymers such as con-
ducting PANi-poly(methylmethacrylate)
(PMMA) and PTH-PMMA crosslinked
films can also be prepared by electropoly-
merization (Karakisla et al., 1996).
Continuous sheets of conducting PYRo
film can be produced electrochemically
using cells with partially immersed rotating
electrodes. This process is shown in Fig.
14-8. The CP is deposited on a carbon-
loaded sheet of microporous polyurethane.
By ultrasonic pre-treatment of the polyure-
thane sheet with the electrolyte, electro-
deposition of the CP is directed into the
pores of the substrate sheet and higher con-
ductivities can be obtained. The carbon-
loaded polyurethane was initially 150 or
510 |im thick, 11cm wide, and up to
Figure 14-8. Method for producing continuous
sheets of conducting polymer using a partially
immersed, cylindrical, horizontal revolving electrode.
Key: (1) electrochemical cell, (2) working electrode,
(3) counter electrode, (4) electrolyte, (5) power sup-
ply, (6) microporous membrane, (7) roller, (8) poly-
pyrrole impregnated film, (9) roller, (10) squeezing
rollers (Kathirgamanathan et al., 1994).
8 - 1 0 m long. The sheet was fed through the
rotating electrode at velocities of less than
1 mm to over 1 cm/s at current densities of
60-230 mA/cm2, usually at room tempera-
ture, giving conductivities of 10~3 to
10"4 S/cm (Kathirgamanathan et al., 1994).
Conducting sheets are available commer-
cially from Porvair (Norwich) and are quite
stable under ambient conditions.
Polymerization can also be carried out on
conventional polymeric and inorganic sur-
faces, which is commercially useful for con-
ductive antistatic coatings on fabrics, etc.
The polymerization mechanism of pyrrole
has been outlined above, and involves oxida-
tion of the pyrrole monomer to the radical
cation and the coupling of a neutral monomer,
beginning the chain sequence which contin-
ues until terminated by a side reaction or a
lack of monomer. The polymerization is typ-
ically carried out at a potential of 1.2 V vs.
SCE, in an aprotic solvent, e.g., acetonitrile
containing a soluble electrolyte, e.g., a tetra-
alkyl ammonium salt. The final material is
stable in air, making it suitable for applica-
tions. PYRo is perhaps the most useful of the
 14.4 Processing Soluble Conducting Polymers for Films
conducting polymers because crosslinking
occurs during the electrochemical polymer-
ization, which gives the films toughness and
mechanical strength. The mechanical prop-
erties and chemical stability can be optimized
and controlled by changing the counter ion
in the p-doped (oxidized) PYRo.
PTH and PANi can also be prepared elec-
trochemically to give continuous sheets of
conducting polymer as in Sec. 14.3.2, which
are stable in air in the p-doped conducting
state. PTH is often made with polyanions as
the dopant counter ions for practical purpos-
es (Tourillon, 1986).
The PPV type polymers can also be depos-
ited electrochemically from a solution of
the di-bromomethyl arene monomers. The
polymer is formed via the quinodi-
methane intermediate and copolymers and
blends with PVA (polyvinylalcohol) can also
be made (Utley et al., 1995). Similarly, PPP
can be formed by electrochemical anodic
oxidation from benzene or biphenyl. It can
also be formed by the cathodic reduction of
dihalobenzenes, e.g., dibromobenzene; the
conductivity of these films was about 1CT3
to 10"5 S/cm (Goldenberg et al., 1990).
14.4 Processing Soluble
Conducting Polymers for Films:
Soluble Polymers and Solubility
Induced in Polyaniline by 'Soaps'
One method for overcoming the intract-
ability of CPs is to synthesize polymers with
modified chemical structures (Sec. 14.2.2)
having alkoxy or alkyl side chains, the so-
called 'hairy rod' polymers which are solu-
ble; although other strategies for dealing
with these materials are possible, such as the
'precursor route' method (discussed in Sec.
14.5). Many of the so-called solutions of
CPs in the acid-doped state are colloids,
however, e.g., the alkoxy substituted PTH-
675
polyacid mixture is a colloidal suspension
in aqueous solutions and can be cast to give
a CP film (Aldissi, 1993 a). When the side
chains occupy greater than approximately
0.5 of the bulk of the polymer main chain,
the material becomes soluble (in the neutral
state) in common organic solvents, e.g.,
chloroform and THF, and they can also
become fusible. Such polymers include
(2,5-dialkoxy)PPV, (3-alkyl)PTH, and sub-
stituted PPPs. For example, films of soluble
(3-hexyl)PTH can be prepared by dissolv-
ing the material in chloroform, dichlorom-
ethane, toluene, or THF, and casting it onto
glass or ITO coated glass substrates from
these solutions by evaporation of the sol-
vent. Films of soluble polymers are also
obtained by the normal techniques of spin
coating or blade coating onto a substrate (the
methods for the solution processing of con-
ventional polymers are given elsewhere), as
shown in Fig. 14-9. Films of polymer blends
(Sec. 14.7) containing CPs can be formed
from mixtures of soluble polymers.
Although PANi (base) itself is soluble in
NMP and concentrated sulfuric acid, an
important method for obtaining a soluble,
processable CP has been developed for
PANi, where solubility can be induced in the
emeraldine base form of PANi by doping
with a 'soap' type functionalized acid, so
giving the conducting form of the material
without the need for further doping (Cao
et al., 1991 a, 1992 a; Cao and Smith, 1993);
for example, camphor sulfonic acid (CSA)
or dodecylbenzene sulfonic acid, containing
a chemical unit that is compatible with the
common nonpolar or weakly polar organic
solvents, or even with different polymer
melts. In fact the doping produces 'hairy
rod' type molecules by the complexation of
the acid anions, which are analogous to the
other soluble polymers having solubilizing
side chains and these solutions even show
(lyotropic) liquid crystallinity due to the
676 14 Conducting Polymers and Applications
Evaporating solvent
Doctor blade
Liquid film
Liquid reservoir
Moving substrate
stretched, rigid-rod-like nature of the mole-
cules. Typically, the (unprotonated) emeral-
dine base form of PANi, thoroughly mixed
with a 0.5 M equivalent of CSA under an
inert atmosphere to give the conducting
emeraldine salt form, was dissolved in m-
cresol to give 2 or 4% solutions. This meth-
od gave superior homogeneity in conduct-
ing films cast from solution (Reghu et al.,
1993), with a high conductivity of about
300 S/cm, which even showed some metal-
lic temperature dependence. When the eme-
raldine base form of PANi is doped with
CSA at a level of 30%, the onset of metal-
lic conduction behavior (i.e., a negative
coefficient with respect to temperature) is
observed, and at a doping level of 60% the
metallic behavior persists down to a temper-
ature of 135 K (Holland et al., 1996).
Optical quality transparent conducting
films have also been produced using this
process, from PANi alone or from solutions
containing other amorphous, conventional
polymers, e.g., poly(methylmethacrylate)
(PMMA) (Cao etal., 1992b; Yang et al.,
1993). These solutions can be cast or spin-
coated onto flexible polymer substrates,
e.g., poly(ethylene terephthalate) (PET).
The film thickness of PANi or of the blend
can be controlled by varying the spinning
conditions and the solution concentration,
which controls the conductivity of the films.
By varying the thickness and the volume
Driven spindle
Figure 14-9. Schematic
representation of the doctor
blade coating method.
fraction of PANi in the blend, the conduc-
tivity can be varied over a wide range. These
transparent conducting PANi films make
suitable electrical contacts (anodes) for p-
type semiconducting polymers, for exam-
ple, in LEP devices with (2,5-dialkoxy)PPV
as the emitting layer which have been fab-
ricated in a flexible form on PET substrates
(Gustafsson et al., 1992).
In fact by adding a second 'soap' dopant
molecule, which places itself between the
molecules of the primary dopant, different
colors can be obtained in LEP applications.
This doping method gives a material that is
soluble in some conventional insulating
polymer melts, e.g., PP, and because the
PANi molecule chains are extended or
' stretched out', these blends show useful con-
duction at very low volume fractions of the
PANi. This is the basis of the commercial
Neste complex for antistatic applications
(see Sec. 14.11.3). Water-soluble conducting
PANi can be made by a template polymer-
ization on a polymeric acid, which then acts
as the dopant (Angelopoulous et al., 1993).
14.4.1 Soluble Polymers by Chemical
Polymerization: (3-Alkyl)Polypyrroles
and Polythiophenes
As well as the chemical oxidative
coupling method (usually by FeCl3),
coupling polymerizations catalyzed by orga-
 14.4 Processing Soluble Conducting Polymers for Films
nometallic palladium and nickel complexes
can be used to synthesize the soluble side-
chain substituted conjugated polymers com-
posed of aromatic type rings, e.g., PYRo,
PTH, and PPP, for example, using the 3-alky 1
substituted dihalo-monomers such as 3-
alkyl-(2,5-dibromo)thiophene to give solu-
ble polythiophene. The nickel-catalyzed
coupling method gives the regular structure
of head-to-tail coupled monomers in the
polymer, while coupling with palladium has
been used to give a random product, as is
usually the case for the oxidative method,
although under carefully controlled condi-
tions this can also give a regular coupling of
monomers. For example, the regio-regular
structure having 94% head-to-tail linkages
has been achieved by the oxidative polymer-
ization of the 3-(4-octyl-phenyl)thiophene
monomer with ferric chloride. By adding the
FeCl3 slowly as a slurry in chloroform to the
monomer in chloroform, it is possible to
achieve a 'soft' regio-selective polymeriza-
tion by keeping the Fe3+/Fe2+ ratio low, thus
also keeping the oxidation potential low dur-
ing the polymerization process (Andersson
et al., 1994). The side-chain substituents can
contain acid groups, to give the self-doped
polymers in a conducting state (Arroyo-
Villan et al., 1995).
PTHs with a regio-regular structure hav-
ing greater than 90% head-to-tail (HT) link-
ages have smaller band gaps (1.7-1.8 eV)
than the normal random structure (having a
band gap of 2.1 eV), and they also have the
highest undoped conductivity of about
10"6 S/cm, three orders of magnitude high-
er than the random polymer. These were
produced by nickel(phosphine) dichloride
coupling of the zinc complex of the dibro-
mothiophene monomer with a side-chain
substituent. These iodine-doped PTHs had
conductivities of up to 1350 S/cm or
450-750 S/cm, depending on the side
chains (Wu et al., 1995).
677
A variation of the nickel-catalyzed
dehalogenation polymerization technique
involves the coupling of mono-bromo deriv-
atives of thiophene, again using a nickel com-
plex, to give practically 100% regio-regular
head-to-tail monomer orientation in the poly-
mer. The 2-bromo-3-(side-chain substituted)
thiophene monomer was reacted with a
strong base and magnesium bromide at
-78 C to convert the monomer into the Grig-
nard reagent. This was then polymerized with
a catalytic amount of nickel(phosphine)
dichloride at -78 C for 36 h, giving products
with a DP of up to 160. The practical routes
to these polymers are shown below
Ni
X-Ar-X Coupling
(14-5)
A r -f Ar (14-6)
Oxidation
on
Different side-chain substituents on the
polymer can then be used to control the con-
jugation length in the polymer, for example,
alkyl and polyether type groups, since the
substituent controls the amount of steric hin-
derance around the bond connecting the
monomer units. Iodine-doped thin films
(8-20 |am) of such materials, cast by the
slow evaporation of a chloroform solution,
have shown conductivities of up to
5500 S/cm when the films were free of
physical defects such as cracks (McCul-
lough and Williams, 1993).
As well as being synthesized by chemi-
cal coupling polymerization methods, sub-
stituted soluble (3-alkyl)PTH can be synthe-
sized by an electrochemical polymerization
process (Hotta et al., 1987) similar to that
described above for insoluble PYRo, etc. It
is found that the oxidation potential is high-
er and the final conductivity lower for the
(3-alkyl)PTH films with longer alkyl chain
lengths. The conductivity is also strongly
dependent on the polymerization condi-
tions, e.g., the temperature, concentration of
678 14 Conducting Polymers and Applications
monomer and electrolyte, and the potential
(Wang et al., 1990). All the polymers were
amorphous and the highest conductivities
were obtained with the shortest side chains,
when the potential was 10 V and the con-
centration was more than 0.04 M for the
electrolyte and greater than 0.1 M for the
monomer. In another example, (3-hexyl)-
PTH was polymerized directly onto an ITO
substrate from a 0.2 M electrolyte solution
of (3-hexyl)thiophene at 5 C under a dry
inert nitrogen atmosphere. A constant cur-
rent density of 2 mA/cm2 was applied and
the polymerization time was determined by
the required film thickness, 40 s giving thin
films and 40 min giving thick films, the typ-
ical film thickness being 10 |im. The exclu-
sion of oxygen and moisture during poly-
merization results in a significant improve-
ment in the conductivity of the polymer
films, values from 30-40 S/cm up to
500 S/cm being obtained. The solubility of
the materials enabled purification and con-
ventional solution processing, for example,
solution casting of the materials.
14.4.2 Polyaniline and Substituted
Polyanilines
PANi is useful in applications because it
is quite stable in air in the doped state,
although its conductivity is still lower than
the best values obtained for PAC. PANi can
be formed by electrochemical polymeriza-
tion (discussed in Sec. 14.3.2) and by chem-
ical polymerization. By carefully control-
ling and optimizing the polymerization con-
ditions, high molecular weight materials can
be produced with few defects. The undoped
PANi base form itself is sparingly soluble in
NMP (Af-methylpyrrolidone) and a few
other solvents, so it can be solution pro-
cessed and films can be produced and
stretch-aligned to give a material with a con-
ductivity of up to 10 000 S/cm, but the mate-
rial first has to undergo further doping treat-
ment after casting to give a conducting
material (MacDiarmid and Epstein, 1990).
Materials with higher solubilities can be
produced from monomers with pendant side
chains, to give the soluble hairy rod type
polymers, as for the PTHs. An example is
poly(o-methoxyaniline), which is soluble in
organic solvents (Macinnes and Funt, 1988).
The side chains can also contain covalently
bonded counter ions in the doped polymers.
Although these soluble side-chain substitut-
ed PANis have lower conductivities than
PAC, they are still high enough for applica-
tions that use the neat material or even a
microparticulate dispersion of the CP in a
nonconducting polymer matrix (cf. Neste
product and filled polymers), and PANi is
now one of the most widely used CPs. The
soap-induced solubility of conducting PANi
(Sec. 14.4) should be mentioned again
because of its importance in solving the pro-
cessing problems for this material.
14.4.3 Poly[2,5-alkoxy-
(phenylene-vinylene)]s and Soluble
Poly(/;-pheiiylene)s
Because of the intractability of unsubsti-
tuted PPV and PPP, their structures can be
chemically modified to produce soluble
materials as for PTH and PYRo. These PPVs
are commonly synthesized from 2,5-
dialkoxy substituted bis-chloromethyl
monomers with an excess of a strong base,
giving a hairy rod type chain which is free-
ly soluble in common organic solvents; sev-
eral modifications of the structure are pos-
sible (Motamedi et al., 1992; Shi and Wudl,
1990). PPV with phenyl substituents on the
vinyl double bonds is also soluble and
undergoes an interesting oxidative cycliza-
tion reaction with ferric chloride, to produce
a fully aromatic polymer containing phen-
anthrene units (Horhold et al., 1995).
 14.5 Precursor Routes to 'Unprocessable' Polymers
The hairy rod PPP polymers made from
2,5-dialkyl, dialkoxy, or mono-substituted
monomers are also soluble in common sol-
vents, e.g., chloroform. Figure 14-1 shows
the structures of some of the soluble PPVs
and PPPs. Groups such as the iso-pentoxy
substituents can be used attached to the
polymer backbone chain, which also pre-
vents crystallization of the substituents. For
example (Vahlenkamp and Wegner, 1994),
organic solvent soluble hairy rod alkyl and
alkoxy substituted PPP has been made by
the palladium catalyzed 'Suzuki' coupling
of boronic acid and bromo monomers in
solution (Rehahn et al., 1990), and a solu-
ble copolymer which also contains unsub-
stituted phenyl comonomer units has been
made (Jing et al., 1994) and used in the con-
struction of light-emitting diodes. Wallow
and Novak (1991) have used this 'Suzuki'
method to prepare the first water-soluble
carboxylated PPP. Palladium-catalyzed
coupling has also been used for the prepar-
ation of alkyl-substituted PPPs from alkyl-
substituted aromatic bis(trifluoromethane
sulfonate) with l,4-bis(trimethylstannyl)-
benzene, to give a DP of about 11. John and
Tour (1994) used a different method, syn-
thesizing a substituted PPP from enediynes
by thermal polymerization.
^ , Polymerization ^ .,
Monomer > Precursor polymer
Although the side-chain substituents give
solubility, they also lead to torsion about the
monomer-monomer bonds and this limits
the conjugative delocalization along the
polymer backbone chain, which could
decrease the conductivity. Methods of
avoiding this involve the coupling of dial-
kyl fluorene or dihydrophenanthrenes, or
the synthesis of planar ladder polymers (as
shown in Fig. 14-2). If solubilizing alkyl
679
substituents are present in the ladder struc-
ture, then the polymer is obtained with a DP
of around 50 (Chmil and Scherf, 1993).
Nickel-catalyzed 'Yamamoto' coupling (as
described in Sec. 14.3.1) of 2,7-dibromo-
4,9-di-?2-octyl-4,5,9,10-tetrahydropyrene
has recently been used to give a soluble,
modified PPP-type material containing tet-
rahydropyrene units along the polymer
chain. This material is soluble in common
organic solvents and, unlike the hairy rod
type materials, it has a more planar and delo-
calized structure because the monomer units
do not induce torsion about the aryl-aryl sin-
gle bonds. The DP was found to be about 80
phenylene rings, and an even higher molec-
ular weight fraction could be separated from
the product (Kreyenschmidt et al., 1995).
Films of this material may be suitable for
LED (light-emitting diode) applications.
14.5 Precursor Routes
to 'Unprocessable' Polymers
Because many CPs are insoluble and infu-
sible and therefore cannot be processed once
the polymer is formed, another approach
must be used and the polymer can be formed
indirectly via a processable precursor poly-
mer. The scheme is shown below
Conversion _ - , . ^ -.
> Intractable conjugated polymer
(14-7)
Practical precursor routes to PAC, PPV, and
PPP are now well established.
14.5.1 Precursor Routes
to Polyacetylene (PAC) Films
As mentioned in Sec. 14.2.2, doped PAC
is very unstable in normal ambient condi-
tions, which is a great hindrance to applica-
680 14 Conducting Polymers and Applications
F3C CF, F3CCF3 F3C
tions. Normal synthesis of the polymer is in
the undoped form, but even this is not oxi-
datively stable under normal conditions, the
black lustrous material turning to a light
brown material after a few days exposure.
The prototypical precursor route is used for
poly acetylene (Edwards and Feast, 1980)
and is illustrated in Fig. 14-10.
The monomer 7,8-bis(trifluoromethyl)-
tricyclo [4,2,2,0] deca-3,7,9-triene can be
prepared by the thermal addition of
hexafluorobut-2-yne and cyclooctatetraene
at 120 C, and gives the precursor polymer
by ring-opening metathesis polymerization
(ROMP) using a transition metal catalyst.
The precursor is soluble in common organ-
ic solvents such as chloroform and acetone.
The precursor route is useful not only
because it allows processing, but also
because it allows the soluble precursor poly-
mer to be purified before it is converted to
PAC. The conversion is thermal, carried out
at 150-200 C for several hours under vac-
uum. At this temperature the initially all cis-
PAC is fully converted to the all trans form.
The soluble precursor can be processed by
solution casting or spin coating to give films
that are largely amorphous after conversion.
It can also give crystalline, highly aligned
films by stretch alignment during conver-
sion.
Another organic solvent soluble precur-
sor for PAC can be synthesized by the anion-
ic polymerization of phenyl vinyl sulfoxide
to give the poly(phenyl vinyl sulfoxide)
with a very narrow molecular weight distri-
bution, which can be converted thermally to
CF3
Figure 14-10. Schematic diagram of the
precursor route for PAC.
PAC by elimination of the sulfinyl group
(Leung and Tan, 1993).
14.5.2 Precursor Routes to
Poly(phenylene-vinylene) (PPV)
and Heterocycle-Vinylenes
Because the PPV polymer chains are
highly linear, the chains pack well to form
a regularly ordered, dense crystalline struc-
ture, which is insoluble and intractable (as
is the case for PAC, PPP, etc.). The tensile
properties are comparable to those of rigid
engineering polymers, the elastic moduli
and tensile strength being comparable to
those of aramids such as Kevlar (in fact they
were originally developed for engineering
purposes such as the aircraft industry). As
explained in Sec. 14.5, these properties
make the materials unprocessable, but are
desirable for applications such as thin films
which should be tough and robust.
One way to overcome this problem, as
outlined in Sec. 14.4.3, is to make a soluble,
modified form of the material. The other
method is the precursor route. PPV is usu-
ally synthesized by the precursor route
(Wessling, 1985) and a variety of practical
modifications of the method exist. It is still
under discussion whether the mechanism of
these polymerizations is ionic or radical (or
both). The usual precursor route involves
polymerizing a bis(sulfonium halide) p-
xylene salt with a base in water-alcohol as
the solvent. The precursor polymer obtained
is a polyelectrolyte, which involves a sulfo-
nium cationic species on the polymer back-
 14.5 Precursor Routes to 'Unprocessable' Polymers
cr
Heat
Heat, acid
OCH3
=\ i "
CH-CH 2 -
bone, and which is soluble in methanol-
water or another aqueous-solvent system,
and can be purified by dialysis to remove
the inorganic salts and other impurities.The
precursor is then thermally converted to
PPV. This method is shown schematically
in Fig. 14-11. Films of PPV can be formed
from the organic solvent soluble methoxy
precursor polymers followed by conversion
(Tokito et al., 1990), where the methoxy
precursor is normally obtained from the
classic polyelectrolyte precursor by reac-
tion with excess methanol.
Another precursor route to PPV involves
the polymerization of an a-chloro-a'-
arylsulfonyl p-xylene with a base in an
organic anhydrous solvent. This gives a pre-
cursor polymer with sulfonyl groups along
the polymer chain; the precursor materials
were organic solvent soluble (Louwet et al.,
1995). Other organic solvent soluble precur-
sors have been obtained by modification of
the synthetic route.
These soluble precursors can be pro-
cessed, e.g., by spin coating, and then con-
verted in situ to the conjugated polymer. The
conversion is commonly done thermally in
an inert gas atmosphere, but chemical con-
version is also possible.
Although PPV is much more stable than
PAC, further improvements in the atmo-
spheric stability and the processability of
the polymers are expected when the aromat-
ic ring unit in these polymers is replaced
681
Figure 14-11. Schematic diagram of the
precursor route for PPV from the sulfoni-
um polyelectrolyte using thermal conver-
sion, and from the methoxy precursor
using acid and thermal conversion.
with a thiophene or a furan heterocyclic unit,
while no loss of conductivity of the doped
material is expected. Several of these poly-
mers have been made (Gandini and Mea-
lares, 1994) using different methods,
including a Wittig type polymerization and
an aldol-crotonic condensation, as well as
the precursor route method, from a bis(tet-
rahydrothiophenium halide) salt using base
polymerization (as above for PPV). These
precursor polymers have been used for cast-
ing films or spinning fibers. The doping was
performed mostly with iodine, but other
dopants such as FeCl3, SbF5, AsF5, and
acids such as methyl sulfonic acid have been
used. The conductivity was usually up to
50 S/cm, but increased to over 2000 S/cm
when stretch-aligned. As with some other
materials, there was a close correlation
between the mechanical properties and the
conductivity as a function of the draw ratio.
In the fibers there was a close relationship
between the elastic modulus and the electri-
cal conductivity, showing that the degree of
macromolecular orientation has a similar
effect on the tenacity of the filaments and
the electronic mobility.
14.5.3 Precursor Routes to
Poly(/7-phenylene)s and Other Polymers
with/7-Phenylene and Vinylene Units
As for PAC, the preferable method would
be to use a soluble precursor polymer that
682 14 Conducting Polymers and Applications
can be processed and then converted to PPP
by thermal treatment or pyrolysis. An early
example of such a precursor route was based
on the method demonstrated by Marvel and
Hartzel in 1959, in which cyclohexadiene
was polymerized by a 1,4-addition, the pre-
cursor poly(cyclohexadiene) could then be
dehydrogenated to PPP. An improved route
has been developed, giving a soluble pre-
cursor polymer and a high molecular weight
PPP on pyrolysis (Douglas et al., 1992).
An elegant route to PPP is based on the
biologically produced c/s-dihydrocatechol
(Ballard et al., 1988). Derivatives of this,
particularly the bis(methyl carbonate) can
be polymerized with radical initiators to
give a di-functionalized poly(cyclohexene)
precursor, which is soluble in common sol-
vents such as acetone and dichloromethane,
and can be formed into coatings, films, or
fibers. The polymer is produced with a high
molecular weight (greater than 100000 Mn)
and the precursor is converted on heating at
about 300 C to PPP by the loss of substitu-
ents and consequent aromatization, and can
be converted at lower temperatures if an
organic base or inorganic salt catalyst is
added. The route is shown in Fig. 14-12. The
product obtained by the thermal conversion
was pale yellow and in the unannealed state
was 60% crystalline; crystallinities of
75 - 80% can be obtained by controlling the
aromatization conditions, although by per-
forming the conversion below the glass tran-
sition temperature (185 C) of the precursor
can produce a predominantly amorphous
coating film or polymer powder. The oxida-
tive stability of PPP is superior to that of
most other aromatic polymers, and coatings
OH
can withstand temperatures of up to 350 C
in air for short periods. The films can
be either n- or p-doped to the black conduct-
ing state. The n-doping with sodium-
naphthalide gives a conductivity of about
0.006 S/cm, and p-doping with AsF5 gives
about 100 S/cm, while the undoped polymer
is a good insulator with a conductivity of
10~14to 10~15S/cm.
Another precursor route, from a stereo-
regular precursor polymer, involves thermal
conversion with <9-phosphoric acid as the
aromatization catalyst. The PPP films can
be washed with dilute HC1 to remove
83 - 90% of the poly-m-phosphoric acid that
is produced during pyrolysis; the films are
amorphous, of high molecular weight, and
show a completely regular 1,4-linking of the
phenylene units. The washed films show
high thermal oxidative stability and can be
doped with 98% concentrated sulfuric acid
to give air-stable conducting materials
which can be undoped in water (Gin et al.,
1994).
Soluble side-chain substituted materials
can be made by a precursor route involving
the polymerization of the activated ester-
substituted and alkyl side-chain substituted
monomers with a nickel catalyst generated
in situ, giving improved coupling, followed
by chemically catalyzed decarboxylation.
The products have DPs of about 22 up to
100 with the ester side chain alone, which
was high enough to give good films of the
material. These poly(alkyl benzoates) were
soluble in solvents such as chloroform and
were fusible, with melting points between
200 and 300 C. Also, the kinked 1,3-
phenylene polymer can be made in a simi-
Figure 14-12. Schematic diagram of a
precursor route for PPP.
 14.6 Oriented Langmuir-Blodgett and Other Thin Films
lar manner, but in this case decarboxylation
did not occur. Although the substituted
product is soluble, an unsubstituted PPP can
also be made by this precursor route (Kae-
riyama et al., 1995). However, the chemical
decarboxylation, to give an insoluble film,
for example, is still problematic.
Polymers containing two or three para-
linked phenylene units and a hexatriene unit
have been prepared via a precursor polymer.
The soluble precursor is converted thermal-
ly to give the product polymer with the loss
of anthracene (Power et al., 1996). Films
cast from THF were converted at 240 C in
vacuo, were dark orange, and had conduc-
tivities of about 0.001-0.2 S/cm after dop-
ing with a ferric chloride solution. Similar-
ly prepared polymers containing dithio-
phene units had higher conductivities.
14.6 Oriented Langmuir-
Blodgett and Other Thin Films
Highly oriented thin films built up of
monolayers of soluble polymers can be
made by Langmuir-Blodgett (LB) tech-
niques, usually for semiconductor applica-
tions (see Sec. 14-11). Certain rigid rod type
polymers, substituted with flexible side
chains for solubility can be processed by this
technique giving layers with very well
defined thickness, e.g., substituted PTH and
substituted PPP. One of the most important
developments in this area has been the
incorporation of an LB film as the active
semiconductor polymer layer in an FET
device (Paloheimo et al., 1992).
The LB technique involves preparing a
monolayer of soluble conjugated polymer
material on a nonsolvent surface, e.g., on
water (see also Vol. 12, Chap. 12 of this
Series). Polymeric materials will normally
be oriented in the direction of dipping
because of the inhomogeneous flow due to
683
shear stresses on the layer on the water sur-
face during transfer to the substrate. In these
films the polymer chains are therefore
oriented parallel to the substrate surface,
and if the surface tension of this floating
monolayer is held constant, then films can
be deposited onto a substrate by lowering
and raising the substrate through the
monolayer-air interface (Roberts, 1990) to
build up many layers, as each passage
through the monolayer deposits another
monolayer of the polymer onto the sub-
strate. For example, a solution of 0.3 g/1 of
polymer in chloroform was spread onto the
surface of pure water. Clean substrates were
then dipped at a speed of 0.9 cm/min while
the tension on the monolayer surface was
kept constant at 8 mN/m. This technique is
shown schematically in Fig. 14-13.
Extremely thin, oriented films of these
materials can be deposited with this tech-
nique (Rosner and Rubner, 1994), and
recently a substituted PPP was deposited to
give an LED emitting polarized light (Cim-
rova et al., 1996); another polymer deposit-
ed as a highly oriented film is PPV (Era
et al., 1989). The CP film can also be formed
indirectly by first depositing a multilayer of
amphiphilic monomers (e.g., long alkyl-
chain substituted polar monomers, e.g., 3-
alkyl pyrrole) on the substrate and then
polymerizing them in situ, e.g, electrochem-
ically. This method is shown in Fig. 14-14
(Shimidzu et al., 1988).
The layer by layer deposition of ionic
functionalized CP or CP precursors, e.g., a
sulfonated polyaniline polyanion or the sol-
uble PPV precursor polycation and p-doped
PYRo and PANi has been used to fabricate
ultrathin multilayer films (Ferreira and Rub-
ner, 1995). Glass slides with hydrophilic,
hydrophobic, or charged surfaces were used
as substrates and prepared by thorough
cleaning and pre-treatment. The multilayer
films were deposited on the substrates by
684 14 Conducting Polymers and Applications
t
Air
Water Water
Substrate
Water
Figure 14-13. Conventional schematic diagram of
the LB technique. In the first step (A), a suitable
amphiphilic polymer or monomeric molecule is dis-
solved in a volatile solvent, which is then spread at
the air-water interface to form a Longmuir monolay-
er. (B) A substrate is passed through the interface a
given number of times, with each pass adding another
monolayer to the LB film (C and D).
alternately dipping them into dilute aqueous
solutions containing the polycations and
polyanions. Each step of the multilayer de-
position process involves the adsorption of
a charged polymer from solution onto an
oppositely charged surface on the substrate.
The p-doped PANi and PYRo CPs were pro-
duced continuously by in situ oxidative poly-
merization. The solutions used were made
by dissolving ferric chloride oxidizing agent
in water with a little acid, followed by the
monomer, e.g., pyrrole. The polyanion used
in this case was sulfonated polystyrene.
Each bilayer consisting of one positively
charged layer and the corresponding nega-
tively charged polyanion layer was about
Pyrrole monomer ITO
Pt Substrate
electrode
Figure 14-14. Electropolymerization of LB multi-
layers of amphiphilic monomeric pyrrole derivatives
in an electrochemical cell. Note that the polymeriza-
tion starts at the bottom, where the LB film is in con-
tact with the electrolyte, and moves up the substrate.
20-60 A (2-6 nm) thick, depending on the
dipping time. Conductivities of 20-80 S/cm
were found for films consisting of several
bilayers of PANi or PYRo and sulfonated
polystyrene, although conductivities of up to
300 S/cm could be obtained in ultrathin
films. It was possible to pattern the CP onto
the substrate in well-defined regions by
selectively pre-treating the surface. Recent-
ly, self-assembled monolayers of conducting
(3-octyl)PTH have been deposited on gold
electrodes (Gao et al., 1995).
A different method for obtaining highly
ordered thin films is the vapor deposition
method. This is, however, only applicable
to oligomeric (and monomeric) materials

rather than high molecular weight polymers.
In some cases the monomers are then poly-
merized in situ. It is useful in studying new
types of structures, e.g., pentacene (an olig-
omeric model of a one-dimensional graph-
ite). The material is essentially sublimed
onto a substrate by heating the sample under
vacuum, usually giving films of the order of
a hundred angstroms thickness. Vapor dop-
ing can then be performed by iodine, etc.
14.7 Processing Fusible
Polymers, Polymer Blends,
and Latexes
The chemical structure of some conduct-
ing polymers can be modified to enable
them to melt (as well as producing solubil-
ity), i.e., to have melting points that are rea-
sonably low so they can then be processed
by the normal techniques used for plastics
either alone or in blends. Examples include
the side-chain PTHs, e.g., (3-octyl)PTH
having a melting point of 165 C. Blends
with conventional thermoplastics, e.g.,
polyethylene, polystyrene, polypropylene,
and polyvinyl chloride are produced which
can easily be processed by conventional
techniques such as extrusion and injection
molding; they have a moderate conductiv-
ity after doping with iodine, ferric chloride,
or sulfonic acid, etc., of up to 0.01 S/cm
(Isotaloet al., 1993). (The processing meth-
ods for conventional polymers are given
elsewhere.) The ability to use these simple
conventional processes would enable the
manufacture of conducting objects, for
example, for antistatic and electromagnetic
screening uses. Another example is the CS A
doped PANi base (Yang et al., 1993), which
can form a blend (or a microparticulate dis-
persion) with conventional polymer melts
and shows conductivity at very low volume
fractions of PANi/CSA. This is the basis of
14.8 Forming Polymers into Fibers 685
the commercial Neste complex for antistat-
ic applications.
Solution-cast blends of soluble (2,5-
alkoxy)PPV and (3-alkyl)PTH, as well as
poly(9,9-dialkylfluorene), can be produced
with conventional polymers such as PMMA
and show marked conductivity changes as
the proportions of the CPs in the blends
are changed (Gu et al., 1995). The (3-
alkyl)PYRos can be formed in a similar
manner, but electrochemical deposition of
PYRo on a polymer-coated electrode to
form a composite is more common. Conduc-
tivities of around 100 S/cm have been
achieved by controlling the potential
(Yoshikawaet al., 1990). Another method is
also possible, i.e., casting from a solution
containing the polyvinyl acetate matrix
polymer, pyrrole monomer, and FeCl3. This
gives a conducting network material with a
conductivity of around 10 S/cm with only
5%. PYRo (Hashimoto et al. 1982), and the
matrix polymer crosslinks to form a stable
material with a conductivity that was con-
stant for over one year.
So-called blends of PAC with polyvinyl-
butyral can be produced (Kobryanskii and
Tereschko, 1991). In these materials the
PAC is not actually dissolved in the matrix,
but is in the form of microparticles of
100-200 A (10-20 nm) dispersed in the
host polymer. This material is also soluble
in organic solvents and is stable against
atmospheric oxidation for more than one
year (Paraschuk et al., 1995). The post dop-
ing of sterically stabilized PAC latexes is
also possible (Armes and Vincent, 1988).
14.8 Forming Polymers
into Fibers
Fibers of (3-methyl)PTH can be formed
in an electrochemical flow cell, shown
schematically in Fig. 14-15 (Li et al.,
686 14 Conducting Polymers and Applications
Inlet
Pt Anode
3 mm
, R Cathode
Outlet
Figure 14-15. Schematic drawing of the electro-
chemical flow cell used to grow conducting poly(3-
methyl)PTH fibers. A centrifugal pump is used to
pump the electrolyte solution through the cell (Li
etal., 1993).
1993). This electrochemical process has pro-
duced electrically conducting fibers of
0.1 -0.7 mm diameter and more than 10 cm
in length. The cell consists of a capillary of
3 mm internal diameter, with platinum elec-
trodes at each end. The cell is oriented ver-
tically with the anode at the top, and the ace-
tonitrile electrolyte solution containing the
(3-methyl)thiophene monomer is pumped
downwards from the top of the cell. Signif-
icantly stronger fibers can be grown by using
the polymeric sulfonated polystyrene anion.
Soluble CPs can be processed by conven-
tional methods for fiber-spinning, e.g.,
PANi fibers can be spun from solution in
concentrated sulfuric acid (Andreatta et al.,
1988). Among the hairy-rod-type polymers,
organic, soluble [2-methoxy-5-(2-ethyl)-
hexyloxy]PPV (denoted as MEH-PPV) has
been solution spun into fibers (Motamedi
et al., 1992). The solubilizing side groups
allow the processing of this polymer direct-
ly in its conjugated form by conventional
processing methods. High molecular
weight, chemically synthesized MEH-PPV
was dissolved in chloroform or THF to give
a 3 wt.% solution. This could be wet spun
into hexane to give fibers, and then dried in
a vacuum oven at room temperature to give
fibers of 170 |im diameter. The fibers had a
Young's modulus (E) of 2.6 GPa and a ten-
sile strength of 0.056 GPa before stretching
and doping. They could be doped with
iodine to give =0.6 GPa, a strength of
0.033 GPa, and a conductivity of 13 S/cm.
After stretching (see next section) to a draw
ratio of two in the undoped state, E was
7.9 GPa and the strength was 0.18 GPa, and
after doping, E was 2.5 GPa, the strength
was 0.083 GPa, and the conductivity was 70
S/cm. This material shows an increase in
conductivity on stretching, but a decrease in
mechanical properties on doping, as for the
related fiber materials discussed next.
14.9 Post-Forming Treatment
for Conductivity and Strength:
Polymer Doping and Stretch-
Aligning
Some type of further treatment of the
polymer may be necessary after it is formed.
 14.9 Polymer Doping and Stretch-Aligning
The polymers need to be doped to make
them usefully conducting if they are not
formed in the doped state, and the conduc-
tivity and mechanical properties can be
improved by tensile processing. Surface
treatment of the polymers, for example, to
improve adhesion with metal electrical con-
tacts, may be necessary.
For many applications it is an advantage
to align the polymer chains in the films so
that the macroscopic properties are
enhanced, for example, for increasing the
conductivity and NLO (nonlinear optical)
effects as well as for improving the mechan-
ical properties. (See also Chap. 11 of this
Volume.) Other examples are for LED
devices; when the polymer chains are well
aligned in the film plane the emission is
strongly polarized, and oriented PANi
blends can be used as 'plastic' IR polariz-
ers (Cao et al., 1994).
Highly oriented films of PPV and poly-
(thiophene-vinylene) have been produced
(Tsutsui et al., 1991) by spin coating the
organic solvent soluble, methoxy-substituted
precursor polymers onto insulating polymer
substrates. These methoxy precursors are
stable at room temperature. The films were
partly converted and then, while the polymer
substrates were stretched at around 100 C,
the precursor was fully converted by a stream
of HC1 gas, giving oriented films of about
0.1 |im thickness. These showed optical
anisotropy in the spectra and the K-TV* band
shifted to a longer wavelength, showing an
increase in the ^-conjugation length. A typ-
ical organic solvent soluble precursor for
(2,5-dimethoxy)PPV is poly[2,5-dimethoxy
/?-phenylene(l-methoxyethylene)]. The wet-
spun films of this precursor polymer can give
a conductivity of 1200 S/cm when doped and
converted simultaneously in a temperature-
controlled, continuous drawing system. The
Young's modulus (E) and tensile strength of
stretch-aligned PPV films produced from the
687
methanol-water soluble polyelectrolyte pre-
cursor have reached 40 GPa for E and
0.5 GPa for the tensile strength. Films of
phenyl-substituted PPV can be stretch-
aligned by drawing above their softening
points, although some crosslinking occurred
during the thermal conversion at 230 C, to
give conductivities of about 10~4 S/cm when
vapor-doped with iodine or SbF5 (Garay
et al., 1995).
Ordered and aligned PTH has an
increased conductivity of about 1000 S/cm
(McCullough and Williams, 1993), and
aligned PYRo has a conductivity of up to
about 10000 S/cm.
So far, PAC has shown the highest values
for mechanical properties as well as conduc-
tivity. Films of PAC from the Ziegler cata-
lyzed route (Sec. 14.3.1), particularly the
nonsolvent method, can be drawn to give
highly conducting materials. The dry films
can be drawn at room temperature at
1 cm/min under a nitrogen atmosphere, with
the thicker films having a draw ratio of up
to 6 - 8 times. Higher draw ratios can be
obtained by soaking the films in a plasticiz-
er, such as hexadiene or a cumene and
toluene mixture (Cao et al., 1991b). This
gave draw ratios of up to 15 for the thicker
films. The mechanical properties vs. the
draw ratio are shown in Fig. 14-16.
A linear correlation between the conduc-
tivity and the mechanical properties such as
the Young's modulus and the tenacity has
been observed, as shown in Fig. 14-17. Both
the tensile strength and the conductivity
generally increase as the chain orientation
increases (refer to Chap. 11 of this Volume,
where the ultimate tenacity is discussed and
is also controlled by the molecular orienta-
tion). Values of the modulus were approxi-
mately 100 GPa and for the tensile strength
0.9 GPa for stretched films, although if a
linear correlation with the draw ratio is
assumed, an extrapolated value for the mod-
688 14 Conducting Polymers and Applications

2 4 8 4 8
Draw ratio Draw ratio
Figure 14-16. (Left) Young's modulus versus draw ratio for (a) mainly cis PAC and (b) aW-trans PAC, prepared
by the nonsolvent method. (Right) Tensile strength versus draw ratio for (a) mainly cis PAC and (b) a\\-trans PAC
(Kyotani et al., 1988).

a) 20000 ulus would be about 300 GPa. The conduc-

tivity vs. draw ratio and the conductivity vs.
the conjugation length are shown in
Figs. 14-18aand 14-18b, respectively.
"f 10000 The mechanical properties and morphol-
"o ogy of stretched films have been investigat-
13
o
c
ed (Kyotani et al., 1988), and the refined,
o purified, and iodine-doped PAC has a con-
O
ductivity of up to about 105 S/cm when
10 20 30 40 50 highly stretch-aligned (Naarman and
Young's modulus (GPa)
Theophilou, 1987). Conductivities of
20000-30000 S/cm are achieved for draw
ratios of 10-15, with film thicknesses of
b) 20000
30-3 |im, while a high anisotropy of the
conductivity is observed of around a factor
of 250 parallel to the draw direction com-
pared to the perpendicular direction, as
.^10000 shown in Fig. 14-19.
Further improvements in materials pro-
cessing with a reduction in disorder could
o
O lead to truly metallic conducting polymer
morphologies. If the data such as that in
0 0.2 0.4 0.6 0.8 1.0
Tenacity (GPa) Fig. 14-18 is extrapolated to the 100%
aligned material, a conductivity of a little
Figure 14-17. Electrical conductivity of polyacety-
lene versus (a) the modulus and (b) the tensile strength over 105 S/cm is expected.
(Cao et al., 1991 b). Reprinted with permission from Tensile drawn fibers of doped PAC (Cao
Elsevier Science Ltd., Oxford, UK. et al., 1991 b) have conductivities of about
 14.9 Polymer Doping and Stretch-Aligning
1 10 20
Draw ratio
20 40 60 80 100 120
Conjugation length (A)
Figure 14-18. (a) Electrical conductivity of iodine-
doped polyacetylene (parallel to the draw direction)
versus the draw ratio; solid points, thin films of thick-
ness 3-5 jLtm; circles, films of thickness 25-30 Jim
(Cao et al., 1991b). Reprinted with permission from
Elsevier Science Ltd., Oxford, UK. (b) Conductivity
of iodine-doped (3.5%) polyacetylene plotted against
the conjugation length (Roth, 1991). Reprinted with
permission from Elsevier Science Ltd., Oxford, UK.
3xlO4 S/cm, while the mechanical proper-
ties of the doped fibers are still good, with
high modulus and strength (Andreatta et al.,
1990).
Fibers of (2,5-dimethoxy)PPV (PDMPV)
have been prepared from the poly[2,5-
dimethoxy /?-phenylene( 1 -methoxyethyl-
ene)] precursor by the wet-spinning process
as follows: the purified precursor polymer
was first dissolved in chloroform to give
about 5 wt.% and the viscous solution was
pumped at 13 dnrVmin through a 0.5 mm
diameter needle into a nonsolvent such as
hexane. The resulting fiber could be taken
689
300
200
100
10
Draw ratio
Figure 14-19. Anisotropy of electrical conductivity
of iodine-doped polyacetylene versus the draw ratio
(Cao et al., 1991b). Reprinted with permission from
Elsevier Science Ltd., Oxford, UK.
up onto a bobbin at 30 cm/min. The fiber
was then dried in a vacuum oven for 12 h,
giving a pale-green precursor fiber of about
50 |im diameter. Drawing and conversion
were carried out using a temperature-
controlled, continuous drawing tube fur-
nace (as above), with hydrogen chloride gas
passed through the furnace to catalyze the
conversion. The optimum conversion tem-
perature was 230 C, and at temperatures
below this the fibers were not fully convert-
ed (Tokito et al., 1991). The draw ratio was
controlled by changing the speed of the inlet
and outlet motors as the fiber passed through
the furnace, with the residence time in the
furnace being about 5 min. At 230 C, the
maximum draw ratio was eight and at this
value the modulus (E) was 40 GPa and the
tensile strength was 0.7 GPa, while the
unstretched fibers had a low modulus of
1.3 GPa and a tensile strength of 0.07 GPa.
As can be seen in Figs. 14-20 and 14-21, the
mechanical properties and the conductivity
of the fibers both increase with the draw
ratio (compare the MeHPPV fibers in
Sec. 14.8). The degree of orientation as
determined by X-ray scattering gives an
orientation function for this system close to
0.96, similar to the value for oriented PPV
films.
690 14 Conducting Polymers and Applications
2 3 4 5 6 7 8 9 10
(a) Draw ratio
4 5 6 7
(b) Draw ratio
Figure 14-20. Mechanical properties versus draw
ratio for (2,5-dimethoxy)PPV (PDMPV) (Tokito
et al., 1991): (a) Young's modulus, (b) tensile strength,
(O) for PDMPV fibers, () for PDMPV fibers doped
with iodine. Reprinted with permission from Elsevier
Science Ltd., Oxford, UK.
The (2,5-dimethoxy)PPV fibers could
then be doped with iodine vapor as described
below. While the undrawn iodine-doped
fibers had a conductivity of about 20 S/cm,
the conductivity increased with the draw
ratio up to a maximum of 1200 S/cm at a draw
ratio of eight, similar to the situation found
for films, and the mechanical properties
decreased slightly after doping to E=25 GPa
with a tensile strength of about 0.7 GPa. As
shown by the graphs in Figs. 14-20 and
14-21, significant improvements are also
expected for the PDMPV fibers by extrapo-
lation, if the maximum possible intrinsic
mechanical properties and conductivities can
2 3 4 5 6 7 8 9 10
Draw ratio
Figure 14-21. Electrical conductivity as a function of
the draw ratio of PDMPV fibers (Tokito et al., 1991).
Reprinted with permission from Elsevier Science Ltd.,
Oxford, UK.
be achieved by further improvements in the
preparation and processing of the materials.
It would be possible to improve the
mechanical properties and the conductivity
if higher draw ratios could be achieved, but
the high density of entanglements limits the
draw ratio of the polymers; one solution to
this problem is dilution of the CP in a poly-
mer 'gel', for example, ultrahigh molecular
weight polyethylene (UHMW-PE). This
produces a lower entanglement density than
found in polymers produced from the melt,
which remains low after removal of the sol-
vent in solution casting; these gel-processed
films and fibers can be tensile drawn to draw
ratios of about 200 (Smith and Lemstra,
1980). Using a solution of MEH-PPV and
UHMW-PE in decalin or xylenes to produce
a blend, the material could be highly ordered
by tensile drawing (Hagler et al., 1991); (3-
octyl)PTH with UHMW-PE has also been
processed by this method (Moulton and
Smith, 1992 a, b). The reduction in disorder
is due to mesoepitaxy, by the epitaxial orien-
tation of the conjugated polymer on the
internal surfaces of the gel-processed poly-
ethylene.
Post-synthetic doping is sometimes need-
ed when the polymer is synthesized chemi-
 14.9 Polymer Doping and Stretch-Aligning 691

cally. PAC can be doped by treatment with

iodine or other agents to give very highly
conducting material. This can be carried out
by a gas or vapor phase doping process or
by a solution doping process, for example,
films of PAC can be exposed to iodine vapor
or soaked in hexane containing iodine,
nitromethane containing FeCl3, or nitrome-
thane with NOSbF5, and the doping level
can be determined by weight uptake after
drying. The conductivity of films doped
with various oxidizing agents is shown in
Fig. 14-22 a for unstretched PAC materials,
and the effect of temperature is shown in
Fig. 14-22 b. Doping decreases the mechan-
ical properties, however, both the Young's
modulus and the tenacity for PAC being
0 1 2 3 4 5 6 7 8 reduced by a factor of 4 - 5 .
(a) Dop. concentration (mol%)
PPP (Mohammad et al., 1996), PPV, and
other polymers can be similarly doped,
10 iodine being a common dopant. In some
DC conductivity of applications the 'doping' actually takes
iodine-doped cis-(CH)x
10 2 place in situ in the device application, e.g.,
in electrochromic windows, as explained in
18.7% Sec. 14.11.2.3.
101
The case of PANi is a little different.
Because conducting PANi can be in a wide
range of different doped base or (protonat-
ed) salt forms, it is an exception among CPs
and its conductivity depends on both its oxi-
dation state and its protonation state, which
are important in applications such as sen-
sors (see Sec. 14.11.4).
The so-called self-doped polymers can be
synthesized by introducing an ionic acid
group into the polymer structure, e.g., as the
side-chain substituent in PTHs and PYRos
(to give truly 'intrinsically' conducting
polymers). For example, (3-alkylsulfonic
2 3 5 10 20 30 50 100 200 400 acid) PTHs have been studied and have con-
Temperature (K)
ductivities of about 0.1 S/cm, although they
Figure 14-22. (a) Change of the electrical conductiv- have an amorphous structure. They also
ity of polyacetylene upon doping with various doping
agents (Ehinger, 1984). (b) Temperature dependence show increased stability towards photo-
of the conductivity of iodine-doped polyacetylene for chemical degradation due to oxygen
various doping levels (Ehinger, 1984). (Arroyo-Villan et al., 1995).
692 14 Conducting Polymers and Applications
14.10 Other Conducting
Polymers: Polymer Electrolytes
Highly conducting conventional polymer
electrolytes should be mentioned as well as
conducting, filled conventional (insulating)
polymers, these forming two separate class-
es of conducting polymers.
Conventional solid polymer electrolytes
are high molecular weight polymers contain-
ing specific donor groups at appropriate
intervals along the chain to allow coordina-
tion to the alkali metal (or other) cations of
a salt with which the polymer forms a com-
plex. The material can therefore be thought
of as a solid solution of a salt, and the con-
ductivity is governed by dissociation of the
salt and the mobility of the ions through the
polymer matrix. The best known example is
poly(ethylene oxide) with a lithium salt, e.g.,
LiSO3CF3 or LiClO4; the structure is shown
schematically in Fig. 14-5. Lower molecu-
lar weight polymeric materials are highly
viscous liquids which can be used in electro-
chromic displays (ECDs) and batteries
as 'semi-solid' electrolytes. Conductivities
greater than 10~3 S/cm have been achieved.
The main application of these materials is
for lightweight, compact lithium batteries,
which can have a high potential of around
3 V and a high energy density. In these appli-
cations, a high conductivity must be accom-
panied by a high mechanical strength and
dimensional stability, because the materials
must be able to separate the electrodes and
prevent a short-circuit. Polymer electrolytes
are also being pursued for other applications,
for example, electrochromic devices, sen-
sors, and photoelectrochemical cells. These
materials will not be discussed further here.
14.10.1 Filled Polymers
One other method of obtaining conduct-
ing materials is to mix conventional con-
ducting fillers, e.g., carbon black or metal
particles such as aluminum, silver powder,
or steel fibers, into an insulating, conven-
tional polymer matrix. CPs can also be used
as the conducting fillers, for example, PANi
powder. An interesting example of PYRo in
a conducting composite is obtained by a dif-
ferent process. The PYRo is coated onto an
aqueous dispersion of insulating 10 |Lim
polyethylene spheres by adding iron (in)
chloride and pyrrole monomer to the mix-
ture. The PYRo was produced by oxidative
polymerization on the spheres, which were
then washed repeatedly to give a pure PYRo
coating. The thickness of the PYRo coating
was about 0.02 |nm. Mixtures of different
proportions of coated and uncoated polyeth-
ylene microparticle materials were then hot
pressed (Yoshino et al., 1993) at 90-130 C
and 2950 kg/cm2. The conductivity of the
pressed, coated material having a PYRo
content of only 1% was 0.2 S/cm. The gen-
eral method is analogous to making blends
of conventional polymers with CPs, and fur-
ther examples are given in Sec. 14-7.
In general the filled polymer mixture
becomes conducting when the filler concen-
tration is high enough for continuous con-
duction paths to form. However, the load-
ing, i.e., the proportion of filler required, is
normally so high that the mechanical prop-
erties of the material are poor. It is also dif-
ficult to control the conductivity because the
conduction rises so sharply with the filler
loading at the point where the conduction
becomes useful. Conventional filled con-
ductors will not be discussed further here.
14.11 Applications
Most of the CPs discussed have already
found commercial applications, while the
others are being actively pursued for poten-
tial applications, e.g., as light-emitting
 14.11 Applications 693

polymers and electrochromic devices (Scro-
sati, 1993). These polymers are usually
stable in the undoped state and relatively
stable in the doped state, except for highly
conducting PAC, which has found no prac-
tical application so far due to its instability.
The stability refers mainly to the reactivity
towards oxygen and moisture. PYRo, PTH,
and PANi usually having conductivities less
than 1000 S/cm, are quite stable and there
are many applications for them. Presently,
the most widespread applications are in
'electrolytic' capacitors and in the copper
plating of printed circuit boards, although
batteries, transistors, and LEPs are now a
major focus of attention (Harper and Samp-
son, 1994; Burnett et al., 1991). The tech-
nological process involved in the printed
circuit application and the photopolymer-
ization involved in photolithography will
both be described, while the others mostly
use the processes already described for
forming films, such as electrochemical de-
position or spin coating from solution (fol-
lowed by conversion if necessary) and the
LB technique for electronic applications.
Table 14-2 summarizes the properties
required for particular applications of CP
films.
14.11.1 Photopolymerization
and Photolithography
Photopolymerization of CPs is important
for a potential application in photolithogra-
phy, in which the conducting polymers can

Table 14-2. The specific film properties required for some particular conducting polymer applications a

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Electrochromic
Sensors
Battery materials
Load leveling installations
Capacitors
Electric power conductors
Electric power cable sheathing
Electromagnetic interference shielding
Photovoltaic devices
Photoconductors
Protective coatings
Piezoelectric polymers
a
Smyrl and Lien (1993).
694 14 Conducting Polymers and Applications
be patterned onto substrates by photopoly-
merization, for example, the 'wet' solution
photochemical or photoelectrochemical
techniques (Chap. 13 of this Volume; Soane
and Martynenko, 1989; Thompson et al.,
1994; Harper and Sampson 1994), or laser
irradiation (Segawa et al., 1989; Shimidzu,
1989, 1990). This fabrication of conducting
polymer networks is important in the area
of electronics and can be used as a general
method for small-scale integrated circuits.
Conventional multi-step photoresist proce-
dures can also be used with CPs.
Direct photopolymerization of isothia-
naphthene has been investigated and the
photosensitized polymerization of a coating
of pyrrole on an insulating polymer has been
performed using a mixture of a photosensi-
tizer with an oxidizing agent which is not
able to oxidize the pyrrole directly. The sen-
sitizer was Ru(bpy)3+ (bpy = bipyridyl),
which is converted to the oxidized
Ru(bpy)3+ form (with an absorbance maxi-
mum of 450 nm) when photoexcited, and
this oxidatively polymerized the pyrrole
monomers. A photomask of micrometer-
scale dimensions was used to give the CP
pattern in a negative form.
The photoinduced insolubilization by
crosslinking polymerization of (3-alkyl)-
PTHs has been used to form conductive
PTH-type patterned films (Arroyo-Villan et
al., 1995). Soluble conducting polythio-
phenes functionalized with methacrylate
side chains have also been used. These were
coated onto a substrate and irradiation with
UV-visible light photochemically cross-
linked the film and made it insoluble. The
conductive material could therefore be pat-
terned with a photomask and the remaining
unexposed polymer dissolved away. Imag-
ing by conventional semiconductor photo-
lithography could be performed, giving pat-
terned image coatings with a film thickness
of 75 nm at a resolution of 3 \im (Lowe and
(PTH)
Solid substrate
Polymerization
(FeCI3)
I
Irradiation
I Crosslinking
insolubilization
UV-vis
Photomask
Dissolution
Oxidation
Electronically conducting
plattern
Figure 14-23. Photolithographic process for obtain-
ing negative images.
Holdcroft, 1995). The pattern can then be
doped by further treatment if necessary to
give electrically conducting films. The pro-
cess is outlined in Fig. 14-23. Conductive
patterns can also be directly generated pho-
tochemically in polybutadiene films (Dai
et al., 1996). Use of CPs in electron beam
lithography is mentioned briefly in Sec.
14.11.7.
14.11.2 Conducting Polymer Film
Devices in Electronics
Semiconductor applications of conjugat-
ed polymers include Schottky diodes,
metal-insulator-semiconductor (MIS) di-
odes, MIS field effect transistors (MIS-
FET)s, light-emitting diodes (LED) using
light-emitting (electroluminescent) poly-

mers (LEP), and photoconductive and pho-
tovoltaic devices, all of which use thin films
of semiconducting polymers rather than
externally doped conducting forms of the
polymers. The availability of easily pro-
cessable, film-forming polymers is quite
recent and this is now an important and rap-
idly expanding area of research, which will
soon become a major application area
(Greenham and Friend, 1996).
These materials are processable, have
useful electronic properties, and offer the
possibility of tuning the electronic proper-
ties to particular applications. The advan-
tage of polymers over organic molecular
materials is their robustness compared to the
brittle (and often crystalline) molecular
materials, and the interest shown in these
polymers by commercial companies as well
as academic institutions is mainly due to the
potential for low cost fabrication of large
area, thin-film electronic devices (e.g., flat
screen color displays). Not only must it be
possible to process the polymers into thin
films (typically 10-1000 nm), but they
should be dense, free of pinholes, and of
very high purity. The polymer should also
of course be chemically and physically
stable, with a high glass transition temper-
ature; a precursor route is often used to
obtain these materials. Further applications
are in the areas of molecular electronics
(Williams et al., 1993) and so-called
'intelligent' materials. When they are in the
form of thin films, the stability of these
materials to ambient conditions is impor-
tant. Fortunately, the devices are usually (or
can be) encapsulated, which protects the
films. The long-term stability varies
depending on the polymer, PAC being
unstable while PPV and PTH are quite
stable, although PPV shows some photoox-
idation.
For other applications, e.g., rechargeable
batteries and electrochromic devices
14.11 Applications 695
(ECD), doped forms of the polymers are
required. When the CP is in the chemically
or electrochemically doped state, it can
accommodate ions. These are more com-
monly anions, to counterbalance the posi-
tively charged polymer obtained by oxida-
tive p-doping. The diffusion rates of these
inserted ions limit the conductivity and the
rate of switching from the insulating to the
conducting state. This determines the rate of
several important processes in these devic-
es, e.g., the switching in electrochromic
devices and the charging rate of secondary
storage batteries and electrochemical (so-
called 'electrolytic') capacitors. In general,
increased ion diffusion rates enhance the
performance of these materials. Therefore
control of the structure and morphology of
the films by the processing method is cru-
cial in controlling the diffusion and the per-
formance.
14.11.2.1 Polymer Transistors
These devices can use thin films of semi-
conducting polymers such as PAC (Friend,
1993) in diodes or transistor devices and of
PTH or oligomeric thiophenes in FETs (Tsu-
mara et al., 1988). Although the carrier
mobilities in polymer FETs are quite small
compared to those in silicon-based devices,
they have the advantage of being easy to
deposit over large areas using solution pro-
cessing methods, and they can be electro-
chemically deposited for substituted PTH.
These films are predominantly amorphous
when formed from solution, showing only
nanometer-scale microcrystallites. A typi-
cal MISFET device structure is shown in
Fig. 14-24. Note that the metal contacts in
this case are doped silicon, the semiconduc-
tor is PAC, and the insulating layer is sili-
con dioxide, allowing a high electric field
to be applied. Although the crystalline
oligomeric material sexithiophene has a
696 14 Conducting Polymers and Applications
Source Drain
Aluminum
Polyacetylene
/ electronic hybrid MISFET using poly-
higher carrier mobility, approaching that of
silicon, the polymers have the advantage
over amorphous molecular materials in that
they remain amorphous and do not recrys-
tallize after deposition.
The LB technique of oriented film depo-
sition has been used in fabricating semicon-
ductor FET devices with (3-hexyl)PTH
(Paloheimo et al., 1992), and while the
devices based on LB films cannot compete
with the present generation of inorganic sin-
gle crystal devices, if they do prove to be
reliable they could have important applica-
tions in the addressing of large area displays
or as interfaces to other films in highly spe-
cific sensor devices. The advantage of these
films -is the ability to tailor their electrical
properties to the required application at both
the synthesis and the deposition stage. By
building up multilayer structures of differ-
ent polymers in the layers, new devices or
materials can be engineered at the molecu-
lar level.
14.11.2.2 Light-Emitting Polymers
There has been much activity in the field
of light-emitting polymers since the obser-
vation of electroluminescence from PPV by
the Cambridge group in 1989 (Burroughes
et al., 1990); commercialization and devel-
opment are being carried out by several
teams, including UMAX in the U.S.A. and
Figure 14-24. Construction of an organic
acetylene showing the structure. Dimen-
sions shown are to scale, except for the
channel width (20 Jim) and length
(1.5 Jim). Reprinted with permission from
Nature (Burroughes and Friend, 1988).
Copyright 1988 Macmillan Magazines
Limited.
Cambridge Display Technology. Devices
made from light-emitting polymers (LEPs)
are in fact light-emitting diodes, showing
electrical rectification (Sundberg et al.,
1990; Friend, 1993) due to the semiconduct-
ing nature of the polymer. The color of the
light-emitting polymer device can be
changed by the choice of emitting polymer
and chemical tuning of the LEP band gap to
give emission from red to green or blue;
LEPs are now available covering the visible
spectrum (Holmes et al., 1993), which
would be useful in multi-pixel color display
screens.
Devices based on polymers can cover
large areas by coating from solution, but
these largely amorphous films do not under-
go recrystallization, which is a problem for
amorphous molecular film devices and
leads to a degradation in their performance.
Common conjugated polymers used in these
devices are PPV and the soluble 2,5-
disubstituted PPV types, giving green and
red emission. Processable LPPPs have also
been used as emitting polymers in LEDs
(Huber et al., 1994), but although PPP or
LPPP materials give blue luminescence in
solution or solid solution, they tend to give
lower energy emissions (often yellow) in the
solid state (films) when neat due to inter-
chain effects (Jing et al., 1994; Tasch et al.,
1996). Blue emission is obtained from
copolymers, e.g. of the LPPP type when

Transparent Cathode Anode
Indium/tin oxide pO|y(phenylenevinylene) |-V +V
/ ^ - Metal
Glass substrate
Figure 14-25. Schematic picture of a poly(phenyl-
ene-vinylene)-based light-emitting diode (LED). The
device is fabricated on a glass substrate with a trans-
parent coating of indium/tin oxide as the positive,
hole-injecting contact. The polymer is deposited by
spin coating the precursor polymer from solution in
methanol and heating to convert it to the conjugated
form, typically 100 nm in thickness, and the top con-
tact is deposited by thermal evaporation. Low work-
function metals such as aluminum, magnesium, and
calcium are chosen for this contact to enable electron
injection (Burroughes et al., 1990; Friend et al.,
1992).
short PPP units are present, or from PPV
copolymers with short PPV units.
LEPs can also be coated onto flexible
polymer substrates, even using a thin film
of a CP as the transparent electrical contact
(e.g., ITO coated PET or PANi coated PET),
to give flexible devices (Herold et al., 1994;
Gustafsson et al., 1992). The polymer solu-
tions are normally spun, cast, or coated
(Fig. 14-9) onto a transparent conducting
substrate using an adjustable doctor blade,
e.g., ITO coated glass. In the case of PPV,
the precursor is then converted to the final
polymer film. The second (top) contact is
usually a metallic contact which is vacuum
evaporated or sputtered on top of the poly-
mer. A typical electroluminescent polymer
LED structure is shown in Fig. 14-25.
Although the device lifetimes are some-
times short for certain polymers and device
configurations, long lifetimes have been
reported for some devices and these are
presently being improved. High quantum
efficiencies of 1 % or more have also been
reported, for example, with MEH-PPV, and
devices with further layers of hole-injecting
14.11 Applications 697
or electron-injecting materials between the
emitting polymer and the electrodes have
been used to give higher efficiencies.
A metal contact has also been fabricated
on melt-processable (3-octyl)PTH. This
was formed by heating the polymer struc-
ture to the melting point of the polymer,
about 165 C, and then pressing the metal
contact onto the melted polymer until adhe-
sion was achieved. The structure was then
cooled and showed no significant differ-
ences to a device with a sputtered metal con-
tact. For some applications it is an advan-
tage to align the polymer chains in the films
so that a desirable macroscopic property is
enhanced. Recently, polarized light emis-
sion has been obtained in these polymer
LEDs by using stretch-aligned PTH (Dyrek-
lev et al., 1995) or an LB processed soluble
PPP (Cimrova et al., 1996).
In fact, even white light emitting devices
can be made from a blend of several substi-
tuted PTH polymers, each emitting a differ-
ent color to give white light in combination,
mixed with a conventional insulating poly-
mer (e.g., PMMA) (Granstrom and Inganas,
1996). The great advantage of LEPs com-
pared to other flat panel displays is that they
do not require any external source of light-
ing, unlike ECDs or LCD devices, and they
can still be made very thin. Screens contain-
ing many small LEP pixels can display text
or graphics, while a small number of large
LEP blocks could show more simple pat-
terns or messages, or single blocks can be
used as back lighting for other (e.g., LCD)
displays.
Another type of device is the light-
emitting polymer electrochemical cell,
which is constructed in a multilayer config-
uration containing an electrolyte (similar to
an ECD or a battery), although a solid elec-
trolyte such as poly(ethylene oxide) con-
taining a lithium salt can be used (Pei et al.,
1995).
698 14 Conducting Polymers and Applications
14.11.2.3 Electrochromic Devices
An electrochromic material is one which
shows a reversible color change when a
potential is applied due to an electrochemi-
cal reaction, and that persists in this colored
state until a different potential is applied
without the need to consume power
(although in practice there may be a slow
decay of the color due to instability of the
doped state of the polymer and electrical
leakage, requiring further application of the
potential). CPs are therefore suitable mate-
rials for electrochromic devices (ECDs),
because they can be reversibly driven from
a doped to an undoped state with a high con-
trast in color. In practical applications the
switching time between the two states
should be very short and the material should
retain its properties over many switching
cycles. The switching time depends on the
rate of ion migration through the material,
so the rates are not very high; the best
switching times are above a few millisec-
onds. The stability of the doped state, which
can lead to fading of the color, is also a fac-
tor determining the total number of switch-
ing cycles. PTH is useful because of its high
stability in the doped state, and in thin films
it has a switching time of about 30 ms; it can
be cycled more than one million times, rep-
Can be Optional lonically Primary ITO Glass
reflective secondary conductive electrochromic support/
counter electrochromic electrolyte layer (solid)
electrode layer (solid) _
resenting a lifetime of two years at one cycle
per minute.
The device basically consists of two elec-
trodes, one of which is the CP, with an elec-
trolyte between them. In practice the CP is
normally a film coated on a conducting sup-
port, e.g., ITO on glass (which is transpar-
ent), and the electrolyte can be either liquid
or a solid polymer type. A typical device
structure is shown in Fig. 14-26. This
arrangement is in fact an electrochemical
cell (EC) or a rechargeable battery. The
potential of this battery is similar to the orig-
inally applied potential. The counter elec-
trode can be metallic if the device operates
in reflective mode, or transparent (as well
as the electrolyte) if operating in transmis-
sion. The color changes occur when the
device is charged or discharged, normally
by applying a potential of a few volts. In
practice the devices are normally p-doped
because the n-doped forms are less stable
and greatly influenced by the nature of the
counter ions. Thin films of CPs prepared by
electrochemical oxidative polymerization
from monomers, such as PANi, PYRo, or
PTH, are all doped with counter ions and are
in the conducting state; they are all poten-
tially electrochromic. PYRo films are yel-
low in the undoped state and green in the
oxidized state. For PTH films, the colors can
hv
Figure 14-26. Schematic diagram
of an EC mirror operating in
reflectance mode (with the reflec-
tor as the counter electrode). With-
out the mirror, the cell could have
a transparent ITO electrode and
window work in transmittance mode, (hv is
the radiation energy.)

be tuned by changing the substituents on the
polymer chains, for example, PTH is red
when undoped and blue in the oxidized
state, while (3-methyl)PTH is purple when
undoped and pale blue when oxidized. PANi
films undergo many reversible color chang-
es as the potential across the film is varied,
from transparent yellow to green to dark
blue to black. In practice electrochromic
devices made from PANi use only a restrict-
ed potential range, showing the clear yellow
and green states.
The application of electrochromism in
displays is an alternative to LCD technolo-
gy, which could be used in large as well as
small displays, offering good contrast, large
viewing angle, and color persistence with
(ideally) zero current (power) consumption.
Large electrodes could be used to show sim-
ple blocks of color, or a greater number of
small electrodes could be used as pixels to
display text or images. However, external
lighting is still needed for visibility, as for
LCDs, but unlike LEP materials. A liquid
electrolyte is also often used, leading to con-
struction and storage problems.
Electrochromic devices have found appli-
cation in optical information displays. Large
area window glazing for energy control is
being developed (for example, by Pilking-
ton), consisting of very thin polymer and
electrolyte layers sandwiched between two
layers of (ITO) glass. When an electric
potential is applied, the window tints and the
degree of tinting is controlled by the poten-
tial. Antiglare rear-view mirrors and sun
roofs for cars are available, and even con-
sumer sunglasses (Monk et al., 1995).
14.11.2.4 Polymer Battery Electrodes
and 'Electrolytic' Capacitors
The electrochemical doping of conduc-
tive polymers can be applied to battery tech-
nology, because the doping level can be con-
14.11 Applications 699
trolled, is reversible, stable, and both p- and
n-doping are possible. Both electrodes in a
battery can therefore be made of (the same)
CP, and these factors make CPs suitable
electrode materials for batteries. Polymer
electrode batteries can be lightweight and
'clean and green', with no polluting metal-
lic components. The perfection of such bat-
teries could make the electric car a reality,
since the main problem so far is the weight
of the batteries required. Research is still
continuing with PAC (Nigrey et al., 1981;
Maclnnes et al., 1981); a schematic repre-
sentation of the battery is shown in Fig.
14-27.
At present, PANi is used commercially in
battery electrodes (Bridgestone-Seiko).
These batteries are rechargeable 'button'
type cells, with one PANi electrode and a
lithium-aluminum alloy electrode. They
show low self-discharge, high voltage, and
high long-term reliability.
PYRo is already used for electrodes in
batteries (BASF) and PYRo in the form of
dispersed latex materials is being investigat-
Li Li+conducting Conducting
electrolyte polymer
Figure 14-27. Schematic diagram of a lithium bat-
tery with a conducting polymer electrode.
700 14 Conducting Polymers and Applications
ed for cathodes for solid-state lithium bat-
teries (DeLaBouglise, 1995), as are manga-
nese dioxide-PYRo composites for use as
cathodes in rechargeable lithium batteries
(Gemeay et al., 1995).
Batteries without liquid electrolytes are
being developed which could lead to high-
er long term reliability due to the absence of
corrosive liquids or gases. These all-plastic
batteries might also be flexible. The liquid
electrolyte in this case is replaced with a
film of solid polymer electrolyte (see
Sec. 14.11.2.3, which is doped with a salt)
to provide a separation barrier between the
two electrodes as well as an ionic conduc-
tion path. Alternatively, this layer can be
absent and the formation of a lithium iodide
salt at the interface of the doped PAC and
lithium metal electrode can act directly
as the electrolyte (Scrosati and Owens,
1987).
Similar advantages and properties of CPs
make them suitable for use in capacitors,
and solid films of PYRo are also used as
'electrolytic' capacitor electrodes, although
these can contain no liquid electrolyte (Mat-
sushita).
14.11.3 Antistatic Fabrics, Coatings,
Filled Matrices, and Shielding
Coatings of PYRo are used as antistatic
curtains, radar camouflage nets (used by the
military in the Gulf War), antistatic tiles, etc.
(Milliken). Conductive sheets are made by
Ciba-Geigy, while antistatic bags and films
are made of PTH (by Hoechst). CPs such as
PANi, PYRo, and PAC are effective for
shielding from electromagnetic interference
(Joo and Epstein, 1994).
Microparticulate dispersions of PANi for
extrusion processing with conventional
polymers are now commercially available,
e.g., from Americhem Co., Zipperling-
Kessler, Neste, and Hexcel. These can give
optically transparent and conducting films
and coatings, or they can be used in conduc-
tive polymer blends with conventional poly-
mers which can be formed into antistatic
components; the CPs can be used as field
shielding layers in electrical cables.
14.11.4 Chemical Detectors
and Electrode Sensors
There are several factors that make CPs
suitable for use as chemical detectors. Their
ability to change their physical properties
and conductivity by selective interaction
when a chemical is adsorbed onto the sur-
face of the polymer is essential to their use
as detectors. These changes can be produced
by redox or acid-base interactions. Ideal
sensors should also exhibit a fast reversible
response and stability. Conducting poly-
mers can be used for ion-selective electrode
materials, as thin films formed by electro-
chemical deposition on the electrode sur-
face, or as blends, e.g., poly(phenylacety-
lene) in PVC/PVAcetate/PVAlcohol. CPs
can also be used in multi-element chemical
and gas sensors in the form of films, and as
a host matrix for enzymes in medical sen-
sors, for example, in the detection of glu-
cose (Compagnone et al., 1995), urea, and
creatinine. These 'biosensors' are based on
enzymes immobilized in electropolymer-
ized CP films (Trojanowicz et al., 1995;
Schuman, 1995; Alegret et al. 1996).
PANi is already used in commercial elec-
trodes (Echema), being useful because its
conductivity depends on both its oxidation
state and its protonation state; PYRo can be
used in gas sensors (Costello et al., 1996).
PTH has been used for the detection of
hydrogen peroxide in acetonitrile (Tatsuma
et al., 1996), and PAC can be used for the
detection of nitrate ions in acid solutions
because the conductivity is changed by the
intercalation oxidation.

CPs such as PTH and polyfuran are
expected to find applications as humidity
sensors and radiation detectors, as the con-
ductivity of these materials rises when
exposed to humidity or radiation.
14.11.5 Copper Electroplating
for Printed Circuits
P YRo is used in through-hole copper plat-
ing processes for manufacturing printed cir-
cuit boards, e.g., by Blasberg and Atotech.
A large proportion of all the electronic prod-
ucts in Europe contain printed circuit boards
(PCBs) made using this technique, which is
perhaps the largest present application of
CPs. Coating through the holes in the PCBs
was in the past a particularly costly process,
but using a chemically deposited PYRo
layer to form the electrode, on which the
copper is then deposited to form the con-
ducting tracks of the PCB, has greatly sim-
plified and speeded up the process (Gottes-
feld et al., 1992; Harper and Sampson,
1994). The effect of the composition of the
PYRo layer on the copper (or nickel) elec-
troplating has been investigated (Hepel
et al., 1996).
14.11.6 Nonlinear Optics and Photonics
Nonlinear optical (NLO) devices can be
made from conjugated polymers, because
these materials have very large xO) suscep-
tibility coefficients in the undoped state,
which are enhanced by the linear conjugat-
ed structure when the polymer chains are
aligned. PAC, of all the conjugated poly-
mers to date possesses the largest third-
order nonlinear optical coefficient. These
polymers can also show nonlinear photo-
refractive index properties, e.g., in poly-
diacetylene-type materials. These proper-
ties are essential for all optical data network
devices and optical computers (Shi and
14.11 Applications 701
Garito, 1994; Rochford et al., 1991;
Proudley, 1992).
Ultrafast modulation or switching of light
has been demonstrated in devices based on
electrooptically active polymers which will
soon enter the commercial market, having
switching rates in the gigahertz region.
Functionalized CPs are being investigated
for these applications (Shimidzu, 1995;
Thackara et al., 1994).
14.11.7 Miscellaneous
Since Little (1964) proposed that high
temperature superconductivity was possible
in materials having a conducting backbone
to which polarizable side groups are
attached, it has been an area of active
research. The conjugated 'one-dimensional
graphite' polyacene polymers can also ful-
fill this requirement (Hu, 1993), and the pos-
sibility of superconductivity at low and
'high' temperatures is being investigated.
They can also be used with the ceramic-
type, high temperature superconductors in
layer assemblies which modulate the super-
conductivity onset temperature, Tc, for
example, using PYRo (Haupt et al., 1993).
CPs have possible applications as temper-
ature sensors and light sensors, as they show
photoconductivity in transparent conduct-
ing films, for example, photoconductivity
has been measured in situ in PANi films
(Genies et al., 1988). They are also possible
piezoelectric materials.
They could be used as potential drug
delivery systems, the principle being that if
the drug can be a dopant ion in the CP then
it could in principle be released by applying
a potential to the doped polymer. CPs can
be used in hydrogen storage systems as fuel
or energy sources, as possible corrosion
control materials, shape-selective heteroge-
neous catalysts, and for electron earthing in
electron beam lithography (Angelopoulous
702 14 Conducting Polymers and Applications
et al., 1993). Dispersions of CPs (e.g.,
PYRo) in various fluids have electrorheo-
logical properties and have possible uses in
stop valves, clutches, and brake systems
(Teare and Ratcliffe, 1996). These have
potential advantages over conventional
materials because they are noncorrosive and
nonabrasive.
In conclusion, to end this brief survey of
the applications of these remarkable mate-
rials with a pointer to the future, molecular
engineering on a nanoscale could lead to
molecular electronics applications (Bloor,
1991), and the electronic applications
already outlined will no doubt become even
more important. Applications such as LEP
devices are now being developed (Romero
et al., 1995), and the possibility of others on
a nanoscale are being investigated, e.g.,
electronic and photoelectronic devices
using CPs as 'molecular wires' (Shimidzu
et al., 1996).
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15 Materials Science of Pressure-Sensitive Adhesives
Costantino Creton

Laboratoire de Physico-Chimie Structurale et Macromoleculaire, ESPCI, Paris, France

List of Symbols and Abbreviations 708

15.1 The Adhesion of Polymers 710
15.2 Pressure-Sensitive Adhesives (PSAs) 711
15.2.1 General Principles and Main Applications 711
15.2.2 Formulations 712
15.2.3 Processing 712
15.3 Theoretical Modeling : 714
15.3.1 Thermodynamics of Adhesion 714
15.3.2 Crack Propagation in a Viscoelastic Medium 715
15.3.3 Cavitation and Fibril Formation 716
15.3.4 Bond Formation 721
15.3.5 Relationship Between Adhesive and Bulk Properties 724
15.4 Effect of Experimental Test Parameters 724
15.4.1 Peel Test 725
15.4.2 Quick Tack Test 727
15.4.3 Shear Test 730
15.4.4 Surface Properties of the Substrate 730
15.5 Effect of the Molecular Structure of the Adhesive 731
15.5.1 Molecular Origin of Viscoelasticity 731
15.5.2 The Glass Transition Temperature 733
15.5.3 The Molecular Weight 733
15.5.4 The Degree of Branching and Crosslinking 736
15.5.5 The Incorporation of Polar Groups in the Adhesive 736
15.5.6 The Tackifying Resin 737
15.5.7 Triblock Copolymers 738
15.6 Summary 739
15.7 References 739

Materials Science and Technology

Copyright WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
708 15 Materials Science of Pressure-Sensitive Adhesives

List of Symbols and Abbreviations

aT time-temperature superposition coefficient

A true area of contact
A* maximum true area of contact
D diameter
E Young's modulus
F force
G shear modulus
G' shear storage modulus
G" shear loss modulus
Go plateau shear modulus
G* critical value of G for perfect contact under zero force
\G*\ complex shear modulus
h thickness of the adhesive layer
AL displacement
M average molecular weight
Me average molecular weight between entanglements
Mn number-average molecular weight
Mw weight-average molecular weight
P pressure
R radius
t time
time of contact
T temperature
T glass transition temperature
f g disentanglement time of a fibril
dis
^ext extension time of a fibril
time to failure
V crack velocity
vc critical transition velocity
*cav crosshead velocity above which cavitation does not occur
v flb average fibril drawing velocity
w total adhesion energy
wadh thermodynamic energy of adhesion
wcoh thermodynamic cohesive energy
coordinate

7a surface energy of the adhesive

7s surface energy of the substrate
7as interfacial energy of the adhesive-substrate interface
adhesion parameter
strain rate
0 monomer friction coefficient
r\ viscosity
 List of Symbols and Abbreviations 709

0 angle
X extension ratio of a rubber
A extension rate
^max maximum extension ratio of a fibril
E, average surface roughness
<7 a d h maximum stress sustainable by the interface
crcav critical stress for internal cavitation
Tc characteristic time of a process
(p multiplicative factor of the adhesion energy
X Flory interaction parameter
co frequency

JKR Johnson - Kendall - Roberts

LDPE low density polyethylene
NR natural rubber
PBA poly(n-butyl acrylate)
PIB polyisobutylene
PS polystyrene
PSA pressure-sensitive adhesive
SBR styrene-butadiene rubber
SIS styrene-isoprene-styrene block copolymer
TEM transmission electron microscopy
VA-EA vinyl acetate-2-ethylhexyl acrylate copolymer
vdW van der Waals
WLF Williams - Landel - Ferry
710 15 Materials Science of Pressure-Sensitive Adhesives
15.1 The Adhesion of Polymers
A thorough study of the processes in-
volved in the adhesion of polymers bridges
across several fields of the physical scienc-
es, that is, physics, chemistry, mechanical
engineering, and materials science. It is the
author's opinion that an inherently cross-
disciplinary view of adhesion is necessary
to understand its basic principles, and such
an attempt is presented here with special
emphasis, however, on the influence of the
materials' properties. The proper formula-
tion of good adhesives comes under the
heading of polymer processing but, as in
many other parts of this Volume, we will
rather focus on how processing of polymers
produces a particular microstructure with
well-defined properties.
One talks of adhesion when a measurable
amount of mechanical work is necessary to
separate two surfaces of different chemical
composition or shape. Before discussing the
different mechanisms of adhesion and the
types of adhesive, it is useful to formulate
some general concepts on adhesion. Al-
though the maximum force necessary to
break the bond may be defined as a meas-
ure of adhesion, the typical measure of the
strength of an adhesive bond across an inter-
face is the amount of energy necessary to
break it, i.e. to separate the two surfaces.
Such a separation may involve the breakage
of chemical or van der Waals bonds, as well
as the plastic deformation of one or both of
the bulk materials on either side of the inter-
face. Typically in all cases where good ad-
hesion is obtained, the fraction of energy
necessary to break the bonds at the interface
is a very small fraction of the total energy
necessary for the separation of the two sur-
faces; most of the mechanical work is used
to deform, under stress, the material adja-
cent to the interface. Therefore the meas-
ured energy of adhesion will be dependent
on the ability of the interfacial bonds to sus-
tain stress, as well as on the amount of plas-
tic deformation caused locally by the above-
mentioned stress (Brown, 1991). (Note: The
elastic deformation caused by the stress
does not cause any irreversible work to be
done over and above that required to break
the bonds joining the interface.)
If the two surfaces are of the same mate-
rial, we speak of self-adhesion or auto-
hesion. However, in the case of polymers,
self-adhesion is usually dependent on the
time of contact and, at infinite time, will
eventually become the cohesive strength of
the material rather than an adhesive proper-
ty. In the more general case, where the two
materials are dissimilar, adhesive bonds can
be divided according to their strength (struc-
tural, permanent, and nonpermanent) and to
the nature of the adhesive/adherend pair:
glassy polymer/glassy polymer,
glassy polymer/nonpolymer,
glassy polymer or nonpolymer/elastomer
or polymer melt,
polymer melt/polymer melt.
Polymer/polymer adhesion in glassy
polymers has been the subject of much inter-
est recently (Brown, 1991; Wool, 1991). Its
main applications are in the development of
alloys and blends made from immiscible
polymers, and where the interfacial proper-
ties between the two phases are crucial to
the performance of the material. The ability
of the interface to sustain stress is depen-
dent on the number of well-entangled poly-
mer chains that cross the interface, and sev-
eral approaches have been proposed to in-
crease that number effectively. The mecha-
nisms by which these connecting chains
were active in reinforcing the interface in
glassy polymers has also been demonstrat-
ed in a series of elegant experiments (Brown
et al., 1993; Char et al., 1993; Creton et al.,
1992).
 15.2 Pressure-Sensitive Adhesives (PSAs)
Glassy polymer/nonpolymer adhesion is
typically the situation arising in structural
adhesives, where an adhesive strength equal
or superior to the cohesive strength of the
base materials is required. Because interdig-
itation of the polymer chains is not possible,
the surface of the solid material and not
equilibrium thermodynamics determines
the topology of the interface, so that surface
roughness becomes an important parameter
for this type of adhesion. In the absence of
surface roughness, the chemical interac-
tions between polymer and solid play the
role of stress transfer agents and the fracture
energy is usually due to the resulting plas-
tic deformation of the polymer. An excel-
lent review of the technological side of this
subject is given in the book by Kinloch
(1987).
Polymer melt/polymer melt adhesion is
mostly relevant for the processing of elas-
tomers prior to the crosslinking process, and
is of particular importance to the tire in-
dustry. This type of adhesion is sometimes
called tack or green strength and has been
reviewed by Hamed (1981).
Finally, polymer melt/solid adhesion is
typical of nonpermanent and relatively
weak adhesion and is often called pressure-
sensitive adhesion, because once a certain
amount of pressure has been applied, a mea-
surable adhesion between the two surfaces
is observed..Interdigitation of the polymer
chains is impossible, so chemical interac-
tions, surface roughness, and the rheologi-
cal properties of the adhesive are respon-
sible for the measured energy of adhesion.
By the variety of problems involved, span-
ning polymer physics, rheology, and contact
mechanics, as well as surface chemistry, this
subject is ideally suited to demonstrate the
usefulness of a materials science approach,
which is the object of the following sections.
Furthermore, although the subject of pres-
sure-sensitive adhesion is of great techno-
711
logical importance, its inherent complexity
has discouraged more systematic funda-
mental work and relatively few reviews are
available on the subject (Dahlquist, 1969;
Kaelble, 1969b; Krenceski et al., 1986;
Zosel, 1992).
The purpose of this chapter is to present
a relatively unified view of the subject with
a clear bias, however, towards the under-
standing of the molecular mechanisms re-
sponsible for adhesion. Detailed mechani-
cal analyses of the test geometries are pur-
posely avoided in order to concentrate as
much as possible on materials' properties
and microdeformation mechanisms.
15.2 Pressure-Sensitive
Adhesives (PSAs)
15.2.1 General Principles
and Main Applications
Pressure-sensitive adhesives have in
common the property of developing mea-
surable adhesion to a surface simply upon
contact or by the application of a light pres-
sure. In this type of adhesion, no chemical
reaction generally takes place between the
substrate and the adhesive, no curing of the
adhesive is necessary, and finally, no sol-
vent is lost during the adhesion process.
Such properties imply that intimate contact
between the substrate and the adhesive must
be established rapidly and under slight pres-
sure, but also that the energy necessary to
separate the adhesive from the substrate
must be sufficient for the specific applica-
tion. Such a combination of properties is
uniquely found in polymers above their
glass transition temperature, and a balance
between compliance and fracture energy is
the key when tailoring the properties to a
specific application.
712 15 Materials Science of Pressure-Sensitive Adhesives

Broadly speaking, pressure-sensitive ad-
hesive applications fall into three catego-
ries:
1) Removable PSAs: For this application,
a high compliance is required in order to es-
tablish contact very easily, but, conversely,
low adhesion is necessary. In addition, the
separation must be completely adhesive to
avoid residues of the adhesive layer on the
substrate. The most well-known application
is the Post-It note, but masking tape or
mounting spray adhesives are also good ex-
amples.
2) General-purpose, semi-permanent: This
is the most common type of adhesive, where
medium compliance and a relatively good
adhesion are necessary, but no long-term re-
sistance to the environment is needed as the
lifetime is typically of a few months at the
most. The standard office tape, label, or the
ubiquitous finger bandage fall into this cat-
egory. The adhesive is said to be permanent
if, upon removal, the backing will fail be-
fore the adhesive bond.
3) Permanent, semi-structural: In this case,
the critical property is very high adhesion
and very high creep resistance, as well as
good resistance to the environment. In this
type of application, the PSA's ease of appli-
cation is the motivation to use it as a substi-
tute for more conventional adhesives. How-
ever, the high compliance required usually
necessitates a more careful bonding process.
15.2.2 Formulations
Industrially, the desired properties are
usually obtained by formulating a miscible
blend of uncrosslinked or partially cross-
linked (up to the gel point) polymer, a tack-
ifying resin, a plasticizer, and various stabi-
lizers. The polymer forms the backbone of
the adhesive and provides the long term
creep resistance and the tensile strength nec-
essary for adhesive rather than cohesive sep-
aration. The tackifying resin, which is usu-
ally an oligomer that is fully miscible with
the polymer, has the function of substantial-
ly increasing the tack of the polymer, while
the plasticizer is usually added for process-
ing purposes.
The polymers used fall into four broad
families, each having its specific advant-
ages: polyacrylates, silicone polymers,
polydienes and random copolymers [natural
rubber (NR) and styrene-butadiene rubber
(SBR)], and, finally, block copolymers of
styrene -diene. NR and SBR are cheaper but
always require a tackifying resin, silicones
can be used over a very wide range of tem-
peratures and are often used for medical ap-
plications, while the properties of polyacry-
lates can easily be tailored by proper choice
of the co-monomer and the appropriate
co-polymerizations, polyacrylates do not
usually require the presence of a tackifying
resin. Styrene-isoprene-styrene block co-
polymers have been developed recently,
mainly because of their physical crosslink
structure, which makes them good candi-
dates for hot-melt processing. Other poly-
mers used for PSA application include
poly(vinyl methyl ether), polyisobutylene,
and vinyl acetate, which is often used as a
co-monomer with an acrylate.
For the tackifying resins, rosin deriva-
tives, such as the pentaerythriol ester of
highly stabilized rosin and the polyterpenes
(of a-pinene or /3-pinene) are often used.
Their molecular weight is usually between
500 and 1500 and is chosen to avoid phase
separation between the resin and the poly-
mer. Some examples of polymers and tack-
ifying resins are given in Fig. 15-1.
15.2.3 Processing
As the overhelming majority of PSAs are
supplied as some form of tape, an important
 15.2 Pressure-Sensitive Adhesives (PSAs) 713

Polymers and monomers

CH3 CH3 CH3

--CH2--C=:CHv si
I
CH3 CH 3
Natural Rubber Polyisobutylene Polydimethylsiloxane
H
-f-CH2-C=CH-
1-x

Styrene-Butadiene random copolymer

CH2=CH CH2=CH CH2=CH

C=O C=O

Acrylic monomers
O
CH 2
?C H
4 9
OH

C2H5-CH
C4H9

2-ethylhexyl acrylate n-butyl acrylate acrylic acid

Resins

Indene (aromatic) Dicyclopentadiene

(aliphatic)

abietic acid
(rosin derivative)

(3-pinene (terpene resin)

Figure 15-1. Common polymers and tackifying resins used in PSAs.

part of the design of PSAs includes a suit-
able processing method to apply the adhe-
sive on the tape, usually called backing.
Three types of processes are commonly
used: application from solution, from aque-
ous emulsion, and hot melt. Application
from solution is the simplest and was also
the first historically; however, because of
environmental concerns, there is more and
more demand for systems that can be pro-
cessed without the use of a solvent. Aque-
ous emulsions have become increasingly
popular, particularly for acrylic adhesives.
The coating process is more difficult, how-
ever, as water wets low-energy surfaces
poorly and gives rougher coatings. Further-
714 15 Materials Science of Pressure-Sensitive Adhesives
more, because of the surfactants, which are
part of the formulations, these adhesives
usually have a poor water resistance.
Another alternative is the holt-melt pro-
cess, where the bulk adhesive is directly
coated on the substrate. The requirements
for such a system are for the adhesive to be
sufficiently fluid at the processing temper-
ature while retaining a high creep resistance
at the usage temperature. Keeping in mind
that the processing temperature is limited by
degradation of the polymer, it becomes clear
that the material must have a discontinuous
jump in viscosity. Styrene-isoprene-sty-
rene (SIS) triblock copolymers form a phys-
ically crosslinked network below the glass
transition temperature of the styrene block
while flowing readily above it when the
permanent network is melted, and therefore
constitute a prime example of hot-melt
PSAs.
15.3 Theoretical Modeling
This section contains the largest original
contribution from the author and deserves a
few lines of introduction. From the large
body of experimental work on PSAs, many
qualitative conclusions have emerged on the
influence of the different experimental as
well as molecular parameters. Here a cer-
tain number of mechanisms are proposed
that are consistent with the available experi-
mental data and clearly show which param-
eters should be relevant for a specific pro-
cess, therefore giving a more fundamental
meaning to well-known empirical correla-
tions. These sections are organized to go
from more general concepts, e.g., the ther-
modynamic work of adhesion and the prop-
agation of a crack in viscoelastic media, to
some problems that are more specific to
pressure-sensitive adhesives, e.g., the pro-
cess of bond formation under pressure and
the mechanisms of fibrillation. Considering
the general interest in the prediction of the
adhesive properties of PSAs from their bulk
properties, Sec. 15.3.5 reviews the main ad-
vantages and shortcomings of this metho-
dology.
15.3.1 Thermodynamics of Adhesion
In this section, it is implicitly assumed
that the contact between the adhesive and
the substrate is perfect, i.e., that there is no
surface roughness and that the bond forms
instantaneously upon contact. This assump-
tion is clearly not true and has significant
implications for the measurement of quick
tack, which will be treated in Sec. 15.3.4.
However, it is easier to concentrate on the
perfect contact case first, which is a reason-
able assumption when interpreting peel test
results.
The study of the molecular interactions
between two surfaces has been the object of
numerous reviews aimed mostly at relating
the chemical structures present on the sur-
face to the thermodynamic energy of adhe-
sion. Although a detailed review of the ther-
modynamics and chemistry of adhesion is
beyond the purpose of the present text, it is
useful to review some basic concepts.
In the simplest case of the contact of an
adhesive A and a rigid substrate B, which
do not react chemically nor have specific
interactions, the process of forming A - B
contact and then separating the surfaces in-
volves the formation and then destruction of
van der Waals bonds. The energy necessary
to break these bonds per unit area of surface
is given by
= /a + 7s " 7as (15-1)
where ya and ys are the surface energies of
the adhesive and of the substrate, respec-
tively, and 7as is the interfacial free energy.
If the forces are purely dispersive, the inter-

facial energy is approximately given by
7as^ 7a + 7s- 2 (7a7s) 1/2 (15-2)
so that the thermodynamic energy of adhe-
sion is given by
w _ J (y y \l/2 / i <r o\
adh V/a/s/ v A ^ ~v
On the other hand, the cohesive energy of
the adhesive will be given by
WtcohA (15-4)
Two main observations should be made
from these results. First, the adhesion ener-
gy is predicted to increase with the surface
energy of the substrate and, second, such an
approach would predict cohesive failure in
the adhesive if Ys>Ya- None of these simple
predictions have actually been quantitative-
ly confirmed experimentally.
Furthermore, it is well known that the
measured adhesion energy W is usually
several orders of magnitude higher than
what is predicted by the thermodynamic
equations.
15.3.2 Crack Propagation
in a Viscoelastic Medium
The above-mentioned discrepancy comes
from the energy dissipated in the bulk ma-
terials during the separation process. In the
case of a pressure-sensitive adhesive, the
adhesive is usually much more compliant
than the substrate, so that it is a reasonable
approximation to consider that nearly all
the energy is dissipated in the adhesive
layer.
The viscoelastic properties of a polymer
are usually characterized by its complex
modulus as a function of frequency and/or
temperature. If the amount of deformation
is small, the viscoelasticity is linear (histo-
ry independent) and the WLF time-tem-
perature superposition principle applies
(Ferry, 1980).
15.3 Theoretical Modeling 715
Historically, the first approach to the
problem of viscoelastic losses was to as-
sume that when a crack propagates at the
interface between a rigid substrate and a vis-
coelastic rubber, the measured fracture en-
ergy is directly proportional to the magni-
tude of the thermodynamic energy of adhe-
sion Wadh (Andrews and Kinloch, 1973 a, b;
Gent and Schultz, 1972), and the viscoelas-
tic losses in the rubber appear simply as a
multiplication factor of Wadh, so that the ad-
hesion energy W is given by the empirical
relation
W = W d h [l + 6(T,V)] (15-5)
where the multiplicative factor (j) is depen-
dent on the temperature, the rate of separa-
tion, the molecular structure, and the experi-
mental geometry. The implicit assumption
of such a relation is that the deformation is
homogeneous in the adhesive and the ener-
gy per unit volume dissipated during the de-
bonding process is directly proportional to
the loss modulus G"(a)) at a characteristic
frequency co directly proportional to V.
What is equally assumed is that van der
Waals forces act over a relatively short dis-
tance across the interface, a distance that is
not likely to depend much on the adhesive-
substrate pair. Therefore it can be assumed
that W.ddh is proportional to the maximum
stress (Jadh that the interface can sustain
before failure. Furthermore, the expected
proportionality of the fracture energy on G"
implies that the temperature and the rate of
deformation of the adhesive are related by
the time-temperature superposition princi-
ple.
More recently de Gennes (de Gennes,
1988) pointed out, however, that for an in-
finite sample and sufficiently high veloc-
ities, there is always a zone of maximum vis-
coelastic dissipation which simply moves
away from the crack tip with increasing
crack velocity. According to his analysis, W
716 15 Materials Science of Pressure-Sensitive Adhesives
should increase linearly with V up to a crit-
ical value which is inversely proportional to
the characteristic relaxation time of the
polymer and then become a constant at high
velocity. This would imply that there is
no direct correlation between W(V) and
If the characteristic size of the sample is
finite, however, the "lossy" zone can be
driven out of the sample at sufficiently high
velocities causing W to decrease sharply.
This result has been confirmed by an
elegant mathematical analysis (Hui et al.,
1992), but has yet to be demonstrated con-
clusively experimentally.
It should finally be pointed out that the
assumption of homogeneous deformation of
the adhesive made in the previous para-
graphs is more typical of the adhesion
of crosslinked rubbers on rigid substrates
(Andrews and Kinloch, 1974). In the case
of the adhesion of PSAs, there is often the
possibility of cavitation in the adhesive
layer with subsequent fibril formation,
which clearly involves large inhomogene-
ous deformations, so Eq. (15-5) would not
necessarily be expected to hold in this
case. Nevertheless, it is a well-established
experimental fact that the curves of adhe-
sion energy as a function of temperature or
peel rate obey the WLF time-temperature
superposition quite well, even in regimes
where fracture occurs by extensive fibrilla-
tion (Aubrey and Sherriff, 1980; Kaelble,
1969 a).
film
I
\ Figure 15-2. Schematic
t<0
15.3.3 Cavitation and Fibril Formation
As first pointed out by Kaelble (1965), the
formation of fibrils is crucial to the amount
of energy dissipated by the adhesive during
deformation, and it is important to under-
stand the mechanisms of nucleation and
growth of these fibrils.
The best experimental geometry for vis-
ualizing the mechanism of cavitation is that
of the probe tack, where a thin film of ad-
hesive bonded on one side to its backing is
first brought into contact with the substrate
(a probe in this case) and then removed, as
shown schematically in Fig. 15-2. In this
process the film is subject to a hydrostatic
tensile stress. If the adhesion forces to the
substrate are sufficient to sustain a stress of
the order of the shear modulus of the adhe-
sive, cavities will nucleate in the adhesive
layer and possibly grow so that the deform-
ed adhesive will evolve towards a fibrillar
structure.
The nucleation and growth of cavities
under a hydrostatic stress can be considered
for two limiting cases: the viscous liquid and
the elastic solid. Considering the high de-
formation rates involved, the treatment
based on rubber elasticity developed by
Gent and co-workers (Gent and Lindley,
1958; Gent and Wang, 1991) seemed the
most appropriate for PSAs in their normal
conditions of use and is presented here. For
the viscous liquid treatment, which could be
relevant at high temperatures or for low vis-
diagram of the probe tack
t>tc experiment.

cosities, the reader is referred to the theo-
retical work of McEwan (1966) on the peel-
ing of a viscous adhesive, or the experimen-
tal work of Erb and Hanson (1960) on probe
tack testing of low molecular weight visco-
elastic liquids.
When a spherical cavity in a rubber is
subjected to internal pressure, it expands in
a highly nonlinear fashion, and the applied
pressure is related to the expansion ratio of
the cavity radius X by
P/E = - (15-6)
where P is the inflating pressure and E is the
Young's modulus of the rubber at small
strains.
This relation predicts that the cavity will
expand without limits when the pressure ex-
ceeds 5 76. Although this result was later
corrected to account for the surface tension
of the rubber and its increasing stiffness at
high strains (Gent and Wang, 1991), it gives
a qualitatively correct result, namely, that a
rubbery material subjected to hydrostatic
tension will start to cavitate in order to re-
lax the elastic energy when the applied
stress becomes of the order of 3 G, where
G is the shear modulus. The shear modulus
depends on the rate of deformation of the
adhesive , such that the critical stress for
cavitation also increases with the rate of
deformation. Assuming that the debonding
stress responsible for adhesive separation at
the interface between the substrate and the
adhesive is rate independent, we expect a
transition from cavitating to noncavitating
fracture when the rate increases above a crit-
ical value cav . If the rate of deformation is
given to a first approximation by the de-
bonding velocity over the thickness of the
adhesive layer, the critical velocity Vcav is
expected to increase with the adhesive
thickness, as shown schematically in Fig.
15-3. Furthermore, at usual deformation
15.3 Theoretical Modeling 717
-rav
a
adh
v v
cavl cav2 V
Figure 15-3. Critical cavitating stress (taken as 3G)
as a function of the crosshead velocity for different
thicknesses of the adhesive layer (h). Note that the
critical velocity Vcav, above which cavitation does not
occur, increases with the thickness of the adhesive.
rates and temperatures for PSA, the shear
modulus is inversely proportional to the av-
erage molecular weight between entangle-
ments (Afe) of the adhesive, such that Vcav
is expected to decrease with increasing Me.
This latter argument would, however, no
longer hold at temperatures too close to Tg,
where G becomes independent of M e .
If the critical cavitating stress is actually
reached, the cavities will increase in size
and turn into fibrils, forming a structure of
thin fibrils parallel to the tensile direction,
as shown in Fig. 15-4.
The exact morphology of these fibrils will
be greatly dependent on the nucleation pro-
cess, and this process will depend not only
on the adhesive and the experimental geom-
etry, but also on the substrate. In particular,
a porous substrate will give an entirely dif-
ferent fibrillar structure to a nonporous one
(Urahama, 1989).
It is helpful here to make an analogy
between the growth of PSA fibrils and the
growth of crazes in a glassy polymer. Fibrils
in crazes nucleate under hydrostatic stress
at density fluctuations or local defects, and
grow in length by the meniscus instability
mechanism and in width by pulling new
material in the craze at a constant extension
ratio from a softened zone called the active
718 15 Materials Science of Pressure-Sensitive Adhesives
rti rfc
Cavitation
zone (Kramer and Berger, 1990). Qualita-
tively, there is evidence that PSA fibrils fol-
low a similar formation mechanism and the
similarities between the two situations are
now examined in more detail.
The critical molecular parameter control-
ling the formation of crazes is the average
molecular weight between entanglements
(Kramer, 1983). Experimentally, nearly all
glassy polymers, for which the main defor-
mation mechanism is crazing, have a high
Afe. There is good experimental evidence
which is also true for PSAs for the reasons
developed in the preceding paragraph
(Zosel, 1985).
However, some important differences are
also present: the characteristic size of the
PSA fibrils is typically three to four orders
of magnitude larger than the size of craze
fibrils. This large fibril size is not consistent
with the craze fibril growth model proposed
by Kramer even considering the much lower
drawing stress of the PSA (Kramer, 1983).
The craze tip growth models based on the
Saffman-Taylor instability (Donald and
Kramer, 1981; Fields and Ashby, 1976)
appear to be more sucessful at predicting
the characteristic fibril spacing of PSA
although the lack of reliable experimental
data on fibril size precludes any detailed
comparison.
Furthermore, in most cases, the formation
of crazes in glassy polymers involves a sub-
Figure 15-4. Schematic
diagrams showing fibril
formation in a PSA layer
tested in the probe tack
Fibrillation test.
stantial amount of chain scission so that if
chemical crosslinks are introduced, they do
not influence the deformation mechanisms
until the density of crosslinking points be-
comes comparable to the density of entan-
glement points. In contrast, for PSA the
introduction of chemical crosslinks much
beyond the gel point of the polymer (at
which stage crosslink density is still much
lower than the entanglement density) mod-
ifies the deformation mechanism and a
fibrillar structure is no longer observed.
With certain systems, the same result can
actually be obtained by increasing the mo-
lecular weight above a certain limit. These
observations imply that while the molecu-
lar weight between entanglements is an im-
portant parameter in the control of fibril nu-
cleation, the terminal relaxation time will
control fibril growth and, if this relaxation
time is too high, no fibrils can successfully
grow and the interface fails with little plas-
tic deformation. While no direct experimen-
tal evidence exists, the available experimen-
tal observations are consistent with the hy-
pothesis that fibrils grow mainly by chain
disentanglement. This necessary disentan-
glement mechanism can limit the use of very
high molecular weights or of highly
branched polymers in an attempt to increase
the creep resistance, as previously stated.
Another important question is fibril
growth and breakdown. TEM observations

in glassy polymers show that the growth of
craze fibrils occurs at a constant stress and
up to a constant extension ratio, which is
uniquely dependent on Me (Kramer, 1983).
They do not creep during the growth pro-
cess, but rather incorporate new material
from the unstrained bulk polymer neighbor-
ing the craze. Due to a stress concentration
within the fibrillated material, the fibrils
then fail catastrophically (by disentangle-
ment or chain scission) when the stress on
the fibril reaches a critical stress.
In PSAs so far, however, there is little ex-
perimental evidence to indicate whether the
fibrils grow mainly by fibril drawing from
the bulk (process 1) or by fibril creep (pro-
cess 2), as shown in Fig. 15-5. Good and
Gupta (1988) have argued that the fibril will
grow completely by creep and that, eventu-
ally, strain hardening occurring in an elon-
gational deformation will be sufficient for it
to debond from the substrate. However, such
(a)
I fibril creep
fibril drawing
Figure 15-5. Schematic diagrams showing (a) fibril
creep and (b) fibril drawing.
15.3 Theoretical Modeling 719
a strain hardening only occurs significantly
in elongation experiments when the materi-
al is tested at a constant strain rate. When
the material is stretched at a constant cross-
head speed, which is normally the case in
adhesion tests, a fibril growing solely by
creep will experience an exponentially de-
creasing strain rate. Under these conditions,
only a moderate amount of strain hardening
was observed by Ziille et al. (1987) on an
LDPE melt. Therefore such an argument
would lead to a nominal stress that de-
creases with a nominal strain, and could
never lead to adhesive fracture. It seems
more plausible from the experimental data
of Zosel (1989) showing clearly that the
nominal stress remains practically constant
during the debonding process, that the fi-
brils are mostly drawn at a constant stress
from the undeformed bulk of the adhesive
layer.
From these experimental observations,
the following picture can be proposed: Dur-
ing fibril growth, two processes are compet-
ing: fibril drawing to a constant extension
ratio at the fibril/bulk interface, and fibril
creep at a constant stress once the fibril is
formed. The competition between the two
processes can best be viewed by a represen-
tation of the characteristic time versus def-
ormation rate. To a first approximation, the
characteristic disentanglement time tdis will
increase with molecular weight and de-
crease with temperature
^dis ~ (15-7)
where 0 is the monomer friction coeffi-
cient, but will be relatively independent of
the thickness of the adhesive or of the de-
bonding rate as long as the effective stress
on the fibril remains constant.
However, the characteristic extension
time text (i.e., the time to draw all of the
material to an extension ratio Amax) is ap-
720 15 Materials Science of Pressure-Sensitive Adhesives
proximately given by
(15-8)
A vflb
where h is the thickness of the adhesive layer
and Vfib is the average fibril drawing veloc-
ity. If ^dis<^exf th e fibrils will fail before
all of the bulk material has been extended
and cohesive fracture of the fibril will be
observed. In the other case, the fibril will
eventually become completely extended at
A=Amax and then a strong strain hardening
is expected as further elongation of the
fibril requires disentanglement and not sim-
ply an extension of chain segments between
entanglement points. This sudden increase
in stress can cause debonding of the fibril
from the interface with the substrate if the
interfacial forces are relatively weak, or it
can cause the fibril to fail cohesively and
catastrophically. In this model, the dis-
(thin-highM w )
(thin-low M w )
Figure 15-6. Characteristic disentanglement and extension times as a function of the crosshead rate in a probe
tack test.
entanglement time, tdis is independent of the
fibril drawing velocity, Vfib, while the time
for the fibril to be completely extended, tQxV
is inversely proportional to Vfib. Therefore,
a decrease of the drawing velocity will even-
tually always lead to cohesive failure even
in interfacial forces are weak.
If it is assumed that in a probe tack ex-
periment Vfib is proportional to the probe ve-
locity, a critical transition velocity Vc can be
defined, above which the fracture mecha-
nism changes from cohesive to adhesive.
From the arguments set out in the preceding
paragraphs, Vc will decrease with the mo-
lecular weight (affect on tdis) and increase
with the thickness of the adhesive (effect on
ext), as illustrated in Fig. 15-6.
Now that the qualitative behavior has
been examined, it is important to establish
more quantitative trends and particularly
to relate the micromechanical models with

macroscopically measurable quantities,
such as the maximum adhesion force or the
adhesion energy.
It is important at this point to make the
distinction between force and energy in the
context of the adhesion of PSAs. The adhe-
sion force is often used as a measure of ad-
hesion in probe tack tests. In this case, the
force represents either the force necessary
to debond from the substrate, or the force
necessary to nucleate cavitation in the ad-
hesive. On the other hand, in one case the
adhesion energy represents the energy to ho-
mogeneously deform the adhesive before
debonding and, in the other case, the ener-
gy necessary to form the fibrils and to stretch
them to their maximum extension before de-
bonding. These two behaviors are shown
qualitatively in Fig. 15-7. It is clear from
these definitions that, while in the case of
noncavitating adhesives the force and ener-
gy are always proportional, this is not nec-
essarily the case for cavitating adhesives.
In this review we will consider, whenever
possible, the fracture energy W, rather than
the fracture force, to be coherent with the
approach generally taken in adhesion sci-
ence. For a cavitating adhesive, the fracture
energy W is simply the external work nec-
essary to separate the two surfaces. This
work is given, to a first approximation, by
the product of the average fibril drawing
(a) AL (b) AL
Figure 15-7. Force-displacement curve of a typical
PSA in a probe tack test: (a) nonfibrillating adhesive,
(b) fibrillating adhesive.
15.3 Theoretical Modeling 721
stress and the final extension ratio of the
fibrils at fracture, A. If the fracture is adhe-
sive and little creep occurs, the simplest ap-
proximation for the fibril extension ratio is
to consider it as proportional to the extend-
ed length between entanglement points, giv-
ing
A m a x -M e 1 / 2 (15-9)
In the case of cohesive fracture, however, A
could be much higher due to disentangle-
ment.
A prediction of the fibril drawing stress
is harder to determine quantitatively, as
fibril formation requires some disentangle-
ment and plastic flow. However, it seems
clear that the drawing stress should increase
with the monomer friction coefficient and
molecular weight. This also implies a de-
creasing drawing stress with temperature.
While more quantitative models are pos-
sible, they lie beyond the scope of this chap-
ter.
15.3.4 Bond Formation
One of the most interesting experimental
observations on pressure-sensitive adhe-
sives was made early on by Dahlquist (1969)
using his well-known criterion: for measur-
able quick tack, the elastic modulus must be
below a certain fixed value which is fairly
independent of the nature of the adhesive,
the adherend, or the applied pressure.
The property of quick tack is defined as
the result of the following experiment: The
adhesive is brought into contact with a stain-
less steel cylindrical probe and this contact
is maintained for a very short period of time
( I s typically) under a light pressure. The
probe is then withdrawn and the force is
monitored.
The underlying assumption behind Dahl-
quist's criterion is that when the material's
modulus is too high, perfect contact be-
722 15 Materials Science of Pressure-Sensitive Adhesives
tween the adhesive and the substrate cannot
be obtained during the time of contact, and
this results in a decrease of the maximum
stress that can be sustained by the adhesive
bond. The qualitative explanation given in
textbooks is that the adhesive cannot spread
properly on the surface during the time of
contact if its viscosity is too high. The vis-
cosity, however, is normally defined as a
fluid property and implies flow, which
clearly does not happen to a great extent
when the modulus is high.
A better understanding of the effect of the
modulus of the adhesive on the measured
tack can be obtained through an analysis of
the contact between a random rough surface
and a flat plane (Creton and Leibler, 1995).
Following the formalism of Greenwood and
Williamson (Greenwood and Williamson,
1966), the authors assume that all asperity
summits are of a constant radius of cur-
vature R but their heights vary randomly:
the probability that a particular asperity has
a height between z and z + dz above some
reference plane is given by (j)(z)dz with
1 as
(15-10)
The adhesive is modeled as a flat sheet
with a time-dependent shear modulus and
the type of contact is shown schematically
in Fig. 15-8. The behavior of an individual
asperity is known from the JKR equations
'plane of the
adhesive
Y reference plane
in substrate
Figure 15-8. Diagram of the contact between the
adhesive and a model random rough surface with a
distribution of asperity heights and a constant radius
of the asperities. The lightly shaded area of the asper-
ities is indented in the adhesive.
(Johnson et al., 1971) and if the thermo-
dynamic work of adhesion between the two
materials Wadh and the standard deviation
of the distribution of heights are known, the
true contact area between the two surfaces
can be calculated as a function of the ap-
plied nominal pressure and of the shear
modulus of the adhesive. Because the ad-
hesive is viscoelastic, this contact area
increases with contact time. If the time-
dependence of the shear modulus (as mea-
sured in a creep experiment) is known, the
true contact area can be calculated for a
given adhesive-substrate pair as a function
of the applied pressure and time of contact.
Creton and Leibler argued that this area
of contact established during bonding is the
relevant quantity to be considered for the
debonding process because no substantial
reduction in contact area can occur during
the very rapid release of the applied pres-
sure.
Their contact mechanics analysis predicts
two limiting cases: If the modulus is high so
that van der Waals forces can be neglected,
the area of contact A is predicted to increase
A-^ (15-11)
and to become constant when
vl/2
(15-12)
where p is the applied pressure. In this re-
gime, tack is predicted to scale with \IG at
constant given pressure and debonding rate.
This is consistent with experimental results
of Zosel (Zosel, 1992) on various PSAs as
shown in Fig. 15-9.
When the elastic modulus decreases, van
der Waals forces can no longer be neglected
and the area of contact becomes indepen-
dent of the applied pressure. In a limiting
case, the area of contact can be at its maxi-

103
2
Jm"
102
\ D
1O- 0
\
w n
Iff1- k
1 106 107
Figure 15-9. Tack fracture energies of various poly-
acrylates in the contact limited regime plotted vs. the
corresponding values of the elastic Young's modulus
(Zosel, 1992).
mum (perfect contact) under zero applied
pressure. This situation occurs when the
modulus falls below a critical value G*
given by
Rl
~ ^adh
Physically, this critical modulus G* is a
lower limit below which one expects tack to
be always independent of pressure. With
R= 100 (Lim, =2 |um,and Wadh = 50 mJ/m2,
typical of the stainless steel probe tack used
for tack experiments (Hammond, 1989), G*
becomes approximately equal to 0.2 MPa,
in reasonable agreement with Dahlquist's
criterion obtained empirically.
The detailed results of Creton and
Leibler's calculation for intermediate cases
is presented in Figs. 15-10aand 15-10b, and
show the progressive influence of van der
Waals forces when the modulus and/or the
applied pressure are decreased. The pres-
sure p is normalized by Wadh/, which cor-
responds to the additional pressure due to
van der Waals forces alone. Taking the
15.3 Theoretical Modeling 723
Pa 10
^
0.01
0.001
10 100
G/G*
Figure 15-10. a) True area of contact A for various
shear moduli as a function of the nominal pressure p
(Creton and Leibler, 1996). b) True area of contact A
(15-13)
under various nominal pressures as a function of the
rubber shear modulus G. The area is normalized by
the maximum area of contact A*, the load is normal-
ized by VKadh/<J, corresponding to the pressure com-
ponent due to van der Waals forces, and the modulus
is normalized by the modulus G* giving A = A * at zero
load.
numerical example above would give a van
der Waals pressure of Wadh/ = 0.025 MPa.
These results appear at odds with the
classic work of Fuller and Tabor (Fuller and
Tabor, 1975) on adhesion of crosslinked
rubber on a rough substrate. Their analysis
predicted that the adhesion energy should
always be independent of the applied pres-
sure. They did not, however, take into ac-
count any effect of the adhesion hysteresis,
i.e. they assumed that the bonding and
debonding process occurred reversibly. For
724 15 Materials Science of Pressure-Sensitive Adhesives
the very fast rates of debonding typically
used for PSAs, there will be large hysteresis
losses which will prevent the contact area
from returning to its equilibrium value after
removal of the load.
These results have been recently confirm-
ed by Zosel in a series of tack experiments
using different probes with controlled
roughnesses on the same adhesive (Zosel,
1997).
15.3.5 Relationship Between Adhesive
and Bulk Properties
Recently, a great deal of effort has been
put into trying to directly correlate adhesive
properties with easily measured bulk
materials' properties, such as the dynamic
mechanical properties or the tensile strength
(Chang, 1991; Dale et al., 1989). Although
such an approach does not provide any in-
sight into the details of the deformation
mechanisms, it does provide valuable gen-
eral guidelines for the design of pressure-
sensitive adhesives, and as such it should be
examined in more detail.
The idea put forward by Chang is that of
a viscoelastic window of use for PSAs. The
value of the storage modulus G' at the tem-
perature of use and at the frequency corre-
sponding to the time scale of the mechani-
cal test affects two important properties: the
ability of the material to establish good con-
tact with the substrate and the shear resis-
tance. If G' is too high, the adhesive will
lose its tack, while if G' is too low, the shear
resistance of the material will be reduced.
Similarly, the loss modulus G" is taken as
an indication of the amount of viscoelastic
losses during debonding and therefore
needs to be as high as possible for high ad-
hesion. It should be noted that G' and G"
cannot in general be varied independently
over a wide range, therefore a very high G"
usually implies a high G' and a loss of tack.
Although knowledge of the viscoelastic
properties is a useful guide for predicting
the adhesive properties, care should be tak-
en in generalizing such conclusions in the
analysis of systems where the viscoelastic
losses are clearly nonhomogeneous.
Particularly in view of the recent progress
that has been made in the understanding of
the correlation between molecular structure
and bulk mechanical properties, it is better
whenever possible to reason in terms of mo-
lecular structure and debonding micro-
mechanisms in order to understand the prop-
erties of pressure-sensitive adhesives.
15.4 Effect of Experimental Test
Parameters
The aim of this section is to survey the ef-
fect of all the experimental parameters that
do not pertain to the molecular structure or
the formulation of the adhesive. Consider-
ing then that such experimental parameters
are linked to specific experimental geome-
tries, it seemed natural to organize this sec-
tion by type of test, with the exception of
Sec. 15.4.4 which treats the effect of the
substrate.
The properties required from a pressure-
sensitive adhesive can be divided into three
classes along with their specific test methods:
1) adhesive strength (debonding process)
tested by peel tests,
2) conformability (bonding process) tested
by quick tack tests, and
3) cohesive strength of the adhesive tested
by a shear experiment.
From an industrial point of view, the main
concern is to obtain a value from each test
for comparative purposes. Wherever pos-
sible we will interpret the result of the test
in more fundamental terms to give the read-
 15.4 Effect of Experimental Test Parameters 725

er a better understanding of the factors af- F

fecting the result.

(
15.4.1 Peel Test C )
The peel test, which simulates the remov-
al of an adhesive tape, is the standard indi-
cator of the fracture energy of the adhesive Tack
bond (i.e., the debonding process) and is
mainly sensitive to the viscoelastic losses in
the adhesive. A thin layer of adhesive is ap-
plied to a backing tape which is usually (b)

much stronger than the adhesive. The tape
is then carefully bonded to a substrate (stain-
less steel polished to 2-|um roughness) and,
finally, it is peeled in a manner shown in
Fig. 15-11. The peel force per unit width of
tape measures directly the energy per unit
area to separate the adhesive bond. Unfor-
tunately, peel test results are also sensitive
to the angle 0 at which the tape is removed
and to the stiffness of the backing tape, mak-
ing it difficult to directly compare results
from different manufacturers or research la-
boratories. The mechanics of the peel test
have been the subject of ongoing research
by solid mechanics researchers and several
approaches are available (Aravas et al.,
1989; Gent and Hamed, 1977; Gent and
Kaang, 1987; Williams, 1993). Kaelble
(1965) has also specifically investigated the
deformation of a PSA layer during the peel
test.
The peeling rate and the temperature have
been the most widely investigated experi-
mental parameters. Figure 15-12 shows the
peel energy of an SBR adhesive on a Mylar
substrate as a function of the peeling rate
and at different temperatures (Gent and
Petrich, 1969). It is clear from the data that,
similarly to the viscoelastic properties, the
peel energy data can be superimposed on a
single master curve using the WLF time-
temperature superposition (Ferry, 1980), as
shown in Fig. 15-13. Such a result is fairly
rr
Backing
.Adhesive
t
N
Substrate
Peel
(c)
Shear
Figure 15-11. Diagrams of the experimental set-ups
for (a) the quick tack test, (b) the peel test, and (c) the
shear test.
typical from peel tests of PSA tapes and im-
plies that the measured energy of adhesion
is very sensitive to the viscoelastic losses in
the polymer used for the adhesive layer. As
PSAs are viscoelastic materials, this result
may at first appear obvious, however, it
should be pointed out that the equivalence
between time and temperature is a feature
typically associated with linear viscoelas-
ticity, and the deformations involved in the
debonding of an adhesive tape are well into
the nonlinear regime where the mechanical
history of the material should affect its be-
havior.
726 15 Materials Science of Pressure-Sensitive Adhesives

4UUU

3000 -
-
-5c y
/
10 C

A
J
23 C

2000

1000
- yy d 1 - A
Figure 15-12. Peel fracture energy
against rate of peel R for SBR adher-
ing to Mylar. OD A: cohesive failure;
: adhesive failure. [Data from
n Gent and Petrich (1969).]
-7 -6 -5 -4 -3 -2
ee
logio{P l rate(m/s)}

4000
(a) Fibrillar
cohesive

3000 - (b) Fibrillar

adhesive

2000 -

(c) Nonfibrillar
adhesive

1000 -
T
Figure 15-14. Schematic diagrams of the three main
deformation mechanisms observed in PSAs: (a) fibril-
lar cohesive fracture, (b) fibrillar adhesive, and (c)
nonfibrillar adhesive.

log10{Ra T(m/s)}
Figure 15-13. Master relation for peel fracture ener-
gy W against rate of peel R reduced to 23 C for
SBR adhering to Mylar. [Data from Gent and Petrich
(1969).]
Studies of the fracture mechanisms oc-
curring during the peel of pressure-sensitive
adhesives (Aubrey and Sherriff, 1980; Au-
brey etal., 1969; Gent and Petrich, 1969;
Kaelble and Reylek, 1969) found three main
mechanisms of fracture, as illustrated in Fig.
15-14:
(a) At low rates of peel or high tempera-
tures, the bond typically fails cohesively in
the adhesive layer by fibril formation with
eventual breakdown (Fig. 15-14 a). In this
regime the peel energy increases monoton-
ically with the rate of peel.
(b) When the rates of peel are increased or
the temperature is decreased, the debonding
mechanism may experience a transition to a
situation where fibril formation is followed
by debonding of the fibrils from the sub-
strate (Fig. 15-14b). This transition is not
always observed. It may be characterized by
 15.4 Effect of Experimental Test Parameters
a very sharp drop in the peel energy, but this
drop does not occur for all systems,
(c) Finally, if the rates are increased further,
all adhesives undergo a transition to fracture
without fibrillation and with a very small
amount of deformation. The latter transition
has been associated with the glass transition,
but can simply be a reflection of an increase
of the fibrillation stress to above the value
that will cause debonding. In this regime,
the peel energy is either fairly insensitive to
the rate or increases more moderately with
the rate.
Another important experimental variable
is the thickness of the adhesive layer. Au-
brey et al. (1969) found that for a po\y(n-
butyl acrylate) (PBA) the 90 peel strength
was independent of the adhesive thickness
(in the 15 - 85-|am range) in the low peel rate
regime, but that the rate at which they ob-
served a transition from cohesive fibrillar
fracture to adhesive nonfibrillar fracture in-
creased with thickness. This result can be
interpreted in light of the micromechanisms
developed in Sec. 15.3.3. At low rates of
peel, the adhesive is below Vc as well as be-
low Vcav, so that the disentanglement kinet-
ics of the fibrils control the maximum ex-
tension of the fibrils and thus the fracture
energy. In this regime,the fracture energy
should be independent of the adhesive thick-
ness. The transition to a smooth nonfibril-
lating adhesive fracture is a reflection of the
occurrence of Vcav, which indeed increases
with the thickness of the adhesive as pre-
dicted.
A different example is given by the re-
sults of Gardon (1963) in a T-peel test of a
commercial acrylic adhesive, which showed
a very strong dependence of the peel ener-
gy on the thickness at low as well as high
peel rates. The thicknesses investigated
were between 1 and 250 |Lim. Although no
description is given of the fracture mecha-
nism, the peel energy, in this case, does not
727
decrease sharply when the fracture becomes
adhesive, but remains constant. Also, the
critical rate at which this transition takes
place increases with thickness. In this case
it appears that cavitation occurs at every rate
of peel. The transition from cohesive to ad-
hesive failure can be explained in the fol-
lowing way: At a given thickness, the time
for extenstion rext decreases with the rate of
peel so that when text < td[s the fracture be-
comes adhesive. If the thickness of the layer
is increased, the extension time is also in-
creased, so that the transition is translated
to a lower peel rate. For a very thick layer,
the fracture is only cohesive.
Although these examples illustrate the
theoretical arguments fairly well, any gen-
eralization of these concepts should be done
with caution in view of the small amount of
data available.
15.4.2 Quick Tack Test
The quick tack experiments probe the in-
stant adhesion and are an indication of the
ability of the material to form a contact very
quickly to the substrate. As pointed out in
Sec. 15.3.3, the tests that have been de-
signed to probe this property can be divid-
ed into two categories: those measuring the
force of separation and those measuring the
energy. The main test probing the force is
that of probe tack (Hammond, 1964) de-
scribed earlier, where a flat cylinder is
brought into contact with the adhesive film
and subsequently removed at a fixed cross-
head speed. In this geometry, the maximum
force of separation is taken as the measure
of adhesion. Alternatively, a loop tack test
has also been used where the adhesive is put
on a tape and the force necessary to unstick
the loop of tape from the substrate is mea-
sured.
Among the tests probing the energy, the
most widely used are the rolling ball test or
728 15 Materials Science of Pressure-Sensitive Adhesives
the rolling cylinder test where a standard-
ized steel ball is allowed to roll from an in-
clined plane on a sticky surface and the dis-
tance it rolls before stopping, or alternative-
ly the largest ball that will not roll on the in-
clined plane, is a qualitative indication of
the energy involved in bonding and debond-
ing the adhesive from the substrate.
In some cases, these standardized tests,
which are widely used in industry, have been
developed further to be analyzed in terms of
more fundamental parameters. Zosel (1985)
has developed a probe tack test that mea-
sures the force of separation as a function of
time, which is particularly well suited as a
measure of the energy of separation (Zosel,
1985). He also observed some features of
the fibrillation process in his experimental
geometry thanks to a high speed camera, and
argued that, similarly to other adhesion
tests, the energy of separation should be the
relevant parameter rather than the force.
Mizumachi and co-workers have ana-
lyzed the rolling of a cylinder on a surface
in a more rigorous way using equations of
motion to extract a rolling friction coeffi-
cient. With a semi-empirical theory of bond-
ing and debonding of the adhesive during
the rolling motion they have been able to
qualitatively simulate their experimental re-
sults (Mizumachi and Hatano, 1989; Tsuka-
tani et al., 1989).
From the point of view of the user, the
quick tack test is designed to evaluate the
aptitude of the adhesive to adhere instantly
and under light pressure to a substrate.
Therefore two new experimental parame-
ters are introduced relative to the peel test,
i.e., the time and pressure of contact. This
complication is a reflection of the fact that
the result of a quick tack test will be a com-
bination of the bonding as well as the de-
bonding properties of the adhesive. Experi-
mentally, we will concentrate on the results
obtained with the probe tack test and the
rolling cylinder test, which are more easily
amenable to analysis.
The main effect of the time of contact as
an experimental parameter is to introduce a
second relevant time scale into the adhesion
process. The amount of relaxation in the ad-
hesive during the bonding process is depen-
dent on the time of contact, tc, while the vis-
coelastic losses during debonding are de-
pendent on the rate of separation. These two
time scales are usually controlled complete-
ly independently, introducing therefore a
decoupling of the effect of the rate of de-
bonding and that of the temperature. While
for a long time of contact, the results of the
peel test are recovered and the WLF super-
position holds relatively well, when tc is re-
duced, bonding becomes incomplete and the
temperature dependence of the bonding pro-
cess affects the results.
The temperature dependence of quick
tack is, in many respects, the most interest-
ing for understanding the process. As illus-
trated in Fig. 15-15, quick tack appears to
go through a maximum when the test tem-
perature is approximately 50-70 C above
Tg (Kim and Mizumachi, 1995 a; Zosel,
1985). This maximum is due to the balance
between two effects: on the one hand, the
true contact area between the adhesive and
the substrate at the time of debonding be-
comes much smaller than the nominal area
when the compliance of the adhesive falls
below a critical value, causing a sharp de-
crease in the measured adhesion, and, on the
other hand, in the regime where the contact
is well established the viscoelastic losses
decrease with temperature. Alternatively, it
can be said that tack increases with decreas-
ing temperature up to a critical temperature
where it quickly decreases to zero. This rel-
atively sharp transition was early on asso-
ciated by Dahlquist (1969) with the compli-
ance and is generally known as the Dahl-
quist criterion. Empirically, when the ten-
 15.4 Effect of Experimental Test Parameters 729

10' 103
Pa Jrri2

10
2
10

10
10'

10' Figure 15-15. Tack W (O, ) and

-10 Young's modulus E ( ) of poly-
w isobutylene (PIB) and polystyrene
10 (PS) as a function of temperature
-10"1 (Zosel, 1992). 1992 Dr. A. Zosel
and Satas & Associates. Reprinted
by permission.
1 io-2
-50 100 150 C 200

sile modulus (measured at 1 s lag time) be- 1 1 i i i

3
comes higher than approximately 1 MPa
2
there is no tack.
The contact time and pressure are two im- y
100
portant parameters in the quick tack experi- 8

ment which do not exist in peel tests. 7

5 \ yS
Following the arguments set forth in Sec.
15.3.4, an increase in contact time will in- 3

crease the true contact area by a relaxation 2

of the modulus of the adhesive, while an in-
crease in contact pressure will increase the
contact area by elastic deformation of the
adhesive layer on the rough substrate. Clear-
ly this increase in the contact area is expect-
ed to directly affect only the measured tack
in the regime where adhesion is contact-
limited, i.e., the area of contact A is smaller
than the maximum area of contact A*.
Experimentally, a longer contact time ei-
ther increases the tack or does not affect it
(Bates, 1976; Gent and Kim, 1990; Ham-
mond, 1964; Sherriff et al., 1973; Zosel,
1985). Its effect is much more pronounced
for very short contact times, as shown sche-
matically on Fig. 15-16, while for very long
contact times the effect disappears and the
results of the peel test are recovered (Gent
, i i i i
10 1000
Ms)
Figure 15-16. Track fracture energy W as a function
of the time of contact. [Data from Zosel (1985).]
and Kim, 1990; Zosel, 1985), as expected. The
increase in tack is due to an increase in the
true contact area by relaxation of the elastic
modulus. In general this increase in contact
area is most effective for tack when the sur-
face is very rough, the applied pressure is
high, or the modulus, at the temperature of
use, has a very sharp relaxation with time.
The effect of the contact pressure is qual-
itatively similar to the effect of the contact
time, i.e., it increases the true contact area.
However, the applied pressure will only
730 15 Materials Science of Pressure-Sensitive Adhesives
i 10 r
s adhesive after a long time. The important
10 r
4 6 8
io 3 io 4 io 5
Pressure (Pa)
Figure 15-17. Maximum stress in a probe tack test
as a function of the contact pressure for two commer-
cial PSAs. : "smooth" PSA; O: "rough" PSA. [Data
from Hammond (1964).]
have an effect when the elastic modulus of
the adhesive is high or the roughness is im-
portant. In the opposite case, a good bond
can rapidly be established, even under near-
ly zero pressure. Experimentally, the effect
of the contact pressure has been mentioned
only sparingly. Hammond (1964) found that
for a "smooth" adhesive the maximum force
of separation increased with the applied
pressure up to a point and then became in-
dependent of the pressure, as shown in
Fig. 15-17. He found, however, that for a
"rough" adhesive the pressure had an effect
over the whole range of measurement.
Zosel found a similar result for a poly-
ethylhexyl-acrylate (Zosel, 1992). This was
confirmed by peel tests that are not sensi-
tive to the pressure at which the samples
were prepared.
15.4.3 Shear Test
Resistance to shear is particularly crucial
for all permanent and semi-structural appli-
cations where a large deformation with time
under moderate stress is detrimental. The
adhesive is tested either in static shear,
where a fixed load is applied and the time
to failure of the adhesive bond is recorded,
or in dynamic shear, where a constant shear
rate is imposed and the force is monitored.
This is basically a creep test and will give
an indication of the cohesive strength of the
experimental parameters in a shear test are
the load and the temperature for the static
shear, along with the shear rate and temper-
ature in the dynamic test. There are, unfor-
tunately, very few available studies that go
into more detail than simply the time to fail-
ure, but some important features can be ex-
tracted from the available data.
If the material behaves as a Newtonian
fluid, the time to failure can be predicted by
a knowledge of the viscosity. Unfortunate-
ly, such a behavior is only characteristic of
relatively low molecular weight polymers
under small loads. Commercial PSAs very
rarely behave in this manner and the shear
deformation of the adhesive layer as a func-
tion of time is usually strongly nonlinear
(Dahlquist, 1989; Zosel, 1994). Similarly,
the adhesive is strongly shear thinning so
that when the shear rate imposed by the
fixed load rises above a certain value, the
rupture is catastrophic.
15.4.4 Surface Properties
of the Substrate
Although the bulk viscoelastic properties
are of primary importance for an adhesive,
a necessary condition for good adhesion is
that the interaction at the interface is suffi-
ciently strong to sustain the stress necessary
to cause extensive plastic deformation in the
bulk adhesive. Several studies were under-
taken early on in order to understand the in-
fluence of the adherend on the peel energy
 15.5 Effect of the Molecular Structure of the Adhesive
and, in particular, the relation between the
thermodynamic surface energy and the
measured adhesion (Andrews and Kinloch,
1973 a, b; Gent and Schultz, 1972). In the
absence of primary bonds at the interface,
the measured peel strength is proportional
to the thermodynamic energy of adhesion
Wadh and the proportionality factor is depen-
dent on the bulk viscoelastic properties of
the adhesive. These findings have been very
well verified for crosslinked adhesives that
did not show any fibrillar fracture. Howev-
er, the correlation was less well established
for PSAs. Toyama and co-workers stud-
ied the probe tack and peel strength of a
poly(?z-butyl acrylate) on a variety of sub-
strates and analyzed the dependence of their
data on the surface energy of the adherends
(Toyama et al., 1970). They found a maxi-
mum in the peel strength when the surface
tensions of the adhesive, ya, and of the ad-
herend, ys, were closely matched and argued
that in this situation the interfacial energy is
minimum.
Other studies have, however, found an in-
crease in the peel strength at low surface
energies of the adherend, followed by a pla-
teau when 7s>7a (Zosel, 1985), or a mono-
tonic increase in the tack with / s (Sherriff
et al., 1973). Two general conclusions can
be drawn from these results: The surface en-
ergy of the adherend should not be below
that of the adhesive, this being particularly
true for tack. If the surface energy of the ad-
herend is comparable or higher than that
of the adhesive, the influence of surface
forces on the measured adhesion is relative-
ly small compared to the effect of the vis-
coelastic losses in the adhesive layer.
As pointed out in Sec. 15.3.4, another
point which is often neglected, but is of pri-
mary importance in the case of tack, is the
effect of surface roughness. Fuller and Ta-
bor (1975) showed that the measured adhe-
sion of a crosslinked adhesive is dependent
731
on its surface roughness down to fractions
of a micrometer, and that a surface rough-
ness of the order of a micrometer could de-
crease the measured adhesion by a factor
of 10. The topology of the surface is never,
however, considered in tack studies and
may be responsible for some quantitative
discrepancies between experimental re-
sults.
15.5 Effect of the Molecular
Structure of the Adhesive
One of the most interesting aspects for a
materials scientist is how the molecular
structure of the polymer affects its proper-
ties in pressure-sensitive adhesion applica-
tions. Although relatively few systematic
studies on the effect of the molecular struc-
ture are currently available, they are suffi-
cient to be able to extract some general con-
cepts for the design of an adhesive. Before
analyzing the adhesive properties, it is use-
ful to briefly review what is known about
the molecular origin of the rheological prop-
erties of polymer melts (see also Chapter 9
in Volume 12 of this Series).
15.5.1 Molecular Origin
of Viscoelasticity
The storage shear modulus G' of a typi-
cal high molecular weight polymer melt
measured at a frequency of 1 Hz is shown
in Fig. 15-18. At low temperatures, the
polymer is glassy and the relaxation times
are usually much longer than the time of the
experiment. When the glass transition is
passed, the modulus falls and the short chain
segments (shorter than the entanglement
length) start to relax. In the plateau zone, the
segments between entanglement points are
fully relaxed, but the chain is only partially
732 15 Materials Science of Pressure-Sensitive Adhesives
G'
\ lecular weight and degree of branching or
rubbery fluid
Figure 15-18. Shear modulus G' of a typical high
molecular weight polymer.
relaxed. The temperature range over which
the modulus remains relatively constant
increases with the molecular weight M,
while its average value Go is inversely pro-
portional to the average molecular weight
between entanglement points M e . Finally,
when the chain is fully relaxed, the polymer
will flow and behave more like a fluid than
a solid (Ferry, 1980).
Each region in the viscoelastic spectrum
is sensitive to different features of the mo-
lecular structure. In the glass transition re-
gion, the modulus is mainly sensitive to the
local structure of the polymer, i.e., at the
monomer level, while in the rubbery plateau
region the modulus is sensitive to the mo-
lecular weight between entanglements or
the degree of crosslinking, and, finally, in
the terminal zone the value of the modulus
is sensitive to the polymer molecular weight
and the degree of branching and crosslink-
ing.
These molecular considerations can now
be applied to the interpretation of the mech-
anisms involved in the standard adhesion
tests. Following the classification estab-
lished above in terms of characteristic re-
laxation times, the molecular features can
be classified in three categories in relation
to their effect on:
A) the short relaxation times, i.e., the
monomer structure and local mobility of the
chain, which will directly affect the Tg;
B) the intermediate relaxation times, i.e.,
the molecular weight between entangle-
ments; and
C) the long relaxation times, i.e., the mo-
crosslinking.
To these three categories one should add the
properties that affect the molecular interac-
tions between the adhesive and the sub-
strate.
When evaluating whether a change of
molecular structure will have an effect on a
specific property involving the deformation
of the adhesive, the first step is to roughly
evaluate the characteristic time rc over
which this deformation takes place at the
temperature of use. If the change in molec-
ular structure affects the viscoelastic spec-
trum in the frequency corresponding to l/r c ,
the property will most likely be affected.
However, if the spectrum does not change
this does not mean that the property is in-
sensitive to the given feature (Dale et al.,
1989). A second and more effective ap-
proach is to identify the type of molecular
motions involved in the specific deforma-
tion mechanism. For example, if large
deformations and disentanglement of the
chains are involved, molecular weight is
likely to be important. On the other hand, in
the bond formation of a quick tack experi-
ment at a low temperature and with a short
contact time, the chains do not have time to
disentangle and the molecular weight is un-
likely to be a relevant parameter. Unfortu-
nately, the exact micromechanisms taking
place in a practical situation are not always
easy to determine a priori and the common
procedure is rather the opposite, i.e., under-
standing the mechanism by testing which
molecular parameters affect the property.
 15.5 Effect of the Molecular Structure of the Adhesive
15.5.2 The Glass Transition
Temperature
For good adhesive properties, the glass
transition temperature must be between
50 C and 70 C below the temperature of
use (Satas, 1989 a; Zosel, 1985). If the Tg is
too far below the temperature of use, the vis-
coelastic losses in the debonding process
will be too low, giving low adhesion, and its
cohesive strength will also be too low. On
the other hand, if the Tg is too close to the
temperature of use, the compliance will be-
come too low, making it difficult to estab-
lish good contact with the adherend. Con-
sidering that most applications for PSAs are
for room temperature or slightly above,
the most useful polymers have Tgs between
-50 and -30 C, with some exceptions.
One common solution for retaining the
useful properties of a polymer while adjust-
ing its Tg involves compounding with tack-
ifying resins that allow the use of polymers
with a lower Tg.
15.5.3 The Molecular Weight
The molecular weight has an important
effect on the adhesion properties through its
influence on the intermediate and long re-
laxation times. A high molecular weight
will favor adhesive separation, which is nor-
mally required from pressure-sensitive ad-
hesives (Aubrey et al., 1969), by slowing
considerably the process of chain disentan-
glement, which is responsible for fibril
creep and eventually cohesive fracture.
However, the molecular weight can also in-
fluence the micromechanical deformation
mechanisms within the adhesive layer
which are eventually responsible for the
measured energy of adhesion. A high Mn
will negatively affect the formation of
fibrils during the debonding process. While
it is generally admitted that the peel resis-
733
"5
8x10
Figure 15-19. 180 peel fracture energy vs. weight
average molecular weight Mw at a peel rate of
l(T 3 m/s (squares) and 8.5xlO~3m/s (circles) for
polyisobutylene. On: cohesive failure; : adhesive
failure. [Data from Krenceski and Johnson (1989).]
tance decreases moderately with molecular
weight, as shown in Fig. 15-19 for a series
of polyisobutylenes (Krenceski and John-
son, 1989), some more dramatic effects can
also occur, as illustrated by the following
example.
Gent and Petrich (1969) performed peel
tests on an SBR polymer on Mylar before
and after a milling operation. The raw poly-
mer had an M n ~70000 with a sizable high
molecular weight fraction, while the milled
polymer had undergone a drastic reduction
of the high molecular weight fraction. As
shown in Fig. 15-20, the measurements of
W versus the reduced peel rate showed two
transitions for the milled sample, while
only one transition was observed for the raw
sample. The high peel rate transition is at-
tributed to the onset of the glass transition.
These results can readily be explained by
the arguments set out in Sec. 15.3. The main
difference between the two polymers is the
terminal relaxation time which must be
longer for the raw polymer. This shift in the
relaxation time inhibits fibril formation
even at low rates. However, the transition in
fracture energy observed for the milled sam-
734 15 Materials Science of Pressure-Sensitive Adhesives
8 The average molecular weight between
-2
log10{Ra T (m/s)}
Figure 15-20. Peel fracture energy-peel rate relation
for SBR adhering to Mylar. The raw material (A) has
a high molecular weight which is reduced by the mil-
ling operation (O). [Data from Gent and Petrich
(1969).]
pie at low rates could be due microscopical-
ly to the transition from high dissipation
fibrillar fracture to low dissipation adhesive
fracture.
Quick tack is more negatively affected by
an increase in molecular weight because, in
addition to the reason already mentioned for
the adhesion properties, a high M will also
increase the modulus at intermediate and
long times, and can negatively affect the
ability of the polymer to form a bond.
Shear resistance, however, is very posi-
tively affected by molecular weight. The
simplest approximation is to correlate creep
resistance with viscosity, and it is now well
established that the viscosity follows the
empirical relation r)cM 3 4 . Therefore a
small change in molecular weight can great-
ly affect the shear resistance.
In conclusion, the general rule is that
within the range of molecular weight that
gives adhesive separation, the tack and peel
strengths decrease moderately with molec-
ular weight while the creep resistance in-
creases. In practice, however, most poly-
mers used industrially have a broad polydis-
persity, and an experimental study on poly-
isobutylenes showed that a wide molecular
weight distribution can have a beneficial ef-
fect on all three properties (Krenceski and
Johnson, 1989).
entanglements is equally important for the
performance of the adhesive. Its effect on
the plateau modulus has two important con-
sequences:
1) A low plateau modulus and therefore a
high Me favor the formation of fibrils dur-
ing the debonding process, therefore in-
creasing the adhesion energy.
2) A high Me also favors bond formation at
very short contact times.
Some classic experiments of Gent and co-
workers (Gent and Lindley, 1958; Gent and
Wang, 1991) demonstrated that for cross-
linked rubbers the critical stress for cavita-
tion is directly proportional to the plateau
modulus of the rubber. By analogy, the val-
ue of Me in PSAs is expected to influence
the degree of cavitation and fibrillation of
the adhesive. Indeed Zosel has observed that
in quick tack experiments a high molecular
weight between entanglements promotes a
high value of tack through easier fibril for-
mation (Zosel, 1985, 1989).
A final example encompassing several
concepts of molecular interpretation is the
study by Aubrey et al. (1969) on different
polymer melts. The peel strength of two
polymers is shown on Fig. 15-21 against the
reduced rate of peel. Aubrey et al. (1969)
distinguish three microscopic deformation
mechanisms. At a low peel rate, the sepa-
ration is fibrillar and cohesive for all poly-
mers. However, at higher rates, the vinyl
acetate - 2-ethy lhexy 1 aery late (VA- E A)
copolymer shows a transition in fracture
mechanism to fibrillar adhesive failure,
while the poly (n-butyl acrylate) (PB A) does
 15.5 Effect of the Molecular Structure of the Adhesive 735

1400
J
1200 0
JL
1000

"a 800 o ,' '}

^ 600

400 0
200 0
Figure 15-21. Effect of
0 peel rate on the peel adhe-
-6 -5 -4 -3 -2 -1 sion energy and mode
of failure for: a) vinyl
log 10 {peel rate (m/s)) acetate-2-ethyl hexyl
acrylate copolymer and
b b) poly(ft-butylacrylate).
1 The adhesive films were on
1400 -
polyester backing and
1200 peeled off clean glass at a 90
angle. O: cohesive fibrillar
1000 - fracture; : adhesive fibril-
i
lar fracture; : adhesive
800 0 - nonfibrillar fracture. The
I 600
vertical arrows show the
high and low values of the
fracture energy in the do-
400 - 0 mains of stick slip fracture

200 where the force oscillates.
0 [Data from Aubrey et al.
1 1 1 1 (1969).]
0
-6 -5 -3 -2 -1

gio

not undergo such a transition. It is impor-
tant to note that this transition is not asso-
ciated with a discontinuity in the fracture
energy versus peel rate.
When the peel rate is raised further, both
polymers go through a slip-stick regime,
which is related to the mechanics of the peel
test, and then undergo a transition to adhe-
sive nonfibrillar fracture. The two polymers
show a very different qualitative as well as
quantitative behavior. Although no indica-
tion of molecular weight is given in the
paper, the differences can be explained in
terms of viscoelastic relaxations. The PBA
fibrillates easily and without much dissipa-
tion at low rates. Its shear modulus must
then be relatively low and the glass transi-
tion temperature relatively low as well. The
fact that no transition to an adhesive fibril-
lar regime occurs is an indication of a short
terminal relaxation time characteristic of a
relatively low molecular weight.
The VA-EA adhesive shows a transition
from fibrillar to nonfibrillar failure at ap-
736 15 Materials Science of Pressure-Sensitive Adhesives
proximately the same peel rate, indicating a
similar shear modulus at room temperature
to the PB A. On the other hand the transition
from fibrillar cohesive to fibrillar adhesive
implies a much larger molecular weight than
the PBA polymer.
15.5.4 The Degree of Branching
and Crosslinking
From these conclusions, it is easy to ex-
trapolate that a slightly crosslinked adhesive
(below the gel point) would increase the
useful range of the adhesive as well as its
cohesive strength while preserving the
entanglement structure responsible for the
easy cavitation. However, when the cross-
linking is too extensive, fibrillation is in-
hibited and the tack and peel strengths de-
crease significantly. The practical difficulty
is therefore to reproducibly obtain a light
crosslinking. This strategy is commonly
used for acrylic systems where the incorpo-
ration of functional monomers during the
polymerization process allows a relatively
easy crosslinking step, and for silicone PSAs
that have a very low cohesive strength when
uncrosslinked (Satas, 1989; Sobieski and
Tangney, 1989). More systematic studies
were performed on a series of poly-
dimethylsiloxanes crosslinked through irra-
diation, and the optimum tack energy was
obtained for a degree of crosslinking close
to the gel point (Zosel, 1991), as illustrated
in Fig. 15-22. It should be noted that the
degree of branching has a large effect on the
elongational flow properties of polymers
and it is therefore not surprising that it should
affect the behavior of a fibrillating PSA.
15.5.5 The Incorporation
of Polar Groups in the Adhesive
Since most common substrates such as
wood, paper, and metal are relatively polar,
3
[-10
10 n
Pa
Jm 2 5
2
10 -\ -10
4
10 - -10
o 3
10 H -10
W G'.G"
-1 2
10 H -10
-2
10 - 10
0 10 2 kGy10 3
D-
Figure 15-22. Fracture energy Wand storage and loss
moduli G' and G" plotted vs. the radiation dose (D).
The dashed line is the gel point (Dg) (Zosel, 1991).
Reprinted with permission.
the incorporation of polar components is a
good strategy to improve the adhesion. This
approach is mostly used for the acrylate
family, where it is common to incorporate a
small amount of acrylic acid as a co-
monomer. The effect of adding a polar co-
monomer is twofold: The bulk properties of
the adhesive are affected through the forma-
tion of bridges and possible hydrogen
bonds, with the result of increasing the vis-
coelastic losses in the adhesive, while the
interfacial properties are also affected by the
strong interactions between the adhesive
and the substrate, so increasing the value of
the thermodynamic energy of adhesion Wadh
(Aubrey and Ginosatis, 1981). A further ef-
fect of polar groups can be a slow build up
of adhesion with time, reflecting the migra-
tion of the polar monomers at the interface
with the substrate and the specific bond for-
mation.
However, a large increase in the propor-
tion of polar component can significantly
reduce the domain of miscibility of the
tackifying resin, resulting therefore in a
 15.5 Effect of the Molecular Structure of the Adhesive
loss of performance (Kim and Mizumachi,
1995 b).
15.5.6 The Tackifying Resin
While in the previous sections emphasis
was put on the properties of pure polymers
to stress the effect of different molecular pa-
rameters on the adhesive properties, most
commercial pressure-sensitive adhesives
are a blend of a base polymer and, at least,
a tackifying resin. In many cases the for-
mulation is completed by the addition of
waxes, plasticizers, and antioxidants. The
tackifying resin, however, as its name indi-
cates, plays a special role in tailoring the
properties of the adhesive and therefore de-
serves to be examined in more detail.
Many commercially important elastomers
such as natural rubber, SBR rubber, or ther-
moplastic elastomers do not have pressure-
sensitive properties. A good tackifying res-
in is therefore designed to modify the vis-
coelastic properties of the adhesive in order
to notably improve the quick tack properties.
The resin must have three important proper-
ties: it must be fully miscible with the base
polymer, have a low molecular weight, and
a Tg higher than that of the base polymer.
Practically, the commercial tackifying
resins fall into three categories (Schlade-
man, 1989):
1) Rosin derivatives extracted from wood;
these are the most versatile resins and con-
sist normally of small molecules or dimers.
2) Aliphatic or aromatic hydrocarbon res-
ins produced from petroleum monomers,
which have molecular weights in the range
of 1000-2000.
3) Terpene resins obtained from the poly-
merization of turpentine derivatives, which
also have molecular weights of the order of
300-2000.
A few examples are given in Fig. 15-1.
737
The effectiveness of a tackifying resin is
related to its ability to modify the viscoelas-
tic properties of the polymer. This modifi-
cation is twofold: At high frequencies, the
high Tg of the resin increases the modulus
of the adhesive, therefore increasing the vis-
coelastic losses at the high frequencies char-
acteristic of a quick debonding process.
At low frequencies, the low molecular
weight of the resin decreases the modulus at
the frequencies characteristic of the slower
bonding process (controlled by the contact
time). Furthermore, the addition of the res-
in also produces a dilution of the entangle-
ment network, which will favor the occur-
rence of cavitation during the debonding
phase. As an illustrative example, the effect
of the addition a poly-jS pinene resin on the
storage shear modulus of natural rubber is
shown in Fig. 15-23. The skeleton of the
high molecular weight polymer provides the
cohesiveness, and the tackifying resin dra-
matically increases the viscoelastic and
plastic losses during debonding, while facil-
itating good contact.
Clearly, the effectiveness of the resin de-
pends on its ability to modify the viscoelas-
tic properties of the polymer. If the resin is
not fully miscible, the second phase will
simply act as a rigid filler, thus raising the
modulus at all frequencies with a risk of los-
ing the pressure-sensitive properties.
The miscibility of the resins with the base
polymers and the resulting modifications of
the viscoelastic properties have been stud-
ied extensively by several groups on natu-
ral rubber systems (Aubrey and Sherriff,
1978, 1980; Sherriff et al., 1973), SBR
systems (Class and Chu, 1985 a, b, c), and
acrylic systems (Kim and Mizumachi,
1995 a, b, c). The miscibility is controlled
by the Flory interaction parameter % be-
tween the rubber and the resin and by the
molecular weight of the resin (Class and
Chu, 1985 a, b, c). While it is always a good
738 15 Materials Science of Pressure-Sensitive Adhesives
LogG'
(N/m2
-3.0 -2.0 -1.0 0 1.0 2.0
Log (oaT
idea to choose a rubber with a degree of po-
larity similar to that of the resin, the choice
of the resin molecular weight has an opti-
mum value. Too low a molecular weight
will lower the Tg of the resin too much with
a risk of losing the tackifying proper-
ties, while too high a molecular weight de-
creases the miscibility.
Clearly this section does not cover all
the possibilities of property modification
through a proper formulation, but the inter-
ested reader can refer to more technologi-
cally oriented texts for further information
(Satas, 1989).
15.5.7 Triblock Copolymers
A new type of polymers has been used in-
creasingly for PSA applications, i.e., ther-
moplastic elastomers. Typically, these poly-
mers are triblock copolymers with a large
diene center block and two small styrene end
blocks. The microphase-separated micro-
structure of these block copolymers makes
them very good candidates for hot-melt pro-
cessing.
Figure 15-23. Shear mod-
ulus Gf vs. log coaT for a
resin/NR mixture: ()
NR, ( x - x - x ) 25% resin,
( ) 40% resin, and
( ) 50% resin (Sherriff
etal., 1973). Copyright
1973 John Wiley &
Sons, Inc. Reprinted by
permission.
3.0 4.0
Because a low viscosity is required for
processing, while a relatively high viscos-
ity is required for good creep resistance and
adhesive properties, most PSAs are manu-
factured through an emulsion or a solution
process. However, recent trends toward
cleaner processing techniques have pushed
the development of solvent-free processing
techniques commonly called hot melt
processing. Within that framework, SIS
copolymers have proved very valuable, as
the physical crosslinks formed by the PS
blocks below the Tg of PS provide a very
high creep resistance, while once heated
above Tg (PS) the zero shear rate viscosity
decreases dramatically, allowing hot-melt
processing.
These polymers have to be compounded
with a tackifying resin to have useful PSA
properties, and their two-phase microstruc-
ture raises some specific questions. The res-
in can be compatible with the diene block,
with the styrene block, or with both, and the
properties will be diversely affected (Ewins
et al., 1989). If the resin is compatible with
the diene block, its effect is very similar to

the classic rubber-resin case examined in
Sec. 15.5.6 (Kraus et al., 1977; Nakajima
et al., 1992). Rosins, terpenes, and aliphat-
ic hydrocarbons usually enter into that cat-
egory. If, on the other hand, the resin is com-
patible with the styrene end block, its role
is then either to increase the range of useful
temperatures (by raising the Tg of the sty-
rene) or to allow hot-melt processing at low-
er temperatures (by lowering the Tg of the
styrene) (Ewins et al., 1989).
15.6 Summary
The formulation of good pressure-sensi-
tive adhesives for specific applications
requires a good understanding of the para-
meters influencing the three classes of
properties of the adhesives, which are:
1) The ability to stick instantly to almost any
surface, even relatively rough, upon appli-
cation of a light pressure. This property
requires a shear elastic modulus smaller
than approximately 0.2 MPa at frequencies
of the order of 1 Hz. It should be noted that
surface and/or adhesive roughness will
strongly influence the ability of the adhe-
sive to stick. Some very low surface energy
substrates may require a surface treatment
for the PSA to stick.
2) The amount of energy per unit area
necessary to debond the adhesive from the
substrate. This property is controlled by:
a) The amount of viscoelastic losses at the
relevant rate of debonding. This rate is
equivalent to higher frequencies of the order
of 100 Hz. The amount of viscoelastic los-
ses and therefore the adhesion energy
required from the adhesive varies greatly
with the application and is typically con-
trolled by the addition of tackifying resins.
b) The thermodynamic energy of adhesion
at the interface Wadh, which can be strongly
15.7 References 739
influenced by specific interactions formed
between the adhesive and the substrate.
3) The cohesive strength of the adhesive,
which is relevant in two relatively distinct
cases:
a) For the long term resistance to an applied
shear, the relevant parameter is the shear
modulus at times comparable to the time of
the experiment. An elastic component to the
long term modulus is often added through a
light crosslinking of the adhesive.
b) A clean debonding of the adhesive from
the substrate (without any residual adhesi-
ve remaining on the surface) is often requi-
red for applications. This result implies that
the fibrils formed upon deformation of an
adhesive film must exhibit a marked strain
hardening at a high level of strain. This
property is controlled by the modulus (or
viscosity) in elongational flow and implies
a specific polymer architecture (some
branching or crosslinking) that will cause
such a strain hardening behavior.
The balance of properties necessary for a
specific application are then obtained typi-
cally by designing materials with a large
molecular weight distribution to provide
both long term cohesive strength and short
term high compliance. Their elastic mod-
ulus is of the order of 0.01 to 0.1 MPa at the
temperature and frequency of use. Polar
additives or comonomers are often used to
control specific interactions with the sub-
strate while low-molecular weight molec-
ules are added to specifically modify the
rheological properties of the adhesive.
15.7 References
Andrews, E. H., Kinloch, A. J. (1973 a), Proc. R. Soc.
London A 332,385.
Andrews, E. H., Kinloch, A. J. (1973 b), Proc. R. Soc.
London A 332, 401.
Andrews, E. H., Kinloch, A. J. (1974), J. Polym. Sci.
C: Polym. Symp. 46, 1.
740 15 Materials Science of Pressure-Sensitive Adhesives
Aravas, N., Kim, K. S., Loukis, M. J. (1989), Mater.
Sci. Eng. A107, 159.
Aubrey, D. W.,Ginosatis, S. (1981), J.Adhes. 12, 189.
Aubrey, D. W., Sherriff, M. (1978), 7. Polym. Set,
Polym. Chem. Ed. 16, 2631.
Aubrey, D. W., Sherriff, M. (1980), J. Polym. ScL,
Polym. Chem. Ed. 18, 2597.
Aubrey, D. W., Welding, G. N., Wong, T. (1969), J.
Appl. Polym. Sci. 13, 2193.
Bates, R. (1976), J. Appl. Polym. Sci. 20, 2941.
Brown, H. R. (1991), Annu. Rev. Mater. Sci. 21, 463.
Brown, H. R., Char, K., Deline, V. R., Green, P. F.
(1993), Macromolecules 26, 4155.
Chang, E. P. (1991), J. Adhes. 34, 189.
Char, K., Brown, H. R., Deline, V. R. (1993), Macro-
molecules 26, 4164.
Class, J. B., Chu, S. G. (1985 a), /. Appl. Polym. Sci.
30, 805.
Class, J. B., Chu, S. G. (1985 b), J. Appl. Polym. Sci.
30, 815.
Class, J. B., Chu, S. G. (1985 c), J. Appl. Polym. Sci.
30, 825.
Creton, C , Leibler, L. (1996), J. Polym. ScL, B:
Polym. Phys 34, 545.
Creton, C , Kramer, E. J., Hui, C. Y., Brown, H. R.
(1992), Macromolecules 25, 3075.
Dahlquist, C. A. (1969), in: Treatise on Adhesion and
Adhesives: Patrick, R. L. (Ed.). New York: Marcel
Dekker.
Dahlquist, C. A. (1989), in: Handbook of Pressure -
Sensitive Adhesive Technology: Satas, D. (Ed.).
New York: Van Nostrand Reinhold.
Dale, W. C , Paster, M. D., Haynes, J. K. (1989), J.
Adhes. 31, 1.
de Gennes, P. G. (1988), C. R. Acad. Sci. (Paris) 307,
1949.
Donald, A. M., Kramer, E. J. (1981), Phil. Mag. A43,
857.
Erb, R. A., Hanson, R. S. (1960), Trans. Soc. Rheol.
4, 91.
Ewins, E. E., St. Clair, D. J., Erickson, J. R., Korcz,
W. H. (1989), in: Handbook of Pressure-Sensitive
Adhesive Technology: Satas, D. (Ed.). New York:
Van Nostrand Reinhold.
Ferry, J. D. (1980), Viscoelastic Properties of Poly-
mers. New York: Wiley.
Fields, R. J., Ashby, M. F. (1976), Phil Mag.A33, 33.
Fuller, K. N. G., Tabor, D. (1975), Proc. R. Soc. Lon-
don A 345, 327.
Gardon, J. L. (1963), /. Appl. Polym. Sci. 7, 625.
Gent, A. N., Hamed, G. R. (1977), J. Appl. Polym. Sci.
21, 2817.
Gent, A. N., Kaang, S. Y. (1987), /. Adhes. 24, 173.
Gent, A. N., Kim, H. J. (1990), Rubber Chem. Tech-
nol. <53, 613.
Gent, A. N., Lindley, P. B. (1958), Proc. R. Soc. Lon-
don A 249, 195.
Gent, A. N., Petrich, R. P. (1969), Proc. R. Soc. Lon-
don A 310, 433.
Gent, A. N., Schultz, J. (1972), J. Adhes. 3, 281.
Gent, A. N., Wang, C. (1991), J. Mater. Sci. 26,
3392.
Good, R. J., Gupta, R. K. (1988), /. Adhes. 26, 13.
Greenwood, J. A., Williamson, J. B. P. (1966), Proc.
R. Soc. London A 295, 300.
Hamed, G. R. (1981), Rubber Chem. Technol. 54, 576.
Hammond, F. H. (1964), ASTM Spec. Tech. Publ. 360,
123.
Hammond, F. H. (1989), in: Handbook of Pressure-
Sensitive Adhesive Technology: Satas, D. (Ed.).
New York: Van Nostrand Reinhold.
Hui, C. Y, Xu, D. B., Kramer, E. J. (1992), J. Appl.
Phys. 72, 3294.
Johnson, K. L., Kendall, K., Roberts, A. D. (1971),
Proc. R. Soc. London A 324, 301.
Kaelble, D. H. (1965), Trans. Soc. Rheol. 9, 135.
Kaelble, D. H. (1969 a), J. Adhes. 1, 102.
Kaelble, D. H. (1969 b), in: Treatise on Adhesion and
Adhesives: Patrick, R. L. (Ed.). New York: Marcel
Dekker.
Kaelble, D. H., Reylek, R. S. (1969), /. Adhes. 1, 124.
Kim,H.J.,Mizumachi,H.(1995a), J.Adhes. 49, 113.
Kim, H. J., Mizumachi, H. (1995 b), /. Appl. Polym,
Sci. 56, 201.
Kim, H. J., Mizumachi, H. (1995 c), /. Appl. Polym,
Sci. 58, 1891.
Kinloch, A. J. (1987), Adhesion and Adhesives. Lon-
don: Chapman & Hall.
Kramer, E. J. (1983), Adv. Polym. Sci. 52/53, 1.
Kramer, E. J., Berger, L. L. (1990), Adv. Polym. Sci.
91/92, 1.
Kraus, G., Jones, F. B., Marrs, O. L., Rollmann, K. W.
(1977), /. Adhes. 8, 235.
Kraus, G., Rollmann, K. W., Gray, R. A. (1979), J.
Adhes. 10, 221.
Krenceski, M. A., Johnson, J. F. (1989), Polym. Eng.
Sci. 29, 36.
Krenceski, M. A., Johnson, J. F., Temin, S. C. (1986),
J. Macromol. Sci., Rev. Macromol. Chem. Phys.
C26, 143.
McEwan, A. D. (1966), Rheol. Acta 5, 205.
Mizumachi, H.,Hatano,Y. (1989),/. Appl. Polym. Sci.
37, 3097.
Nakajima, N., Babrowicz, R., Harrell, E. R. (1992), /.
Polym. Sci., Polym. Phys. Ed. 44, 1437.
Satas, D. (Ed.) (1989), Handbook of Pressure-
Sensitive Adhesive Technology. New York: Van
Nostrand Reinhold.
Schlademan, J. A. (1989), in: Handbook of Pressure-
Sensitive-Adhesive Technology: Satas, D. (Ed.).
New York: Van Nostrand Reinhold.
Sherriff, M., Knibbs, R. W., Langley, P. G. (1973), J.
Appl. Polym. Sci. 17, 3423.
Sobieski, L. A., Tangney, T. J. (1989), in: Handbook
of Pressure-Sensitive Adhesive Technology: Satas,
D. (Ed.). New York: Van Nostrand Reinhold.
Toyama, M., Ito, T., Moriguchi, H. (1970), J. Appl.
Polym. Sci. 14, 2039.

Tsukatani, T., Hatano, Y., Mizumachi, H. (1989), /.
Adhes. 31, 59.
Urahama, Y. (1989), J. Adhes. 31, 47.
Williams, J. G. (1993), J. Adhes. 41, 225.
Wool, R. P. (1991), in: Fundamentals of Adhesion:
Lee, L. H. (Ed.). New York: Plenum.
Zosel, A. (1985), Colloid Polym. Sci. 263, 541.
Zosel, A. (1989), J. Adhes. 30, 135.
Zosel, A. (1991), J. Adhes. 34, 201.
Zosel, A. (1992), Adv. Pressure Sensitive Adhes. Tech-
nol 1, 92
Zosel, A. (1994), /. Adhes. 44, 1.
Zosel, A. (1997), unpublished.
Ziille, B., Linster, J. J., Meissner, J., Hiirlimann, H. P.
(1987),/. Rheol. 31, 583.
15.7 References 741
General Reading
Brown, H. R. (1991), Annu. Rev. Mater. Sci. 21, 463.
Ferry, J. D. (1980), Viscoelastic Properties of Poly-
mers. New York: Wiley.
Kinloch, A. J. (1987), Adhesion and Adhesives. Lon-
don: Chapman & Hall.
Lee, L. H. (Ed.) (1991), Fundamentals of Adhesion.
New York: Plenum.
Patrick, R. L. (Ed.) (1969), Treatise on Adhesion and
Adhesives. New York: Marcel Dekker.
Satas, D. (Ed.) (1989), Handbook of Pressure-
Sensitive Adhesive Technology. New York: Van
Nostrand Reinhold.
Zosel, A. (1992), Adv. Pressure Sensitive Adhes. Tech-
nol. 1, 92.
16 New Processing Technologies
Ian M. Ward

IRC in Polymer Science and Technology, University of Leeds, Leeds, U.K.

List of Symbols and Abbreviations 744

16.1 Introduction 745
16.2 Ram Extrusion 745
16.3 Hydrostatic Extrusion 747
16.3.1 Mechanics of the Hydrostatic Extrusion Process 749
16.3.2 Engineering Possibilities for Hydrostatic Extrusion: Scope and Possibilities 752
16.3.3 Other Physical Properties 754
16.4 Die-Drawing 754
16.4.1 Mechanics of the Die-Drawing Process 758
16.5 Roll-Drawing 760
16.6 Conclusions 761
16.7 References 761

Materials Science and Technology

Copyright WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
744 16 New Processing Technologies

List of Symbols and Abbreviations

B factor in die-drawing analysis
c* constant
d diameter
d0, df die initial diameter, die exit diameter
D diameter of billet
k thermal diffusivity
kB Boltzmann's constant
P hydrostatic pressure
R instantaneous deformation ratio
RA actual extrusion ratio
RN nominal extrusion ratio
T absolute temperature
AU activation energy
v velocity
v0, vf velocity of polymer on entering die, at die exit
V shear activation volume

a die semi-angle
y' pressure coefficient
tan 8 loss factor
strain
* strain constant
strain rate
billet-die friction coefficient
of flow stress
ax, ay principal stress
a* stress constant
Q pressure activation volume
Tf shear flow stress

LPE linear polyethylene

PMMA polymethylmethacrylate
POM polyoxymethylene
UHMW-PE ultra high molecular weight polyethylene

16.1 Introduction
Starting in the late 1960s, several tech-
niques have been explored to produce
highly oriented polymers by plastic defor-
mation in the solid phase below the melting
point.
The simplest of these is tensile drawing,
which was already well-established for the
production of textile fibers and polymer
films of moderate strength and stiffness. A
major reappraisal of this technique (Capac-
cio and Ward, 1973) led to the invention of
processes for high modulus polyethylene
fibers by the melt spinning/high draw
ratio route (presently commercialized by
Hoechst Celanese as CERTRAN fiber). The
aim of this review is to consider techniques
which can be used to produce oriented poly-
mers in larger solid sections rather than
fibers or monofilaments. In historical order
of development, these are ram extrusion,
hydrostatic extrusion, die-drawing and
roller-drawing.
16.2 Ram Extrusion
The principal protagonists of ram extru-
sion of polymers have been two groups:
Takayanagi and co-workers in Japan (Imada
et al., 1971), and Porter and co-workers in
USA (Weeks and Porter, 1974) and their
objectives have been somewhat different.
In ram extrusion, the polymer is deformed
in the solid phase by application of pressure
to a piston which pushes an isotropic plug
of polymer through a die of reducing cross-
section. Mostly simply this is of circular
cross-section but it could be rectangular. In
Takayanagi's group, the behavior of sever-
al polymers were studied, and in general
comparatively modest reduction ratios were
obtained. In polyethylene, however, reduc-
tion ratios as high as 16 were reported, high
16.2 Ram Extrusion 745
crystallite orientation was observed and
Young's moduli as high as 10 GPa.
In addition to examining the structure and
mechanical properties of the extrudates,
Takayanagi and his colleagues (Imada et al.,
1971) also attempted to undertake a quanti-
tative analysis of the mechanics of the
hydrostatic extrusion process. They adopt-
ed a lower bound analysis, similar to the
classic Hoffman-Sachs analysis of the
extrusion of metal (Hoffman and Sachs,
1953), incorporating an empirical relation-
ship between true stress crand plastic strain
of the form
log ((7/(7*) log (/*) =-C* (16-1)
where a*, e* and c* are constants.
As will be discussed later, this approach
is a viable one, but in the theory developed
by Takayanagi and co-workers, the rise in
pressure with increasing extrusion ratio was
not accurately modeled, because no account
was taken of the major effects of strain rate
and pressure on the flow stress.
The ram extrusion technique has also been
developed by Porter and his colleagues from
the early 1970s onwards, with outstanding
results in terms of producing very highly
oriented polymers. In Porter's earliest
experiments with Southern (Southern and
Porter, 1970) ram extrusion of polyethylene
was undertaken under conditions where the
polymer was molten before entering the die.
It was found that very fine strands of highly
oriented polyethylene were produced as the
polymer crystallized from the melt and
became oriented by the action of the reduc-
ing die. In a later study, Keller and co-
workers (Odell etal., 1978) showed that
such behavior was consistent with previous
observations by Van der Vegt and Smit
(1967) where blockage occurred when mol-
ten polyethylene was extruded in a capillary
rheometer under conditions where the poly-
mer would be expected to stay molten.
746 16 New Processing Technologies
Southern and Porter had shown that the large
increase in pressure which occurred was due
to crystallization in the elongation flow field.
In support of this contention the transparent
strand of highly oriented polymer, although
it had a comparatively low overall modulus
of 6.6 GPa at 110 Hz, showed a high melt-
ing component on the DSC trace which could
be assigned to chain extended polyethylene.
Keller and his co-workers repeated Southern
and Porter's work and were able to optimize
the conditions to produce a highly oriented
plug of polyethylene with a modulus of
70 GPa. It was shown that the morphology
of this material was very remarkable. The
comparatively low melting point indicated
that in this case there was no extended chain
material present. Transmission electron
microscopy showed a structure of interlock-
ing lamellae, consistent with the long peri-
od of 300 A calculated from a very clear two
point S AXS pattern. It was proposed that the
high Young's modulus arises due to the con-
straints imposed on the rubber like amor-
phous regions by the parallel lamellae struc-
ture, similar to the situation where sheets of
steel are laminated with thin layers of incom-
pressible rubber.
Porter and his co-workers (Griswold
et al., 1978) made a major advance in the
usefulness of ram extrusion by inventing the
ingenious technique of co-extrusion where
a sheet of polymer is extruded between a
split billet consisting of two hemicylinders
of a second polymer. This technique was
first demonstrated by co-extrusion of linear
polyethylene (du Pont A 7050 grade,
Mw = 59000, Mn= 19900) using the same
polymer for the two hemicylinders forming
the sheath, and a film strip as the core which
was inserted between the two sheath hemi-
cylinders. In these first experiments draw
ratios of ~30 were obtained, and Young's
moduli ~30 GPa, and it was found that much
faster extrusion rates (~ 10 cm/min) could be
achieved. In later experiments much more
spectacular results were obtained. For
example, multiple-stage drawing of reactor
powder of ultra high molecular weight poly-
ethylene (UHMW-PE) was taken to a max-
imum total draw ratio of 56, giving a resul-
tant tensile modulus of 58 GPa (Pawlikow-
ski et al., 1988). Again, the co-extrusion
technique was used as the first stage of a
two-stage drawing process for drawing
solution-grown mats of UHMW-PE to the
remarkable total draw ratio of 120, with a
resultant tensile modulus of 160 GPa (Kan-
amotoetal., 1983).
Porter and his colleagues also showed that
the co-extrusion technique could be applied
to amorphous polymers (Zachariades et al.,
1979). In one series of experiments a film
strip of polystyrene was inserted between
the two hemispheres of Alathon 7050 and
the whole assembly extruded at 126 C in an
Instron rheometer to a maximum extrusion
ratio of 11.6. The drawn film showed a high
birefringence (-2.24x10~2), a tensile mod-
ulus of - 4 - 5 GPa and a tensile strength of
85 MPa. In subsequent experiments by
Appelt and Porter (Appelt and Porter, 1981),
the containing hemicylinders were changed
to polypropylene or nylon 6.6, and two-
stage co-extrusions were explored and com-
pared with results for polyethylene hemicy-
linders. Two-stage co-extrusion enabled
higher total draw ratios to be achieved and
in PE these reached as high as 21.
Other polymers which were successfully
drawn by Porter and his colleagues using the
co-extrusion technique include polyethy-
lene terephthalate (Pereira and Porter,
1983 a, b) starting with both amorphous
films, but also crystalline film which is often
considered too brittle to be drawn by con-
ventional tensile drawing, poly(4-methyl-
pentene-1) (He and Porter, 1987) and nylons
6 and 11 plasticized with anhydrous ammo-
nia (Zachariades and Porter, 1979).

163 Hydrostatic Extrusion
The ram extrusion technique suffers from
two major disadvantages, both of which
stem from the high friction between the
polymer and the metal die. This high fric-
tion limits the process to very low extrusion
rates, and also, as shown by Farrell and Kel-
ler (1977), gives rise to a significant varia-
tion in the structure across the extrudate sec-
tion, due to very high shear deformations in
the billet near to the billet/die interface.
Although the Porter split billet technique
reduces these limitations, only compara-
tively small samples can be produced, pref-
erably thin sheets of polymer. Hydrostatic
extrusion enables a step forward in these
respects, because the pressure is applied not
by a piston, but by a hydraulic fluid, which
can lubricate the interface between the die
and the billet. It has been shown that the de-
formation is then very close to that produced
by tensile drawing where there is a free sur-
face (plug-flow) and essentially homogene-
ous sections are produced. The friction is
also reduced because the billet is only in
contact with a metal surface within the die,
and is otherwise free standing. A schemat-
ic diagram of a typical set up is shown in
Fig. 16-1. It is important to note that the
haul-off force is negligibly small and serves
only to ensure that the extrudates are straight
and do not curve on leaving the die exit.
Vessel
Chamber with
Pressurising Fluid
16.3 Hydrostatic Extrusion 747
In terms of producing oriented polymers
of either academic or industrial interest, the
first attempts to explore the potential of
hydrostatic extrusion were disappointing,
although research at the ICI Petrochemical
and Polymer Laboratory reported by Wil-
liams (1973), showed that polypropylene
rods could be produced with a Young's mod-
ulus of 16 GPa. In 1972, Gibson and Ward,
who had been working at ICI with Williams,
transferred the ICI equipment to Leeds Uni-
versity with financial support from SERC,
and in collaboration with Cole and Parsons
showed that very highly oriented polyethy-
lenes could be produced with Young's mod-
uli of about 60 GPa (Gibson et al., 1974).
This discovery, the invention of high
modulus polyethylene in solid section, as
distinct from fibers and monofilaments, led
to a period of very fruitful collaboration
between the Departments of Physics and
Mechanical Engineering at Leeds Univer-
sity, which had two main thrusts:
(1) Attempts to assess the potential of
hydrostatic extrusion for producing oriented
polymers in the form of rod, sheet and tube.
A particular issue here was the viability of
the technique for polyethylene and other
polymers, including amorphous polymers.
(2) The development of a protocol for
gaining a quantitative understanding of the
mechanics of the solid phase extrusion pro-
cess.
Figure 16-1. Sche-
matic diagram of
apparatus for hydro-
Die Hf'o" static extrusion of
load
polymer (Ward, 1985).
Springer-Verlag.
Heater Reproduced by per-
Bands
748 16 New Processing Technologies
A corner stone in the understanding of the
issues involved in both (1) and (2) above
was the recognition of the importance of the
extrusion ratio. A key process parameter in
the hydrostatic extrusion of circular billets
through a conical die (the simplest proce-
dure) is the nominal extrusion ratio RN, the
ratio of the cross-sectional area of the initial
billet to that of the die exit. It is assumed
that deformation occurs at constant volume,
which is a very good approximation. There
may however be some degree of shrinkage
after the oriented polymer has left the die
(akin to the die-swell observed in melt
extrusion). It is therefore necessary to also
define the "actual" extrusion ratio RA,
which is the ratio of the cross-section of the
initial billet and the final extrudate. In prac-
tice RA is equal to RN to a very good approx-
imation, indeed for high reduction ratios RA
is equivalent to the draw ratio, which is con-
ventionally used as an operational parame-
ter in tensile drawing.
In the studies of tensile drawing of poly-
ethylene (and later other polymers) it was
shown that the modulus of the drawn poly-
mer, related only to the draw ratio, to a very
good approximation. Similar results were
soon produced for hydrostatic extrusion and
it was shown that for a given polymer com-
position very similar Young's moduli were
obtained either by tensile drawing or by
hydrostatic extrusion for a given draw ratio
or extrusion ratio RN these being equivalent.
Figure 16-2 shows results for the Young's
moduli of small-diameter extrudates (Gib-
son et al., 1978), comparing data for samples
of comparatively low molecular weight
(R25, R50 and R140) and a UHMPE grade
(Hostalen GUR). It can be seen tht the mod-
ulus/draw ratio relationship is to a good
approximation independent of polymer
grade for the low molecular weight poly-
mers, similar to results obtained by tensile
drawing (Capaccio and Ward, 1974). This
Figure 16-2. Young's modulus of small diameter
extrudates: A HGUR, RSO, OR25, A R 140(Gib-
son and Ward, 1978). John Wiley & Sons, Inc.
Reprinted by permission.
unique relationship does not hold, however,
when the UHMW-PE grade is included, and
it has been shown that the moduli of high
molecular weight and copolymer grades are
significantly lower than those of the lower
molecular weight materials. It has been con-
cluded that these differences are due to lower
degrees of crystalline continuity and lesser
degrees of crystallinity (Hope et al., 1980).
Two structural models have been proposed
to explain the development of such high
moduli with increasing draw ratio. Histori-
cally the first model was proposed by Bar-
ham and Arridge (1977) and envisages high
modulus polyethylene as akin to a short fiber
composite, with needle-shaped crystals act-
ing as the reinforcing phase. The aspect ratio
of these crystals was considered to increase
affinely with increasing draw ratio, so that
the crystals became increasingly effective in
reinforcing the structure. A particular suc-
cess of the model was that it related the mod-
ulus to the draw ratio quantitatively via this
change in the aspect ratio of the crystals.
The second model, proposed by Gibson,
Davies and Ward (Gibson et al., 1978) was
based on two key structural observations.
First, it was found that the hydrostatically
extruded materials showed the two-point
 16.3 Hydrostatic Extrusion 749

small angle X-ray diffraction pattern, typi-

cal of a periodic structure corresponding to
a long period of about 200 A which depend-
ed on the extrusion temperature but not the
extrusion ratio. Secondly, the average crys-
tal length, measured initially from the width
of the (002) meridional reflection, con-
firmed by dark field electron microscopy,
showed that the average crystal length
increased with increasing draw ratio from
= 100 A to =500 A at draw ratio 30, and
increased with draw temperature in a man-
ner such that the ratio of the average crys-
tal length to the long period for a given draw
ratio was approximately constant. Gibson et
al. therefore proposed their crystal bridge
model, illustrated in Fig. 16-3, where the
periodic lamellar structure is linked by crys-
tal bridges, whose number increases with
draw ratio. Barham has subsequently
shown, on the basis of neutron scattering
measurements, that the crystal bridge model
is most likely a good approximation to the
real structure, and certainly better than
either the Barham and Arridge model or the Figure 16-3. A schematic representation of the struc-
Peterlin model where the lamellae are linked ture of highly oriented polyethylene produced by solid
by tie molecules (Peterlin, 1971). phase deformation (Gibson et al., 1978). Elsevier
Science Ltd., Butterworth-Heinemann. Reproduced
Gibson et al. showed that the plateau by permission.
dynamic modulus at -50 C (i.e. between the
/and a relaxations) could be quantitatively (1) The development of a quantitative
predicted from X-ray diffraction data. It was analysis of the mechanics of the hydrostat-
also subsequently shown (Gibson et al., ic extrusion process.
1982) that the temperature dependence of the (2) The engineering possibilities in terms
dynamic modulus and loss factor (tan 8) of practical processes, and the range of poly-
could be quantitatively predicted by the crys- mers which could be created by hydrostatic
tal bridge model, where the long crystals act extrusion.
like the short fibres in a short fibre compos- (3) Possible enhancement of other phys-
ite (akin to the Barham and Arridge model, ical properties by orientation, e.g., chemi-
but physically quite different, because the cal resistance, thermal conductivity.
reinforcing elements are long crystals with
very small lateral extents (=10 A)).
16.3.1 Mechanics of the Hydrostatic
The production of high modulus polyeth-
Extrusion Process
ylene by hydrostatic extrusion stimulated
developments in three directions which will The mechanics of the hydrostatic extru-
be considered in turn. sion process have been discussed in sever-
750 16 New Processing Technologies
al reviews, notably by Capaccio, Gibson and
Ward (Capaccio et al., 1979) and Inoue
(1985). The first detailed analysis of the
mechanics was given by Coates, Gibson and
Ward (Coates et al., 1980) and what follows
is essentially based on this treatment, which
was developed more comprehensively by
Hope and Ward (1981).
The general starting point for the analy-
sis of the Hoffman and Sachs (1953) lower
bound approach. The force balance on a
thin, parallel sided element in the deforma-
tion zone of a conical die (Fig. 16-4) is given
by
cot a) (16-2)
where \x is the billet-die friction coefficient,
a is the die semi-angle, is the external
strain, and ox and oy are the stresses parallel
to and normal to the extrusion direction. For
low die angles, ax and ay can be assumed to
be principal stresses.
A key step in the analysis is to relate ax
and oy via the material flow stress and hence
reduce Eq. (16-2) to a first order differen-
tial equation in ax which can be solved pro-
vided that the appropriate boundary condi-
tions are specified. In polymers, major com-
plexity is introduced because the flow stress
CTf, unlike that of metals, is strongly depen-
dent on pressure P, plastic strain (strain
d0
A L df
r r
Figure 16-4. Co-ordinate system used to represent
the deformation zone in conical die extrusion (Capac-
cio et al., 1979). Reproduced by permission.
hardening) and strain rate (strain rate sen-
sitivity). We therefore write the yield or flow
stress criterion as
GX-Gy=( e, e,P) (16-3)
It is convenient, and justifiable on physical
grounds based on experimental evidence, to
assume a linear, additive pressure effect so
that we can write Eq. (16-3) as
, e) + fP (16-4)
where y7 is a pressure coefficient.
Alternatively, it may be more appropriate
in considering the deformation of highly
anisotropic polymer to use a Coulomb yield
criterion where the effect of pressure can be
better represented by the effect of the nor-
mal stress oy, so that Eq. (16-4) is modified
to
ox- ay-af(, ) + Y<3y (16-5)
In practice any numerical differences
between the use of Eqs. (16-4) and (16-5)
will be small, but it can be seen that Eq.
(16-5) can readily be used to eliminate a
from Eq. (16-2) giving
(16-6)
dcr, <JX-Gf(,)
(l + / i c o t a )
d 1 + y'
A first step towards solving Eq. (16-6)
involves defining the boundary conditions
for deformation in the die to take into
account the work performed due to shear at
the die entry and die exit. This redundant
work (and redundant strain) has been calcu-
lated by Avitzur (1968). It was found by
Gibson and his colleagues that although the
redundant work has a negligible effect on
the final computed extrusion pressures and
the redundant shear strain has a negligible
effect on the flow stress, the redundant
strains do modify the strain boundary con-
ditions significantly.
To calculate the strain and strain rate in
the conical die, it is assumed that plane sec-

tions remain plane in passing through the
die, i. e., plug flow. The strain x is therefore
given in terms of the instantaneous defor-
mation ratio R at a distance x from the die
exit as
=lnR (16-7)
and the strain rate at the point x by the Avit-
zur relationship
3/2
e = ^- tan a (16-8)
where vf is the die exit velocity and df is the
die exit diameter.
The next issue to be considered is the
determination of the dependence of the flow
stress on , and P or oy. A key assump-
tion, which underpins the analysis of the
hydrostatic extrusion process, and other
solid state deformation processes, is the
assumption of a true stress, true strain, strain
rate relationship for polymers. It is assumed
that the flow stress is independent of the de-
formation history, but depends only on the
total plastic strain (i.e., the current extru-
sion ratio) and the current strain rate. This
assumption implies that at a fixed tempera-
ture (isothermal deformation) the flow
stress can be given a three-dimensional rep-
resentation, as shown for Rigidex 50 LPE at
100 C, in Fig. 16-5. The effect of P or ay is
considered to be additive. Hope and Ward
sec -2
2.5x10
5x10" 3
5x10
16.3 Hydrostatic Extrusion 751
(1981) explored the proposal by Briscoe and
Tabor (1978) that there is a direct correla-
tion between the friction coefficient ji and
the pressure coefficient Y a n d Eqs. (16-4)
and (16-5). It was shown that this correla-
tion implies
(16-9)
where we now require that both ji and Y a r e
in principle strain dependent. The virtue of
this correlation is that it reduces Eq. (16-6)
to an equation in a single parameter y7, giv-
ing
(16-10)
ox-of(,)^
d + /'()
Hope and Ward used the analysis leading to
Eq. (16-10) with appropriate flow stress
data to compare experimental and numeri-
cally calculated extrusion pressures for
linear polyethylene (LPE), polyoxymeth-
ylene (POM) and polymethylmethacrylate
(PMMA). It can be seen from Fig. 16-6 that
the rapid rise in pressure with increasing RN
is quite well modeled, and a number of con-
clusions can be made.
First, Eqs. (16-7) and (16-8) show that
both strain and strain rate increase towards
the die exit. Figure 16-5 shows that the flow
stress for LPE (and this is true for POM and
Figure 16-5. Three-dimen-
sional representation of the
stress-strain-strain rate rela-
tionship for Rigidex 50 LPE at
100C. (Capaccio et al., 1979).
Reproduced by permission.
752 16 New Processing Technologies
200
/POM
P
(MPa)
150
PMMA f Gupta and McCormick (1980) have given
/ '
/ LPE
/ /
100
50
0
1 5 10 15 20
Figure 16-6. Best analytical fits to experimental
extrusion pressure (P) versus extrusion ratio (RN) data
for LPE, POM and PMMA (Hope and Ward, 1981).
Chapman & Hall. Reproduced by permission.
PMMA also) increases markedly with
increasing plastic strain and increasing
strain rate. Hydrostatic extrusion is there-
fore an unfavorable process in terms of the
mechanics of processing polymers in the
solid state.
Secondly, the effects of pressure on the
flow stress also lead to an increase in flow
stress, which is a further argument for the
unfavorable nature of hydrostatic extrusion.
Finally, Hope and Ward concluded that the
friction (and pressure) coefficients predict-
ed on the basis of Eq. (16-10) suggested that
although boundary lubrication occurs at the
die exit (validating the equivalence of fric-
tion and pressure) it is likely that hydrody-
namic lubrication may occur elsewhere giv-
ing lower friction at the die entrance.
Inoue, Nakayama and Ariyama (Inoue
et al., 1981) showed that a much simpler
analysis produced a fit to data for PMMA in
the range RN= 1 -2.5. It was assumed that
the flow stress is pressure dependent, but
constant in form throughout the die (i.e.,
strain hardening and strain rate sensitivity
were assumed to be negligible). A constant
friction coefficient JLI = 0.01 was assumed.
an upper bound analysis of the hydrostatic
extrusion of linear polyethylene. A com-
pletely analytical solution was obtained by
following results obtained by Coates and
Ward (1978) which represented the depen-
dence of flow stress on strain and strain rate
by the Eyring equation for a thermally acti-
vated process. This relationship gives the
strain rate as
= eoexp - (16-U)
where o is a pre-exponential factor, At/ is
the activation energy, rf the shear flow
stress, Vis the shear activation volume, P is
the hydrostatic pressure, Q is the pressure
activation volume, kB is Boltzmann's con-
stant and T is absolute temperature.
As also discussed later by Hope and Ward,
Eq. (16-11) is a useful starting point for rep-
resenting the flow stress behavior, provid-
int that the increase in strain rate sensitivity
with strain is taken into account by making
the shear activation volume dependent on
strain. For comparatively low deformation
ratios (up to RN = 9) V can be considered to
decrease exponentially with increasing
strain, and hence an analytical solution is
obtained via Eq. (16-6), which Gupta and
McCormick showed to give a reasonably
good fit to results for linear polyethylene.
16.3.2 Engineering Possibilities
for Hydrostatic Extrusion:
Scope and Possibilities
It has been shown that good quality extru-
dates can be produced by hydrostatic extru-
 16.3 Hydrostatic Extrusion 753

sion for a range of different polymers,
including LPE, PP, POM and PMMA. For
simple non-circular sections the processing
conditions are very similar to those for a cir-
cular cross-section, but for tubular and
I-beam sections, higher pressures are
required due to higher strain rates in the de-
formation zone and increased die friction.
The major limitations of the hydrostatic
extrusion process have been identified from
the analysis of the mechanics presented
above which explains why isothermal extru-
sion of small diameter material can only
proceed very slowly at rates ~1 cm/min. For
larger extrudates fast rates can be anticipat-
ed because the exit velocity is proportional
to exit die diameter for a given strain rate
(Eq. (16-8) above). Hope and Parsons
(1980) showed that stable extrudates can
also occur in an adiabatic regime and for
R40 grade polyethylene extrudate veloc-
ities up to -50 cm/min were achieved, as
shown in Fig. 16-7 a. Similar results were
presented by Inoue (Inoue, 1985) and are
shown in Fig. 16-7b, where the pressure
drop in stage II was shown to be due to adi-
abatic heating. It was proposed by Gibson
et al. (1978) that the level of adiabatic heat-
ing will be determined by the quantity vfdf/k
where vf is the rate of extrusion, df the die

u
60
10 100 1000
v f (mm min"1)
(b)
S.
LJU 8
DC o
D
CO 200
-

LU o A
DC
D
Q_
D o S3 n
~Z. 150
O - *

CO
D STAGE I STAGE II STAGE III
DC i n n I j 1 i

LJJ
0.001 0.01 0.1 1 10 100
EXTRUSION RATE V in mm/s
Figure 16-7. (a) Extrusion pressure versus extrudate velocity for polyethylene-large scale R40 polyethylene
extrusion (r N = 90C, product diameter 15.5 mm) (Ward, 1985). Springer-Verlag. Reproduced by permission,
(b) Relationship between extrusion pressure and extrusion rate for hydrostatic and ram extrusion of LPE with
RN = 1 at room temperature. Hydrostatic Extrusion: O steel die, A polycarbonate, die nylon die. Ram Extru-
sion: steel die, A polycarbonate die (Inoue, 1985). Chapman & Hall. Reproduced by permission.
754 16 New Processing Technologies

exit diameter and k the thermal diffusivity oriented products show surprisingly high
of the polymer. fracture toughness values for the propaga-
In a recent development it has been shown tion of cracks both parallel and perpendic-
that the potential of the hydrostatic extru- ular to the draw direction.
sion process can be substantially increased
for polyethylene by pressure annealing the
polymer at high temperatures prior to extru- 16.3.3 Other Physical Properties
sion (Powell et al., 1990). The pressure
In addition to enhancement of Young's
annealing treatment has to be optimized so
modulus and strength, molecular orienta-
that thicker lamellar crystals are produced,
tion gives rise to changes in other physical
but without destroying the molecular net-
properties. These results have been revie-
work. The hydrostatic extrusion process
wed extensively elsewhere (Ward, 1985)
aligns the aggregate of highly oriented units
and include improvements in creep behav-
so that a highly oriented structure is pro-
ior, higher thermal conductivity, low axial
duced at comparatively low extrusion ratios
coefficient of thermal expansion, reduced
(-10). In this way high modulus products
shrinkage at high temperatures.
can be made more readily, and for a wider
range of polymer molecular weights. This
development is of particular interest in
understanding the relationship between 16.4 Die-Drawing
structure and deformation in polymers. It
could also have some practical utility for Any solid phase deformation process can
special applications, especially in the bio- be regarded as orienting the polymer by
medical area. taking a particular path across the true
Mention should also be made of the suc- stress-strain-strain rate surface. This is
cessful hydrostatic extrusion of glass-filled illustrated in Fig. 16-8 for hydrostatic extru-
polymers, including polyoxymethylene and
polypropylene (Hope et al., 1982). The
Hydrostatic
important additional factor here is the align- Extrusion
ment of the short glass fibers in addition to
the alignment of the polymer matrix. Prod-
ucts with outstanding mechanical properties
Tensile
are produced. The development of elastic Drawing
anisotropy has been modeled to a good first
appropriation by the aggregate model,
where the development of fiber orientation
follows a simple pseudo-affine deformation
scheme where the axes of the fibers rotate
towards the draw direction in an identical
fashion to lines marked as the polymer
which can be assumed to deform at constant Figure 16-8. Schematic diagram of process flow
volume (Curtis et al., 1982). stress paths for elements of material undergoing
hydrostatic extrusion through a conical die of small
The fracture toughness of glass-filled semi-angle, compared with that for tensile drawing.
POM oriented by hydrostatic extrusion has (Ward, 1985). Springer-Verlag. Reproduced by per-
also been studied (Hine et al., 1993). The

i^ ^
T I ' ' - ....
i
i
d i 1 | 2 i
\ i
i
T HAUL-OFF
/1 "\ * HEATED
HEATED
BILLET DIE
ISOTROPIC
1.
DRAWING ZONES.
Figure 16-9. Schematic diagram of the die-drawing process: 1, 2, 3 are the drawing zones (Richardson et al..
1986). Elsevier Science Ltd. Reproduced by permission.
sion and tensile drawing. As already dis-
cussed, hydrostatic extrusion through a con-
ical die has a path of increasing strain and
strain rate. In tensile drawing, on the other
hand, the highest strain rates are experi-
enced in the neck where the plastic strain is
at an intermediate level and the flow stress
therefore does not reach such high levels.
These considerations indicate that there will
be merit in pulling a polymer through a heat-
ed die and as shown in Fig. 16-9, allowing
it to come away from the die wall and draw
as in free tensile drawing. This leads to three
deformation regimes:
(1) The initial region where contact with
the die wall is maintained and the deforma-
tion is essentially isothermal.
(2) Free drawing within the die, at approx-
imately the die temperature, but some adia-
batic heating is likely.
(3) Continuing deformation outside the
die until the polymer cools and reaches its
final deformation ratio.
This very simple process was first dem-
onstrated successfully for polypropylene
16.4 Die-Drawing 755
(VELOCITY V f) STEADY
DIE-DRAWN
PRODUCT
DRAWING LOAD L)
*[*!
(Coates and Ward 1970, 1979). Key results
are shown Fig. 16-10 a, where the final
(maximum) deformation ratio RA (= origi-
nal/final cross-sectional area) is plotted as a
function of the haul-off velocity for two die
configurations defined by RN = 5 and RN = 1.
RN is the ratio of the original billet cross-
sectional area to that of the die exit. As the
imposed draw speed is increased the extrud-
ing billet leaves the die wall and RA increas-
es markedly reaching a value of 20 for the
RN = 1 configuration. Figure 16-10 b shows
that as in the case of hydrostatic extrusion
and tensile drawing, the Young's modulus
depends to a good approximation only on
the draw ratio, reaching a value of 20 GPa
for RA = 20. It is particularly important to
note that, in contrast to hydrostatic extru-
sion, the highest deformation ratios are
obtained at the highest draw speeds and even
in this demonstration reach values of
50 cm/min.
These results on polypropylene together
with similar results obtained for the die
drawing of polyethylene by Gibson and
Ward (1980) were sufficiently encouraging
756 16 New Processing Technologies
20 40 60
(a) Imposed Draw Speed (cm/min)
A, max
Figure 16-10. (a) Dependence of maximum steady
deformation ratio RA on imposed draw speed for PP
copolymer die drawn at a nominal temperature of
110C. (O,/?N = 7, 15.5 mm die, A,/? N = 5, 15.5 mm
die, A, RN = 5, 1 mm die) (Ward, 1985) Springer-
Verlag. Reproduced by permission, (b) Axial Young's
modulus versus draw ratio for PP copolymer die
drawn at 110C (O, /?N = 7, 15.5 mm die, A, RN = 5,
15.5 mm die, A, RN = 5, 7 mm die). Tensile drawing
results for PP homopolymer fibres (dashed line),
hydrostatic extrusion of PP homopolymers (dotted
line) (Ward, 1985). Springer-Verlag. Reproduced
by permission.
to ensure the construction of a large scale
facility capable of producing oriented rod,
sheet and tube in lengths up to 11 m (Rich-
ardson et al., 1986). In the first stage the
polymer billets were heated to the draw tem-
perature in a 18 m long tubular heating
chamber. A range of dies was available, and
these were treated in an independently heat-
ed block at one end of the heating chamber.
The polymer is drawn through the die,
gripped by suitable means, the gripper unit
being held in a load cell and capable of
travelling along a load bench of 11 m
length. The haul-off velocities can be
increased from a low value ~1 cm min"1
initially up to 2 m min"1 or higher in favor-
able cases.
The batch die-drawing rig has been used
extensively to demonstrate the viability of
the process for a very wide range of poly-
mers, including polyethylene (both homo-
polymers and copolymers) polypropylene,
polyoxymethylene, polyvinylchloride, poly-
vinylidene fluoride, polyethylene terephtha-
late and polyaryletherketone.
The die-drawing process has been used to
produce high modulus and high strength
rods and monofilaments of polyethylene,
polypropylene and polyoxymethylene.
Square section rods of polyethylene can be
twisted in a slowly revolving chuck to pro-
duce "barley sugar" geometry suitable for
reinforcing concrete. This potential applica-
tion has been evaluated by the Department
of Civil Engineering at Leeds University
(Kamal, 1983; Gowripalan, 1987; Gowrip-
alan and Cusens, 1988). Monofilaments of
polyethylene and polypropylene have appli-
cations for ropes, and this part of the tech-
nology has been licensed for commercial
production. It has been shown that very stiff
and strong polyoxymethylene monofila-
ments, suitable for cables, can be produced
by combining die-drawing with a further
free tensile drawing stage.
 16.4 Die-Drawing 757

Oriented sheet products have been pro-

duced by drawing rectangular cross-section
billets, either through a fixed geometry slit
die or the nip of a pair of 65 mm diameter
steel rollers (Richardson et al., 1986). The
(a)
possible application of these products for
earth reinforcement has been explored. The
oriented sheets also show high toughness
and impact strengths comparable with fiber
reinforced composites. An additional fea-
ture is that the sheets can be post-formed in
a fairly wide temperature range below the
polymer melting point, without any signif-
icant changes in structure or properties.
The fracture toughness behavior of these
die-drawn sheets is remarkable in that the
fracture toughness for cracks traveling both
parallel and perpendicular to the draw direc-
tion are greater than for isotropic material,
provided that there is suitable selection of
the polymer grade (Tsui et al., 1992). This
(c)
unusual result appears to stem from both the
molecular structure (in terms of the chemi- Figure 16-11. Tooling configurations for die-draw-
ing tube: (a) drawing to reduced bore; (b) drawing to
cal composition of the polymer) and a sig-
constant bore; (c) drawing to increased bore.
nificant degree of biaxial orientation due to
drawing at constant width.
Some of the most useful potential appli- the die-drawn sheet described above as a
cations derive from the production of orient- biaxially oriented polymer with consequent
ed tubes, especially where there is a high improvements in hoop stress and long-term
degree of biaxial orientation, and substan- stress rupture behavior (Fig. 16-12) (Sel-
tial enhancement of hoop strengths. The wood et al., 1989) Following these results it
initial evaluation of die-drawn tube was was surmised that there would be consider-
undertaken using the batch process, and sev- able benefit to be gained by die-drawing
eral configurations were explored, as shown over a mandrel to a substantially increased
in Figs. 16-11 a, b and c. In the first config- diameter, as shown in Fig. 16-1 lc. More-
uration (Fig. 16-11 a) the initial tubular bil- over it was also appreciated that a continu-
let is drawn through a die of smaller bore ous die-drawing process would be advanta-
than the outside diameter of the billet. This geous in terms of commercial viability. The
is akin to the die-sinking process for metals prototype facility developed at Leeds Uni-
and has been used to encapsulate an optical versity is shown in Fig. 16-13 (Morath
fibre and to contain explosive powder. In et al., 1993). The extruded polymer tube is
Fig. 16-1 l b the tube is drawn at constant cooled in a cooling bath and drawn in the
bore over a mandrel with the same diame- die-drawing chamber between two caterpil-
ter as the inner diameter of the initial billet. lars. A mandrel is located in the centre of
This gives a similar product structurally to the die to expand the tube in the hoop orien-
758 16 New Processing Technologies

tation producing hoop orientation, while the can be produced, which have been devel-
axial haul-off produces axial extension and oped for the manufacture of transparent cans
axial orientation, i.e., a biaxially oriented for fruit packaging. The structure and prop-
products is obtained. As shown in Fig. erties of these tubes have been discussed in
16-12 in polyethylene the major improve- several publications (Taraiya and Ward,
ment in hoop stress is accompanied by the 1991; Selwood et al., 1988). The die-
anticipated improvement in long term stress drawing process has also been used to pro-
rupture behavior (Hansard et al., 1994). duce uniaxially and biaxially drawn tubes
Biaxially oriented tubes have also been pro- from polyphenylene sulphide and poly
duced, with concomitant enhancement of 4-methylpentene-l (Carretal., 1994).
hoop strengths and impact behavior in poly- In the case of polyethylene tubes it has
propylene and PVC. PET transparent tubes been shown that joining by electrofusion
can be successfully performed with no loss
of properties (Hansard et al., 1994). Butt
IU i i
fusion welding, used in the start-up of the
8 A # Expanded continuous process is also feasible and 40%
CO * Bore of the un welded strength of the oriented tube
Q_ A A
6_ AA
A
^^
A A Constant
- is retained, i.e., at least double that of iso-
tropic polymer.
ress

Isotropic Bore
CO \
4-
Q_
O
16.4.1 Mechanics
\
O
X of the Die-Drawing Process
-
i I i The mechanics of the die-drawing pro-
10" 1 10 103 10 5 cess have been analyzed for rod (Motashar
Time (h)
et al., 1993) and for tube (Craggs, 1990;
Figure 16-12. Stress rupture behavior of PE pipes at Kakadjian et al., 1996). The approach in all
80 C: A die drawn constant bore; die drawn biax-
ially oriented expanded bore; + expanded bore not cases was similar to that described for
yet failed (Ward, 1993). Steinkopff Verlag. Repro- hydrostatic extrusion, and starts by analyz-
duced by permission. ing the stresses in a small element of mate-

Mandrel Reheat Heavy Duty

Cooling
Restraint Chamber Caterpillar
Bath (2m) Tube
Cable (1.5m) Haul Off
Welder

Light Duty
Vacuum Caterpillar Conical Mandrel/Die
Calibrator Haul Off

->
Extruded Tube (12m) Biaxially
Drawn Tube
Figure 16-13. Continuous die drawing line for biaxially drawn tube. (Ward, 1993). Steinkopff Verlag. Repro-
duced by permission.
 16.4 Die-Drawing 759

50
Experimental (1=0-3
Theoretical \x=0 4

E^it
Theoretical |i_0-3
Theoretical u,=0-2 |J. U-U
40
Theoretical p.=01 20 1-
Theoretical u. =0-0

?ssure
Ql 10S^ s
30 /^

Die Wai
/ /

D
$20 10 20 30 40 50 60
Distance from Die Entrance (mm)

Figure 16-15. Die wall pressure distribution in poly-

propylene GSE-108 drawn at 90 C through a conical
10 die of 5 semi-angle, billet speed 0.4 mm/s (Motashar,
1993). Society of Plastics Engineers. Reproduced
by permission.

10 20 30 40 50 60 70
Distance from Die Entrance (mm)
Figure 16-14. Axial stress distribution in polypropy-
lene GSE-108 drawn at 90 C through a conical die of
5 semi-angle, billet speed 0.4 mm/s (Motashar,
1993). Society of Plastics Engineers. Reproduced
by permission.
rial in the die. An equation similar to
Eq. (16-10) above was obtained with
(16-12)
where ox is again the axial stress, D, is the
diameter of billet at the points, crf is the flow
stress and
(16-13)
This is slightly different from Eq.
(16-3), where the approximation that the
normal pressure is exactly oy meant that
B = 1 + \i cot a. Equation (16-12) was
derived on the assumption that ox - ay = af,
i.e., a simple Von Mises or Tresca yield cri-
terion.
It was shown in Motashar et al. (1993)
that for die-drawing hydrostatic pressure
effects are negligible. The strain and strain
rate at any point in the die can be obtained
from geometrical considerations, with rela-
tionships exactly analogous to Eqs. (16-7)
and (16-8) above.
As for hydrostatic extrusion, the axial
stress in the die was predicted by a numeri-
cal solution to Eq. (16-12). This was verified
by progressively cutting back the die exit
(giving a shorter die), and a typical compar-
ison of experiment and theory is shown in
Fig. 16-14. It can be seen that the experimen-
tal results are in excellent agreement with a
value of jU=0.1. The theoretical predictions
for the die wall pressure corresponding to
Fig. 16-14 are shown in Fig. 16-15. It can be
seen that this is always quite low compared
with the values of 200 MPa which can be
encountered in hydrostatic extrusion. Hence
there is good justification for ignoring the
influence of hydrostatic pressure on the yield
stress, another very valuable advantage of
the die-drawing process.
Motashar et al. (1993) also used a frozen
grid pattern, making a special billet split
along a diameter and scribing parallel grid
lines 2 mm apart perpendicular to the flow
760 16 New Processing Technologies
direction. It was found that these scribed
lines remained essentially straight through-
out the major part of the die, validating the
theoretical analysis which assumes plug
flow. The lines do, however, become pro-
gressively more curved towards the die exit
and at the exit a pronounced curvature is
observed. This is due partly to die friction
effects and partly due to changes in the mag-
nitude and direction of the velocity field,
i.e., redundant shear, as discussed in the
case of hydrostatic extrusion.
The mechanics of the die-drawing pro-
cess have also been analyzed for biaxially
oriented tube. Craggs (1990) developed the
force balance approach for this case also and
showed that for PET a satisfactory analysis
could be based on the Tresca yield criterion
using uniaxial stress-strain data for amor-
phous PET produced by Foster and Heap
(1957). A similar analysis has been under-
taken for biaxially oriented PVC tube
(Kakadjian et al., 1996). In this case the
biaxial deformation was modeled by the
Ogden equations for hyperelastic behavior,
which had been shown by Sweeney and
Ward (1993) to give a good representation
of stress-strain behavior of PVC at temper-
atures above the glass transition.
Finally, in a further analysis of the die-
drawing of rod, Kukereka, Craggs and Ward
(Kukereka et al., 1992) have taken into
account thermal effects due to the heat gen-
erated by plastic deformation. In the
absence of heat conduction the temperature
U>,<U)2
1cm
rises even for moderate haul-off velocities
(-10 mm/min for initial billet diameters of
40 mm) can be significant (10C), but
these are substantially reduced when heat
conduction is taken into account. Good
agreement was obtained between the theo-
retically predicted drawing stresses and
those determined experimentally for a range
of drawing speeds.
16.5 Roll-Drawing
A comparatively recent development has
been reported by Woodham and co-workers
(Burke et al., 1988) in Canada. This is roll-
drawing where a thick sheet of polymer
(typically 1 cm thick) is drawn between two
sets of heated rolls, as shown schematical-
ly in Fig. 16-16. The first set of rolls acts
essentially like a reducing slit die (akin to
die-drawing) although there is a slow rota-
tion to aid feeding the sheet through the nar-
row gap. The second set of rollers rotates
faster, with the ratio of the rotational speeds
of the two rollers determining the draw ratio.
The roll-draw process has been exemplified
with considerable success for polypropy-
lene, producing sheet with high axial mod-
uli. The moduli/reduction ratio plots look
very similar to those for tensile drawing,
hydrostatic extrusion and die-drawing (see
Fig. 16-10 b) and Young's moduli of 20 GPa
were reported for a reduction ratio of 20. A
third and fourth set of rollers, rotating at
Figure 16-16. Schematic diagram of the
roll-drawing process.

speeds equal to that of the second set, can
conveniently be introduced to prevent relax-
ation of the drawn polymer as it cools down
on leaving the second set of rollers in its
highly oriented state.
It appears from the account by Woodhams
and his colleagues that roll-drawing of PP
produced an essentially uniaxially oriented
product with no change in lateral stiffness.
Structural studies by Yang, Chaffey and
Vansco (Yang et al., 1994) showed that the
structure became fibrous at the higher draw
ratios, distinct fibers being visible in scan-
ning electron micrographs of fracture sur-
faces. The development of orientation in
these roll-drawn PP sheets has also been
studied by shear wave birefringence, the
results showing good agreement with opti-
cal birefringence measurements (Mloszew-
skietal., 1992).
In another study Kaito, Nakayama and
Kanetsuna (Kaito et al., 1987) produced
highly oriented sheets of PP and LPE by
roller drawing. The development of crystal-
line and amorphous orientation was then
determined using infrared dichroism and
visible-ultraviolet dichroism. It was shown
that the deviation from symmetric uniaxial
orientation was small, confirming the con-
clusions made previously by Woodhams and
his colleagues.
Other studies relevant to roll-drawing are
those of Wang and Porter (1991) on ultra
high molecular weight (UHMPE) reactor
powders processed by rolling and tensile
drawing to very high draw ratios (total draw
ratio 86) giving Young's moduli as high as
81 GPa. It is also interesting to recall the
work of Austin and co-workers (1982) who
used hydrostatic extrusion to make a biax-
ially oriented tube of PP, which was then slit,
laid flat and annealed. Magill and co-
workers (Magill et al., 1976) have also
explored the possibilities of rolling for the
production of oriented polymers.
16.7 References 761
16.6 Conclusions
In this chapter four techniques for the pro-
duction of oriented polymers in solid sec-
tion have been reviewed. It is now evident
that considerable enhancement of properties
can be achieved in polymers by orientation
in the solid phase. The techniques are still,
however, at the exploratory stage as far as
commercial developments are concerned. A
great deal of progress has been made con-
cerning the basic science, both in terms of
understanding the mechanics of the process,
and regarding the relationships between
properties and structure. Equivalent
progress is required in terms of practical
engineering if the full potential of the sci-
entific advances is to be realized.
16.7 References
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Phys. B20, 21.
Austin, A. R., Humphries, D. V., Fay, C. L. (1982),
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Barham, P. J., Arridge, R. G. C. (1977), J. Polym. Sci.,
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Briscoe, B. J., Tabor, D. (1978), Polymer Surfaces:
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Burke, P. E., Weatherly, G. C , Woodhams, R. T.
(1988), High Modulus Polymers: Zachariades, A.
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762 16 New Processing Technologies
Farrell, C. J., Keller, A. (1977), J. Mater. ScL 12, 966. Motashar, F. A., Unwin, A. P., Craggs, G., Ward, I. M.
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(1982), Polym. 23, 349.
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Leeds.
Gowripalan, N., Cusens, A. R. (1988), Constr. Build.
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Gupta, R., McCormick, P. G. (1980), J. Mater. Sci. 15,
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Hansard, S. A., Atkinson, J. R., Ward, I. M., Greig,
J. M. (1994), Plast. Rubber Process. AppL 22, 1.
He, T., Porter, R. S. (1987), Polymer 28, 946.
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Hoffmann, O., Sachs, G. (1953), Introduction to the
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Hope, P. S., Richardson, A., Ward, I. M. (1982),
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Leeds.
Kanamoto, T., Tsuruta, A., Tanaka, K., Takeda, M.,
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(1976), Toughness and Brittleness of Plastics
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Richardson, A., Parsons, B., Ward, I. M. (1986), Plast.
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Polym. Sci. 24, 1371.
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(1979), J. AppL Polym. ScL 24, 2137.
General Reading
Ciferri, A., Ward, I. M. (Eds.) (1979), Ultra High
Modulus Polymers. London: Applied Science
Publishers.
Inoue, N., Nishihara, M. (Eds.) (1985), Hydrostatic
Extrusion: Theory and Applications. London:
Applied Science Publishers.
Zachariades, A. E., Porter, R. S. (1988), High Mod-
ulus Polymers: Approaches to Design and Devel-
opment. New York: Marcel Dekker.