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Analysis of the α, β, And γ Relaxations in Polychlorotrifluoroethylene
Analysis of the α, β, And γ Relaxations in Polychlorotrifluoroethylene
Synopsis
Theoretical models for the mC and y c relaxat,ion effects found in chain-folded polymer
crystals (single crystal mats and bulk) are presented and compared with the available
dielectric and mechanical loss data for polyethylene and polychlorotrifluoroethylene.
Details of morphology and crystal structure that can be varied by crystallization and
annealing procedures, e.g., roughness of chain-folded surfaces, number of intercrystalline
links and cilia, number of chain-end defects and dislocations, and the existence of the
extended-chain phase, are brought into the discussion. The m C process, which consists
of two overlapping mechanisms, is a result of motions of chain folds and reorientation
(with translation) of chains in the interior. (Chain twisting also occurs for long chains.)
The theory connects the data on the n-paraffins and their polar derivatives (n-ketones,
esters, ethers) with the results on polymers: the common feature is the chain reorientation and twisting process. A new theory of chain twisting is introduced. The y e
relaxation is a result of reorientation of chains in a loose chain-end induced defect,
(a vacancy row) in the polymer crystal. When the effect of chain twisting is included,
the theory successfully predicts the unusually broad and asymmetric loss curve found
in the polymer, and is consistent with the experimental activation energies. The fl
relaxation arising in the amorphous component of PCTFE is analyzed, and its upward
shift in temperature with increasing crystallinity discussed in terms of the Adam-Gibbs
theory of relaxation in the glassy state. The y a amorphous relaxation, and the 6 relaxation which is found at cryogenic temperatures, are also discussed.
I. INTRODUCTION
Considerable scientific and technological interest attaches to the understanding and manipulation of the physical properties of the class of semicrystalline polymers that consist of inherently crystallizable linear flexible
chains. Polychlorotrifluoroethylene (PCTFE) and polyethylene are
typical members of this class. Our principal objective is to describe the
various manifestations of the a, p, and y relaxation processes in these
polymers, and t o discuss the underlying mechanisms. I n the course of
classifying the loss mechanisms, certain very low temperature (or extremely
high frequency) processes were noted which were clearly not associated
with the a, p, or y effects. These effects are called 6 relaxations and are
discussed briefly a t the end of the paper.
173
174
a, p,
AND
RELAXATIONS
175
I n both PCTFE and polyethylene, samples with a similar degree of crystallinity can sometimes lead to quite dissimilar experimcntal results. Also,
the magnitude and location of the relaxation processes often depend strongly
on the degree of crystallinity. These effects are especially prominent in
PCTFE. These facts place a premium on giving a full disclosure of the
methods of preparation of the samples. The causes of these effects are
interpreted in terms of recent theories of morphology and molecular chain
folding in the case of those relaxations arising in the crystalline phase or
its surface, and in terms of recent theories of the glassy state in the cast
of relaxations arising in the amorphous component.
0.73
up to -200C.
x = 0.80
up to --200"C.
0.73
Specimen 0.44 annealed two
(quench-crystallized
weeks a t 190C
and annealed)
0.80
(isothermally
crystallized)
0.44
up t.o 120C.
0.44
Disk 2 mm. thick heated to
(quench-crystallized) 250C. aiid plunged in ice wat.et
0.12
up to -60C.
0.00
0 . 0 (liquid polymer)
0.12
Film 0.15 mm. thick heated to
(quench-crystallized) 250C. aiid plimged in ice water
Degree of
crystallinity
Method of preparation
Specimen
designation
Type of crystals
Remarks
Specific T , ("C.)
volume from
a t 23"C., 7-T
cm.3/g. data.
TABLE I
PCTFE Specimens
a, p,
AND
KELAXATIONS
177
1.0
.8
.6
X.
.4
.2
.O
TEMPERATURE, OC
(6)
Fig. 1. ( a ) Degree of crystallinity (x)and ( b ) specific volume (P) a s a fuiictioii of temperature for PCTFE specimens. (Data of Scott and co-workers.')
v-5"
178
A. Bulk Polymer Isothermally Crystallized at Low to Moderate Supercooling after Cooling from the Melt (Isothermally Crystallized)
PCTFE specimen 0.80 was crystallized in this manner.
Linear polymers consisting of intrinsically crystallizable units usually
form typical lamellar spherulites when crystallized at low to moderate
supercooling. PCTFE is entirely typical in this r e ~ p e c t . ~ Each
J
spherulite starts at a heterogeneity. The spherulite consists of a set of platelike
lamellae that radiate outward from the heterogeneity. As revealed by
electron m i ~ r o s c o p yand
~ ~ ~low-angle x-ray diffraction,6s8the lamellae in
PCTFE are about 300-800 A. thick, depending on the crystallization
temperature and annealing time with higher crystallization temperatures
and longer annealing leading to thicker lamellae. It is now commonly accepted that the lamellae are basically chain-folded structures, with a fairly
high occurrence of regular folds with adjacent re-entry (see Fig. 2). The
general appearance of the lamellae, including their resemblance to single
crystals, can be explained in terms of the chain-fold model6 Thus, the
basic morphological unit in a spherulite of this type is a chain-folded lamella.
However, this description does not, by any means, encompass all that is
important to dielectric and mechanical behavior in such specimens. The
somewhat idealized kinetic theory of chain folding originally given by
Lauritzen and Hoff man6*9s10
is capable of explaining the existence of chainfolded lamellae in bulk and allows the prediction of the growth rate and
initial lamellar thickness, Zg*. Also, the melting behavior can be explained
after lamellar thickening is tasken into account.6pll This theory in essence is an approximation that applies at low supercooling, where chain
folding with adjacent re-entry is predominant and the fold surface relatively smooth.
More recent developments of the kinetic nucleation theory by Frank and
Tosi,12Price,13and especially Lauritzen et al.14clearly show that one must
expect a spectrum of behavior depending on the supercooling. For
crystals formed at low supercooling, the fold surfacc as initially formed is
relatively smooth, a root-mean-square deviation of 8-12 A. being typi~a1.l~
As the crystallization is carried out at higher supercoolings, the surface as
originally laid down becomes substantially rougher, leading to loose or
looplike folds (still with mostly adjacent re-entry). This effect is especially clear from the work of Price13 and Lauritzen et al.14 At a very
high supercooling, in the simplest approximation approaching AT, =
2aTmo/Ahfb0,the fold period becomes ill defined and the crystals produced
AND
a, p,
RELAXATIONS
I A. .QUENCH CRYSTALLIZED
b
,
179
(0.12. 0.44)
'ROW
VACANCIES
\NUMEROUS
AMORPHOUS
LINKING CHAINS
CHAIN-FOLDED
STRAINED
SURFACES
INTERLAMELLAR
C.
ROW VACANCY
DEFECT^^
ISOTHERMALLY
NEAR T i (0.80)
CRYSTALLIZED
INTERLAMELLAR
/L!NK
CHAIN-FOLDED LAMELLA
REJECTED LOW
M.W. MATERIAL.
Fig. 2. Fine structure of bulk samples of PCTFE prepared under different Grystalliaatioii
conditions (schematic).
will have extremely rough surfaces with loop-type folds (CJ is the lateral
surface free energy, Tm0the equilibrium melting temperature, Ah, the heat
of fusion, and bo the lateral lattice spacing). A t T,, which is Tmo- AT,,
every polymer segment that strikes a surface sticks to it, giving virtually
no regular folds a t all. Here the supercooled liquid simply collapses into a
highly disorganized mass of microcrystallites. The implication that these
microcrystallites are connected to one another on a massive scale by intercrystalline links is clear. When calculated without approximations, the
original theory of Lauritzen and Hoffman gives the nucleation collapse a t
YC.l5 The value of A T , for PCTFE is about 8O"C., i.e., T , is a t about 14OoC.
It is important to bear in mind that the ltinetic nucleation theory of chairifolded growth leads to a wide range of surface roughness and fold regularity
depending on the supercooling.
Returning to the morphology typical of bulk polymer crystallized a t low
to moderate supercooling, it must be noted that recent evidence obtained by
AndersonI6 and Keith and Paddenl7slgmakes it clear that only molecules
exceeding a certain length undergo chain folding: the shorter molecules in
180
a, p,
AND
RELAXATIONS
181
specimens 0.12 and 0.44. Most of the crystallization occurs near thc
growth rate ma.ximum which is usu lly a t about 0.87 Tmo,i.e., roughly
midway between Tmoand T,.6 Sp cimen 0.44 has a higher degree of
crystallinity (and larger crystals) t h n specimen 0.12 because the greater
thickness of specimen 0.44 allowed a longer residence time in the temperature region of maximum growth rate. (The interior of a very thick specimen of P CT FE would resemble specimen 0.80.) I n some polymers, notably polyethylene, the crystallization kinetics are such that it is not possible to obtain specimens of ordinary molecular weight with a crystallinity
as low as 0.12 or 0.44 even by quenching thin films.
According to thc kinetic nucleation theory of chain-folding mentioncd
above, we must expect rather rough surfaces with somewhat looplike folds
in the small crystallites in quenched specimens (Fig. 2). Furthermore,
bccause of multiple nucleation acts, and the large number of crystallites, a
considerable number of the molecules must participate in more than one
crystallite. It is of considerable significance that this picture, which
resembles in one important respect (numerous intercrystalline links) the
classical frin ged-micelle model, is relevant under conditions of very high
supercooling, i.e., crystallization very far from equilibrium conditions,
whereas early attempts to justify this sort of model wcre based on equilibrium theories
The crystalline component in 0.12 and 0.44 samples does not increase
significantly if the specimens are stored near or below T,. Increase in
crystallinity and the formation of larger crystals would require two conditions to bc met: (1) chain motions in the amorphous component would
have to become rapid enough to allow transport to the growing crystal face
and (6)some interchain cntanglcinents in the interlamellar links would have
to bc resolved either by allowing chain motions in the crystallites or by
melting some of the crystallites. These conditions arc met in ICTFE by
annealing a t about 190C. (specimen 0.73).
C. Bulk Polymer Crystallized by Rapid Quenching From Melt and Annealed near Melting Point (Quench Crystallized and Annealed)
1CTFE specimen 0.73 falls in this category.
The crystallites in this specimen are still small, though thc incrcascd
optical scattering indicates that they arc larger than those in 0.44. Some
of the amorphous material has been incorporatcd in the crystallites, but thc
slowness of the crystallization at 190C. (compared to specimen 0.80 a t the
same temperature) clearly implies that retardations due to chain entanglements in interlanicllar links in the amorphous regions hinder the crystallization. The hypothesis that the annealing process (i.c., conversion of
specimen 0.44 t o 0.73) has caused a number of the interlameIlar links to be
drawn rather tight is advanced. Dielectric data to be given later support
this hypothesis. A fair number of the folds are probably looplike. The
crystallites in specimens of this type melt out if heated above about 200210C., and subsequent isothermal crystallization a t 170-190C. yields
a specimen similar to 0.80.
182
111. PLOTS OF
a, p ,
AND
RELAXMTONS
183
A. AMORPHOUS STATE
d '
'
0.2
I
'
0.4
I
"
0.6' To
0.8
I
'
'
1.0
B. SEMICRYSTALLINE POLYMER
-HIGH
X, ISOTHERMAL
0.2
0.4
0.6
0.8
!-
8
J
a:
w
n
a,
._...
0
0.2
0.4
0.6
0.8
1.0
REDUCED TEMPERATURE, T / G
Fig. 3. Dielectric or mechanical loss factor a t 1 Hz. versus reduced kmperature T/T,"
for a linear polymer with no independently rotatable side groups (schematic).
184,
.00
.07
PCTFE
.06
.05
.04
.03
02
.01
0
I.4
DEGREE OF
CRYSTALLINITY
I Hz
100
50
150
2 0
TEMPERATURE , C
(bJ
Fig. 4. ( a ) e versus temperature at 1 IIz. for PCTFE specimens 0.12, 0.44,0.73, and
0 3 0 . (Data of Scott et al.1) ( b ) T Tan 6 versus temperature a t 1 H z . for PCTFE
specimens 0.27, 0.42, and 0.80. (Data of M c C r ~ i r n . ~ ~ )
IV. THE
a,
RELAXATION PROCESS
A. Preliminary Considerations
I n PCTFE, the a, process gives a loss peak a t 1 Hz. a t about 150C. or
0.855 Tmo(Fig. 4). It appears in clearly resolved form in the dielectric
data only in specimen 0.80, which contains large chain-folded lamellae in
typical spherulitic structures. Note also that the mechanical loss data of
l \ I ~ C r u mshow
~ ~ a resolved a, peak onlyfor specimen 0.80, and Crissman and
PassagliaZ4indicate a resolved a, peak for their isothermally crystallized
specimen. Dielectric specimen 0.73, which contains only very small and
probably disordered crystals, shows no resolved peak at 150C. (The peak
a t about 125C. in speciinen 0.73 can definitely be shown to belong mostly t o
the 0class since it has a strongly temperature-dependent activation energy.)
While it is evident that the resolved a, peak in PCTFE is associated with
the crystalline phase, i t does not appear to be entirely a property of the
interior of the crystal. It was therefore concluded by Scott and coworkers
that the molecular mechanism leading to the a, peak in PCTFE probably
arose mostly in the chain-folded surfaces of the 1amellae.l
Recently, S i n n ~ t has
t ~ ~convincingly demonstrated in the case of polyethylene single crystals that one of the two main a, mechanical relaxation
processes that appears in such crystals is associated with the chain-folded
surfaces. On annealing, the single crystals irreversibly thicken, with a corresponding decrease in the number of folds. At the same time the intensity
of the a, relaxation process observed by Sinnott falls. Other authors have
also suggested that the a, process involves the crystal surface^.^^^^^ Sinnott has also shown that as the chain-folded lamellae thicken, the teniperature T,,, corresponding to the maximum in a loss versus T plot for the a,
process shifts to higher temperatures. This means that thickening of the
lamellae leads to higher activation energies and increased relaxation times
a t a given temperature. Taliayanagi and co-worliersZ8have shown that
the a, process of single crystals of polyethylene as measured with frequencies near 1 Hz. actually consists of two superposed processes of different activation energy. (The discussion of Wada et aLZ9and Iwanagi
and Nalranc30on bulk polyethylene suggests that two a, processes, called a
and a', are superposed in mechanical dispersion data a t 1Hz.) Accordingly
we have investigated a class of models which will lead to a decreased absorption with increasing thickness, an increase of T,,, with increasing
thickness, and either one or two relaxation processes in the a, region.
It is of interest to show the a, process on an E" versus logfplot for PCTFE
and obtain the activation energy. The a, dielectric process is readily
discerned in PCTFE in specimen 0.80 in a plot of 6' versus logs between 150
and 190C. This is shown in Figure 5 . The intensity of the ac process is
quite low, especially in relation t o the y process. The activation energy
of the a, process may be calculated by identifying the frequency frnax at the
maximum in the 2' versus log j plot and computing the activation energy as
186
AH*
- R b h fmex/b(l/T)
(1)
LOG,, FREQUENCY, Hr
Fig. 5 .
a, 6,
AND
RELAXATIONS
187
Fig. 6. Log finax versus 1/2 for various PCTFE specimens. (Data of Scott and coworkers.)
probably involves both. The models that we propose below have this
feature.
We proceed by discussing the high-activation energy modes of motion
possible in a chain-folded single crystal of a polyiner such as polyethylene
or PCTFE. I n the first model considered, a, - A, the chain-fold motion is
coupled to motions within the crystal interior. Next, the high activation
energy process that corresponds t o reorientation of a paraffin molecule in
a defect region in the prerottltor state is given, and extended t o the case
of long chain lengths by using a new theory of chain twisting (model ac - B).
With suitable modification, this model is applicable to the case of extendedchain crystals in a bulk polymer. Finally, in modcl a, - C, it is assumed that
the folds act independently of the crystal interior, leading to the relaxations
in a single crystal being represented by model a, - Cf for the folds and
a, - C, for the chains in the interior.
188
;:
and
w~~ = A I e -AQA*(n)/kT
(3)
where A&** and V are taken to be free energies. The dipole moment p i
associated with the fold changes its angle with respect to the x axis from
Of(,) to e,(,, as the dipole jumps from site 1 to site 2. An essential feature
of the model is the assumption that as the fold jumps from site 1 to site 2,
some turning of the chain in the interior of the crystal (accompanied by
some chain translation) is required to attain the activated state. The chain
fold is thus assumed to be coupled to the chains in the interior part of the
crystal. If the fold has extra links in it, the turning of a chain in the interior of the crystal would not be required to allow reorientation of the
fold. If, on the other hand, the fold is a sharp one of minimum contour
length, it will be coupled to the interior. We envision that in turning the
fold to the activated state, the interior chain is translated along the x axis.
SITE I
7
CHAIN FOLD IN
STATE
01 c -
7-
a,
6, AND
1/[2(W,l
e A Q ~ * ( n/ )k T
RELAXATIONS
w121
/[~A(I
(1/A) e
189
+ e-PkT) J
(4)
AQA*(n)/kT
kT
ASA*(n)/keAHA*(n)/
(5)
CI,-B,and
ac - =c
component o f
twisting
C2,-Cc(M)
or chain
/ / component of a;A(M)
or
(0)
(same
rn)
rigid
71I
ac-A,(Yc-Cc
biqh t&
LOG n
(dl
lbl
Fig. 8. Behavior of models aC- A, a - B, and 0 1 ~ - C (schematic).
The use of the rigid-rod approximation at short and moderate chain lengths will be theoretically justified
in Section IV-D and experimentally justified in Section IV-F.
The rigid-rod approximation leads to
AH,*(n)
AHw*
+nAHm*
(6)
+ nASCH2*
(7 1
for the entropy of activation. This gives a free energy of activation that
is a linear function of n:
ASA*(n)
Asfold*
190
AQ,*(n)
Thus, from eqs. (4) or (5) and eq. ( 8 ) )we expect that to the degree that
the rigid-rod approximation holds, a plot of log T as a function of n at a
constant temperature should rise linearly with increasing n (Fig. 8a).
Data showing that eqs. (6), (7), and ( 8 ) )which depend on this approximation, are valid up to surprisingly high values of n will be given subsequently.
We now investigate the behavior of T,,, as a function of n, where T,,,
is the temperature a t which a loss peak occurs in a plot of loss versus T
a t a fixed measuring frequency fm, where 2rfinrm = 1. We now have
from eqs. (5-8):
In T,
In (l/A)
(AHfold*
4-nAHcH,*)
- (ASM"
+ nAScH,*)
R
R T,,,
(9)
or
T,,,
TO(OC,
- A ) [(a
+ n ) / ( b+ n)l
(10)
where
To(a, - A )
AHcH~*/ASCH%*
(11)
a),and
AH~.I~*/AHcH~*
(12)
[R In (AT,) A S r o ~ d * ] / A S ~ ~ z *
(13)
Equation (10) gives a value of T,,, that rises rapidly for small n, and
then levels off to To(a, - A ) as n gets larger (Fig. 8b). This behavior is
a direct result of the assumption that AHA*(n) and AS,*(n) are linear in n,
i.e., the rigid-rod approximation.
If the elementary process is correctly identified, we must expect 2A' = A
to be roughly 10g-1013 events/sec. These estimates are based on the
activated state being (a)a vibrator, with one degree of freedom of vibration
(I/IcT)~" lo9,where 1 is
replaced by one degree of rotation, so that A
the moment of inertia, or ( b ) a vibrator with one degree of vibration being
replaced by translation, giving A
kT/h S
The orientational polarizability (Y is related to the static dielectric
,
the relation
perinittivity, E ~ by
b
es - E ,
E4an(~
(14)
where n is the number of active dipolar units per cubic centimeter and
the high-frequency dielectric permittivity. The quantity [ is
E,
for the Onsager internal field, and may be regarded as essentially constant
for most simple calculations; for E , = 2, [ is 16/9 if es = 2 and 24/9 if
a, p,
AND
RELAXATIONS
191
es = a. For convenience we call the magnitude of the dipolar absorption I,, and define it as the area under a loss peak in an e" versus log .f plot:
I,
J0
e"d l n f
(7r/2)(ts -
em) =
2[7r2na
Thus, the magnitude of the dipolar absorption is for all practical purposes
directly proportional to na, and henceforth we concentrate on calculating
this quantity.
The methods used to calculate na for various types of "site" models have
been detailed elsewhere.37 I n the present case we first quote a simplified
result for the ae - A model that is applicable to dielectric measurements
carried out with the applied electric field in the x direction (Fig. 7). This
corresponds to the manner in which dielectric measurements would often
be carried out on mats of single crystal platelets. The weighted orientatiorial polariaability resolved in the x direction is39
where
p,
Mzu(fold)
192
For the case Aip = 0, I,, varies as 1/Z (Fig. 8c) just as does naz. We
note also t hat if the interior chain of length Z contains but one dipolar
unit, then I,, again varies as 1/1 or l/n. The case where each chain unit
has a dipole moment pl leads to pc2 = ( n p ~ )which
~,
givcs a contribution
to I , from the interior that varies as n (not shown). The case for a dipolar
chain with a helical arrangement of dipoles gives I,, a 1/Z when Z is considerably larger than the helix repeat distance.
The behavior of I p with I is shown in Figure 8c. The variation of I,,
with temperature for two extreme cases of V is shown schematically in
Figure 8d.
I n the simple form presented hcre, the ac- A model produces only a single
dielectric relaxation time. The introduction of a distribution of Z values,
representing chain-folded crystals of different thicknesses, would introduce
a distribixtion of T through eq. (4). Similarly, a distribution of relaxation
times arises naturally when a model with three or more equilibrium orientations is ~ o n s i d e r e d . ~ ~However,
-~~
we have chosen not to complicate the
model presented for the ae - A relaxation, especially in view of the fact that
the observed distribution is not particularly broad (see later). The
situation is quite different in the case of the yc process, which exhibits a
very broad and asymmetric loss peak on an E versus log f plot that mci-its
special consideration.
It is of interest to indicate certain factors relating to the magnitude of
the mechanical absorption. In the case where the mechanical absorption
is weak, i.e., the change of modulus small, the magnitude of the loss will
vary as the number of relaxing elements per unit volume times the
ecVliT)
exp { -V/lcT} (see
factor C1C2/N2 = exp { -V/lcT}/(l
Appendix). Thus, the folds will contribute as (C1C2/N2)[lf/(Zf
Z)] and
the interior will contribute as (C1C2/N2)[Z/Zf
1) J C C l C 2 / N 2as depicted in
Figure 8c. If the interior chain reverts to its original position as the fold
jumps from site 1 to site 2, the interior will be mechanically inactive. Also,
if the crystal symmetry is such that XI - Xz = 0 for a particular stress field
acting on a site model, the overall process will be mechanically inactive (see
Appendix). The factor governing the magnitude of the mechanical relaxation given above is to be multiplied by (hl - hz)2/kT as noted in thc
Appendix.
LY,
p, A N D
1XELhXA'rlONS
193
ifi
LL
a
W
SITE
- _ _----
aC -
1/[2(w,z
021)]
Fs
(l/A)eAQ=*(n)'KT
AHs*(n) - TAXs*(n)
(19)
194
A H B * ( ~ ) = 2AHeg*
and
AS,*(n)
2ASeg*
+ (n - ~ ) A H c H % *
(20)
+ (n - ~ ) A S C H ~ *
(21)
Here AH,,* and AXeg* represent end-group effects. For a given crystal
structure, we anticipate that AHcH,* and ASCH, *for the ac - B mechanism
will be similar to those for the ac - A mechanism.
It is immediately seen that In 7 is a linear function of n at a fixed temperature:
In
7 =
-In A
+ 2[(AH,,*
- TAS,,*)
- (AHcHz* - TASCH,")]
t1 simple calculation then gives
T,,
To(aC- B) [(a'
+ n(AHcHz* - TASCH,")
(22)
+ n)/(b' + n)l
(23)
where
T
a'
6'
~ - (B) ~= AHCH,*/AXCH,*
~
(24)
2(AHeg* - AHCH~*)/AHCH,*
(25)
+ 2(ASeg* - ASCH,*)/ASCH,*
R In (Arm)
(26)
The dominance of the R In A r, term should lead 6 and b' in eqs. (10) and
(23), respectively, to be rather similar. Moreover, the values of To are
identical for a, - A and aC- B. Hence the differenccs that occur arc a
result of differences in AQfo~d*and A&,,*.
The weighted orientational polarizability for the ac - B model for he
case where site 1 and site 2 are 180" opposed is given by
where J4w(r)is the molecular weight of the repeat unit, p, is the total
(resolved) dipole moment associated with a given chain, and x d the mass
fraction of short "defect" chains of the type shown in Figure 9. Herc
C,C2/N2is exp { - E / k T ] / ( I
exp { -E / k T f ) . 2 Theinodelexplicitly implies that the strength of the ac - B relaxation in a single crystal of high
purity would be very small, since X , -+ 0 in such a case. A similar remark
applies to the strength of the mechanical relaxation, the intensity of which
is proportional to (ClC2/N2)Xd,multiplied by the usual factor (A, - Xe)2/lcT
(see Appendix).
The distribution of relaxation times can arise from the distribution in
I and from the presence of more than two orientational sites.
D. Chain Twisting
The rigid-rod approximation cannot remain exact for very long chains.
For sufficiently long chains, one would expect the rotation of one end to
leave the other end unaffected. This will lead log r and T,, to fall
01,
6, AND
RELAXATIONS
195
/RIGID ROD
I
UP
TO
Fig. 10. Departure from rigid rod behavior resulting from chain twisting for sin2 'p
potential (upper curve) and the parabolic potential (lower curve).
below the rigid rod curves a t large values of n or I, and approach an asymptote (Figs. 8a and 8b).
F r O h l i ~ hhas
~ ~given an approximate treatment of chain twisting based
on the assumption that the two potential wells in a two-site model are
parabolic with a cusplike barrier of magnitude AQcH,* between them.
This calculation, when revised to deal with the present situation in model
ac- A and ac- B40leads to AQl*(n) = AQl*
2%AQcH2* tanh (n/2%) where
we regard the AQ% to be free energies of activation. AQl* is 2AQ,,* for
ae - B and &fold* for the ac - A model. a is a chain twisting parameter,
f i = 4 A 2 / A Q o , * (7r/2), where A Zis the chain twisting force constant.33
For values of n considerably less than 2n the rigid-rod approximation is
approached, and when n exceeds 2n, the function 2nAQcH,* tanh (n/2%)
approaches the limiting value Z%AQCH~*(Fig. 10). The model is somewhat
crude, especially in that the barrier between the two sites is a cusp formed
by the intersection of two parabolas (Fig. 10).
A potential barrier of the form U(cp) = Qmax* sin2 cp for a two-position
model seems physically more realistic. Williams and Lauritzen40 have
shown that this leads to
AQ*(n) ==
Z ~ Z A Q ~[ ~
~ E
~ (cos
*I po) - sin2 cp0& (cos p0)] (28a)
Here El (cos cpo) is the complete elliptical integral of the second kind,
&'i (cos po) is the complete elliptical integral of the first kind, defined as
follows:
196
Ez(cos cpo)
(2W
ARi*
+ 2?12ARcl1,* [ ~ ( E&)I
I,
(29)
where aHl*is AHf,,ld* for ae - A and 2AHe,* for ac - B. The heat of activation increases linearly for values of n up to ~ mand
, then tends to level
off. The limiting value for very large n is
AH,,
*(rL) =
AH,* f ~!???AHcH['
a , p,
AND
RELAXATIONS
197
where a = a', b = b', and To are the same as defined for aC- A and ac- B.
Assuming @t is of the order of 20-40, TE",,,,
will increase in accord with the
rigid-rod approximation results up to n = 60-120 and then bend off
with a further increase of n somewhat more rapidly than is predicted by the
rigid-rod approximation (Fig. 8b).
The effect of twisting will be more obvious in plots of I n T against 22,
or in plots of the observed activation energy against n. These plots will
be linear as long as the rigid-rod approximation is valid, but will show a
distinct leveling off when this approximation fails (Fig. 10). Note in
is independent of frL for the rigid-rod approximaFigure 8b that (T,,,),,
tion. However, in the case with chain twisting, (Tmax),+,, depends on
j,n even for a fixed m.
a,- c,
%- c c
Fig. 11. hlotlel for process
aC- C
198
where AHc,* and AScf* are the heat and entropy of activation for the wZ1
transition. These quantities are independent of the length of the chain in
the crystal interior. The above expression leads to
T,,,
AHc,*/(R In AT,
+ ASc,*)
(32)
where the symbols have the same meaning as those discussed under eq. (IS).
This gives a contribution to I , for the whole crystal that varies as 1/Z
(Fig. 8c). The mechanical absorption intensity will vary as (C1C2/N2).
[Zf/(Z
Zf)] (XI - X2)2/lcT. The mechanical manifestation of the aC- C j
relaxation will probably be activated by a shearing motion of one chainfolded lamella with respect to another, which thereby biases the equilibrium
distribution of the folds.
Model 01, - C, (Interior Chain Contribution). I n the case where the folds
have extra links in them, the chains in the interior of the crystal should be
able at least to a limited extent to undergo the translation-rotational
motion discussed in model a, - A and ac - B. This gives in the rigid rod
approximation
T,,,
To(o~c,)[(a
+ n)/(b+ n)l
(34)
where TO(CUC,)
= AHcH~*/AXCI~~*,
a = 2(AH,,* - AHcH~*)/AHcH~*and
b = [R In AT,
2 (AXeg* - AXCH~*)]/ASCH,*. Thus, the In r and
I,,, relationships for ac - A, ac - B, and 0 1 ~- C, depend on n in a similar
manner. By extension of arguments given earlier, we expect a % a % a
and b b
b. The activation energy for the rigid rod approximation is
given by an expression analogous to eq. (6), and with chain twisting it is
given by eq. (29).
The dipolar contribution of ac - C, for two sites 180 opposed is
where the symbols have the same meaning as in eq. (27), except that X C ,
is now the mass fraction of interior chains associated with folds that have
extra links on both ends. The absorption intensity of mechanical relaxation will behave in a manner that is essentially independent of I (Fig. 8c),
i.e., the 0 1 ~- C, effect will act as a bulk contribution.
a, P,
AND
RELAXATIONS
199
If the folded surface is rather rough, then X C ,will be high, and a rather
strong absorption may be expected compared to the ac - B relaxation in
relatively pure n-paraffins, where X , will be small.
The essential difference between model ac - A, which has thc folds
intimately connected to the crystal interior, and model ac - C which has
loose folds that are disconnected from the interior, is that olC - A exhibits
one relaxation time, while the model with independent folds leads to two
relaxation effects, a, - C, (independent motion of loose folds) and ac - C,
(independent rotation of chains in interior).
If a single crystal behaves according to ac - A, it will show one 1osb
maximum in the ae region. Two loss effects, ac - C, arid a, - C,, will
- C representation with
appear in single crystals in the ac region if the aYc
loose folds is correct. A bulk polymer with extended-chain and chainfolded crystals will exhibit two loss effects in the ac region ( a c - A and
ac - B) if the chain folds are connected to the crystal interior, and three
loss effects ( a , - C,, aC- C,, and a, - B) if the chain folds are loose.
The ac - B contribution in each case is due to the extended-chain phase.
The differences in models a, - A, aC - B, and ac - C, arise from differences in AH^^* and ASeg* (or nHfold*and Asfold*) in the various cases.
200
n
3
10
30
100
300
(a,-8)
(CG-Cc)
1000
+ (a5-C,)
u)
20
3
.
0
LOG,, n
Fig. 12. The temperature of maximum loss a t 1 Hz. plotted against log n ( a cprocesses). Mechanical: (h) single crystal mats polyethylenez5; ( X ) bulk linear polyethylene66; (m) n - p a r a f f i n ~ . Dielectric:
~~
(a)Esters43; (As)ethers43; ( 0 )and (A) solidsolutions of ketones and ethers, respectively, in n - ~ a r a f i n s ~(
~9
; solid
) solutions of ethers in
low density p ~ l y e t h y l e n e ~(~6; ) and ( 9 ) oxidized bulk polyethylene and single crystal
mat polyethylene respectively.26 The upper calculated curve (-)
corresponds to the
relation T
, = 342 (0 n]/[14.5 n ] . The dashed lines (R = 40 and R = 30)
falling off this curve correspond to the modification of this rigid-rod approximation to
include chain twisting. Similarly, the lower calculated curve (-.-)
corresponds to
T,,, = 333 [2 n] /[18 n] and the lines 6 = 40 and % = 30 take into account twisting of the chains.
hibit this effect. The hexagonal phasc above the first-order transition is
called the rotator, phase, and the phase below the transition is called the
prerotator p h a ~ e . ~ The
, ~ ~rotational phase transition is an equilibrium
effect in a pure material, just like the melting point. The chain rotation
effects discussed here all refer to the prerotator state, and are connected
with the presence of short-chain impurities as noted. The rotational
transition occurs even in extremely pure materials, and the hindered
molecular rotation in the solid state above the transition temperature is
not dependent on the presence of chain impurities. The relaxation
time in the rotator state is in general much shorter than in the prerotator
state. Short-chain impurities will induce the rotator state in materials
such as n-Cl8HS which would not otherwise exhibit it, but at the low
temperatures where the
process is observed at 1 Hz., there is no possibility for a rotator phase contribution.
The extensive dielectric data of Meakins43 on symmetrical n-ethers,
n esters, and solid solutions of ketones in n-paraffins show that AH* for
01,
p, AND
RELAXATIONS
201
ESTERS
ETHERS
KETONES
(SOLID
SOLUTIONS)
(a1
Pyy/i
0
--
KETONES
SOLUTIONS)
*I 15
a
10
10
20
30
40
( b)
-C-
202
where To = 333, a' = 2 and b' = 18. The fit is shown in Figure 12. The
fit shows again the validity of the rigid-rod approximation at the chain
lengths given (n = 7 to n = 25). A very good fit can also be obtained
with To = 342K.) a' = 0, and b' = 14.5 (Fig. 12).
It is of interest to obtain an estimate of AHCH2*, ASCH,*and A from the
is 700 f 50
data. llleakins' plots of AH* against n indicate that AHcH~*
cal./CH2 for the ketone-paraffin solid solutions, esters, and ethers. This
value should hold approximately-say, within 20 or 30%-for the n-paraffins. Combining this with To = AHcH2*/AScH2*= 333K. for the nparafflns gives ASCH?" = 2.1 e.u./CHn. Then noting that at 1 Hz. that
b = 18 = ( R In A
AS,*)/AScH2* and letting AS,,' = 0 it is found that
A = 2 X lo8 events/sec., which compares favorably with the theoretical
estimates. The experimental value of A from the entropy data is 3 X
109 (Fig. 13). An alternative calculation of AXcH2*may be made from
the experimental result b = 18 by assuming values of A. If A is lo9,
~ S c I T 2is*2.4 e.u./CHz and if A is
AScF12*is 2.9 e.u./CH2. Somewhat
smaller values of ASCH," are found if b = 14.5 is used in the analysis.
The free energy of activation per CH2 group, A&cII~*
= AHcH~*- TAS~H,",
is 280 cal./CHz at 200K. and 70 cal./CHz at 300K. These figures will
be used subsequently to estimate %.
The above estimates of AHcH2*,AScH2*,To,and A must be regarded as
approximate. They are given mainly to give a rough idea of magnitude of
the parameters involved in the ac - B process. The assumptions involved
in comparing dielectric and mechanical loss T,,, data are minimized in the
treatment, but such factors as subtle differences in the crystal structure
of the substances treated could cause errors in the actual values obtained.
Nevertheless, it is clear that the rigid-rod approximation used in a, - B
holds quite well up to at least n
37, and that this approximation is
consistent with the T,, data for chains up to this length. Furthermore,
our assumption that AQ*(n) must be broken up into linear AH*(n) and
AS*(n) terms is justified. The T,,,, data can be fit using this assumption,
but cannot be fit using the concept that AQ*(n) contains a AH*(n) term
linear in n and only a constant AS* term. In any event, the latter assumption is not justified by Meakins' AX*(n) results, and its use leads to a
T,,, value that rises linearly with n, which is contrary to the experimental
results of both Illers and Meakins.
I n a more ideal situation, activation energies of the various short nparafins would be available from mechanical data obtained at various
frequencies so that AHCx2*and AScH2*could be obtained directly for the
paraffin rhain systcm. The different crystal structures of the even-odd
series could be taken into account. Tn the event, we were forced to use
a, p ,
AND
RELAXATIONS
203
dieleclric data on ketones, esters, and ethers to obtain AHcH2*. These data
are internally consistent and imply A H c H ~ *= 700 cal., but some differences
in crystal structure bctwecn these compounds and the n-paraffins are
possiblc, and AHcH~*
for the paraffin chains could be somewhat different
than that applicable to ketones, esters, arid ethers.
Despite the problems caused by gaps in the available data, the conclusion
is drawn that the ac - B model is capable of describing in a t least a general
way the role of impurity chains, and the variation of T,,,, AHcH2*,AXCH**,
and log r with chain length for chains whose length does not exreed IT^.
The distribution of reIaxation times for the ac - B reIaxation is not
large. The half-width OC the dielectric loss peak on an 2 versus log j
plot is about 1.6 decades. (A single relaxation time gives a half-width of
1.1 decades.) The distribution may be attributed partly to the existence of
inore than two orientation s i t e ~ , ~ and
~ - ~partly
*
to a distribution of lengths
of the impurity molecules.
Single Crystals of Polyethylene. The fit of the T,,, data a t 1 He. on
the n-paraffins using the a, - B mechanism results is seen in Figure 12 to
extrapolate up to the vicinity of T,,, for single crystals as observed by
mechanical reIaxation studies. I n singIe crystals, n is taken to be 1/10, i.e.,
it corresponds to the fold period. This extrapolation, which depends on
the rigid-rod approximation, is provisionally valid only so far as n N 60
20 to @z = 40, but a t such chain lengths T,,, values
120, i.e., @z
to n
not far from those observed in polymers have been approached. The
results shown in Figure 12 suggest that the mechanism causing an important part of the ac mechanical relaxation process in single crystals is
closely similar to the aC- B mechanism jn n-paraffins, which is a result of
reorientation of defect chains in the crystal lattice. The link between the
two cases is provided b y a comparison of the T,,, data for n-paraffins
and their polar derivative with the data for single crystal (Fig. 12). When
the fit to the data for the former, in which the mechanism is known to be
a, - B, is extended to higher chain lengths, the fit to the polyethylene
crystal data is reasonably good. This strongly implies that chain rotation
over a barrier (with chain twisting at large values of n) is a principal contributor to the overall
process in chain-folded single crystals. We
had anticipated that a = a = a and b = b = b in the ac - A, and
aC- B and aC- C, models. Also, we had anticipated that To(a, - A)
T0(a,- B) g To(a,- C,] = AHcx2y/AXcH2y. It is difficult to escape the
conclusion that these equalities, which relate ac - A, ac - B, and ac - C,,
are a t least approximately valid. Because the acrelaxation in single crystals
evidently consists of two components (see below), the ae - C, part of
model ac - C is used henceforth for purposes of comparison with thc
ac - B model for paraffin chains.
The T,,, data on single crystals lie in the region where chain twisting is
expected, i.e., n greater than 6&120. Calculation of T,,, using ?n = 30
arid
= 40 with eq. (36) for the cases a = a = 2, 6 = b = lS, and
a = a = 0 and b = b = 14.5 are shown in Figure 12. These calcula-
204
a, p,
AND RELAXATIONS
002
,004
C
. OO06
,008
RECIPROCAL OF LAMELLA THICKNESS, (Ill)
205
Fig. 14. The plot of the area .f G" d ( l / T )for ac process in arbitrary units as a function of reciprocal lamella thickness for single crystal mats of polyethylene. (Data of
Si~inott.~)
+
+
206
01,
8, AND
RELAXATIONS
207
single crystals thicken, and Sinnott has shown that absorption intensity of
the ac incchanical relaxation proccss decreasesz5 (Fig. 14). This is preciscly what is predicted by the a , - A 01- ac - C models as has been discussed earlier. Just the reverse occurs in bulk polyethylcne samples:
according to Illcrs, the mechanical absorption of the main ac mechanical
process increases with annealing and thickening, which processes are associated with an increase of density. These results are not necessarily contradictory. I n the case of Sinnotts mechanical data on single crystal
mats, there is of course little change in the degree of crystallinity as the
lamellar thickness is increased. Therefore the decreasing intensity that is
found with increasing fold period in single crystal mats may be regarded as
being without complications. However, there is a small but definite increase of density in bulk polyethylene that clearly correlates with the
increase of G.27*56We would tentatively attribute the increase of density
and hence G in the ac region on annealing in bulk polyethylene largely
to the following factors: (a) removal of cilia by thickening, which improves contact between the lamellae, and (6) tightening of interlamellar
links caused by thickening.
The amorphous component in the type of linear polyethylene samples
usually prepared never becomes separate and distinct enough to lead to a
Iarge and clear-cut p type Ioss peak such as is found in PCTFE. The
reason is that the rapidity of crystallization of polyethylene of the usual
molecular weight precludes retention of any significant amount of clearly
identifiable amorphous phase even with rapid quenching. The crystallization of PCTFE a t a specified supercooling is much slower than that of
polyethylene at a similar s ~ p e r c o o l i n g and
, ~ ~ ~rapid quenching through the
region of rapid growth (which lies about midway between Tm0and T,) is
capable of preserving a considerable amount of amorphous material which
is then metastable below T,. The increase of density on annealing bulk
polyethylene of the type used by Illers is therefore probably not due to
crystalljzation of truly amorphous material, but rather to removal of
voids caused by smoothing of the chain-folded surface, removal of cilia by
thickening, removal of some looplike folds, and tightening of interlamellar
links. I n quench-crystallized PCTFE, definite evidence for the existence
of an amorphous phase appears in the dielectric and mechanical data,
which show a distinct /3 relaxation (see later).
Dielectric studies reveal an ac process in slightly oxidized bulk polyethylenezGp57
that appears to be quite similar to that discussed by Ishida
and Yamafuji2Gin single crystals. We tentatively identify this as a, - Cf.
It is concluded that two of the ae relaxation peaks found in bulk polyethylene correspond in many respects to the ac - C, and a, - Cf relaxations found in uncomplicated form in single crystal mats, and that these
processes are basically described by the CY. - C model with chain folds as
modified to include chain rotation-translation and twisting in the lamellar
interior. The differences between the behavior of single crystals and bulk
polymer arc suggested to be the result of the effects of cilia and inter-
208
a, 0,
AND
RELAXATIONS
209
Thus, single crystals with slightly rough fold surfaces can give two a,-type
relaxation effects. Bulk polyethylene exhibits the aC - Cc and ac - C f
relaxations and a third mechanism probably arising from the extendedchain phase. Certain additional differences between the behavior of
single crystals and the corresponding bulk polymer are attributed to
effects due to cilia and interlamellar links. The results on PCTFE indicate
that a clearly resolvable ac process occurs only when the chain-folded
lamellae have a reasonably narrow distribution of thickness, and foIds that
are not too looplike. These findings are consistent with the models
presented.
T , (dilatometric)
( t lo5 see.),
"C.
T , (dielectric)
from WLF
analysis, "C.
0.12
0.44
0.73
0.80
-40
50
59
46
65
87
45
T,,,
at 1 IIz.,
"C.
110
125
92
210
LOG,, FREQUENCY,HZ
Fig. 15.
t"
versus log f at various temperatures for PCTFE specimen 0.73 showing the
p process. (Data of Scott and co-workers1)
a, 8,
AND
RELAXATIONS
211
= ceUr*/R(T-T=)
(37)
1,/2..fm
roe U q * / R ( T - - T m )
(35)
where for a given supercooled liquid U,* and U,* and T, are practically
identical. This temperature dependence of the viscosity was noted by
Vogelsg in 1921. More recently, Williams, Landel, and Ferry60 (WLF)
have assigned the approximate values U,,*
4.12 X lo3 cal./mole and
T , G T, - 51.6 to cover the case of many amorphous polymers. These
quantities may vary considerably from one polymer to another, but the
values cited are still useful for the present purposes. Equations (37) and
(38), while quite probably more fundamental in origin than q or T in the
form C exp { AH*(@/RTf, are still altogether equivalent to stating that
AH*@) is temperature-dependent. The temperature dependence of AH*
that accords with eqs. (37) and (35) is
AH*(p)(cal./mole) G 4.12 X 103T2/(51.6
as may be found by taking AH*
substituting the WLF constants.
+T -
(39)
j3 PROCESS
TG=87' C
201
I
50
100
I50
200
TEMPERATURE, 'C
Fig. 16. AH* versus temperature for the p process in PCTFE samples. (Data of Scott
and co-workers.') Solid lines calculated using eq. (39) with Tovalues shown.
The solid lines in Figure 16 show A l l * as calculated with eq. (39) for
the I', values shown. The observed temperature dependence of AH* for
specimens 0.73 and 0.50 is approximately accounted for by the WLF expression for AH*, eq. (39). (The temperature range where
could be
located in specimen 0.44 was too short to allow AH*(@) t o be calculated a t
J;r,LX
212
two widely different temperatures.) We conclude from the above behavior that the relaxation peaks that we have denoted ,8 for specimens
0.80 and 0.73 in Figure 4 are definitely of mostly amorphous phase origin.
Thus, we are correct jn distinguishing the acpeak in specimen 0.80, whose
origin is in the crystaIline phase (surface) and which has an activation
eiiergy that is independent of temperature, from the ,8 peak in specimen
0.73 which originates mostly in the amorphous phase and which has an
activation energy that is highly temperature dependent. There is little
doubt that the ,8 peak in 0.44 is of amorphous origin.
The glass transition temperature evidently depends on the texture and
degree of crystallinity (Table 11). Consider first the set of quenchcrystallized and quench-crystallized and annealed specimens 0.12, 0.44,
and 0.73. T , (dilatometric) increases steadily as x increases. This may bc
attributed to the increasing degree of strain and entanglement found in the
amorphous regions of these specimens (Fig. 2). The amorphous material
in specimen 0.12 is probably only weakly strained, and the T , value must
bc close to that of the completely noncrystalline state. For the reasons
cited earlier, the amorphous material in 0.73 must be in a strained state.
The increased strain in the intercrystalline links decrease the number of
configurations per unit length, and thereby increases T , (see below).
The same trend may be seen in T, (dielectric) in specimens 0.44 and 0.73.
[The shift of T owith x in specimens 0.12, 0.44, and 0.73 is quantitatively
somewhat different depending on whether one uses T o (dilatometric) or
T , (dielectric). The error probably lies mainly in T , (dielectric), which
depends on the validity of the constants in the WLF equation, and is also
doubtless affected somewhat by some mixing with the ar process with
loose folds. Howcver, the trends are similar enough to establish that the
upward shift of the ,8 peak with increasing x is largely a result of a real
increasc in T,. J The increase of T , with increasing x in these specimens is
also reflected as an increase in T,,, (Table 11). Poly(ethy1ene terephthalate) exhibits a similar increase of T , as the crystallinity is raised
from low to moderate values by annealing.6I
The plots of a tan 6 do not reveal an upward shift of T , (Fig. 4). This
shift is however seen in plots of G versus T given by Crissman and Passaglia.24
The situation in specimen 0.SO is entirely different than in 0.44 or 0.73.
In 030, both T, (dilatometric) and T , (dielectric) arc much lower than
they are in 0.44 or 0.73. The explanation of the low T , in specimeii 030 is
possibly as follows. In a specimen crystallized in the manner described for
0.80, the crystals grow slowly in an amorphous medium, and the process
may be quenched at any desired time. The result is a two-phase sample
comprising a normal crystalline and a separate unstrained amorphous
phase, where the amorphous phase has a normal T,. This is in direct
contrast to the quench or quench-annealcd specimens 0.12, 0.44, and 0.73
in which the amorphous phase is highly strained (see Fig. 2). The only
source of high T , amorphous material would be the small fraction of the
a,
0,AN13
RISLAXA'I'IONS
213
0.80 specimen that is in the form of stmined interlamellar links. Evidently this fraction is either so low or so dielectrically inactive that thc
high T , is not seen. Poly(ethy1ene tercphthalate) exhibits a similar drop
in T , for high crystallinities for specimcns that have been isothermally
crystallized.61
The foregoing analysis definitely relates the /3 relaxation process to thc
onset of the glass transition at T , in the amorphous phase. The variation
of T , with x in the quench-crystallized and quench-crystallized and annealed specimens 0.12, 0.44, and 0.73 is due to the varying degree of strain
experienced by the amorphous chains in these materials. T,,, for the
p process at 1 He. is the temperature at which the mean dielectric relaxation
time of the molecular motions involved is 1 per second; T , (dilatometric) is
simply thc temperature where thc mean dipolc reorientation timc is on the
order of magnitude of perhaps lo5 or lo6 sec.
Two basically different approaches have been employed to explain cquations such as eqs. (37) or (38), which are the principal relations governing
the temperature dependence of the 0 process. One approach62assumes
that the change of free volume, vf, is the principal cause of the temperature
dcpcndcnce of 7, and presumably T (dielectric), i.e.,
214
a, 6 ,
AND y RELAXATlONS
215
region, an t versus log f plot exhibits an asymmetric loss peak with a high
~~
frequency tail which is fit quite closely by the D a v i d s o n - C ~ l eempirical
representation. The distribution narrows somewhat with increasing
temperature. It would be of considerable interest to determine if the basic
chain model used by Gibbs and DilliIarzio, modified to include rigid dipoles
on each monomer unit, led to the appropriate distribution, but this involves
extreme mathematical difficulties in the right-angle dipole polymer case.
Zimm67has calculated the distribution of relaxation times for the casc
where the dipole moment is colinear with the chain, and a loss process
rather closely matching the empirical Davidson-Cole function is produced.
With a suitable choice of the form of the friction cocfficient in Zimms
theory, the infinite relaxation time at T, or T , is reproduced.
Note that a correct model of the relaxation processes in an amorphous
polymer with dipoles attached a t a right angle to the main chain is required
t o produce two separable relaxation processes active in principle in both the
mechanical and the dielectric relaxation spectrum: ( 1 ) the P relaxation
where T varies according to eqs. (37) and (38), and which freezes out a t
1 Haz. a t about O.76Tm0,which is well above T , (dilatometric)
0.63 to
0.67Tm0(see Fig. 2) and (2) the y a relaxation which has a low and temperature-independent activation energy that freezes out a t 1 Hz. near
0.50Tm0(Fig. 2).
The fact that relaxation effects due to the simplest liinking type motions are seen at 1 Hz. well below TZ in the glassy state in the y a amorphous
phase process (see following section) implies that the smallest cooperativc
subsystem associated with x* jn the p relaxation process is substantially
larger than that associated with the simplest noncooperative configurational
change. The simplest possible noncooperative configurational change is
the localized kinking motion that causes the high frequency part of ya.
216
011
0 10
0 09
SPECIMEN 0 8 0
0.08
0.07
0.06
6
Q05
004
003
0.02
0 01
0
I
LOG,, FREQUENCY,
10
Hz
Fig;. 17. 2 versus log f at various temperatures for PCTFE specimen 0.80 sliowing
prominent y process. (Data of Scott and co-worlters.1)
01,
0, AND
RELAXATIONS
I
217
r
.07
06
.Q 5
.O4
E
.o 3
.Q 2
.01
01
-I
4
5
6
LOG,, FREQUENCY, H r
10
Fig. 18. Resolution of the yC and ya processes on a plot of d versus log f a t 23C. for
PCTFE. (Data of Scott and co-workers.)
P,,, at 1 Hz., C.
X
0.00 (extrap.)
0.12
0.27M
0.42M
0.44
0.73
0.80and0.80M
1.00 (extrap.)
Dielectric
- 10
-1.3.5
-30
-
-41
-50 (-45)
- 18
-30
-
-40
-
17 1 = A H * ( y a )
10.7
15 8
15.7
14.6
14 0 (14 3) = A H * (re)
2111
B. Model
ye
-A
z = z,*
+ B1 log C(t - t n ) / t o l
(42)
B1
2.303 1 : 7 ' / ( 2 9 ~ ~ / a , )
(43)
wlicrc
=
a, p ,
AND
RELAXATIONS
219
STAGE I
STAGE 2
fcJ
I
LOG
fdl
le I
Fig. 19. (a,b,c) Schematic diagram for the thickening process of a chain-folded
crystal, indicating a mechanism for the injection of chain ends creating a row of vacancies
into the lamella; ( d ) rate of thickening (schematic); (e) edge dislocation a t vicinity of
chain end (schematic).
and t - to is the age of the crystal, and g = 2.54 X lo-* cm. for the carbon
skeleton polymers. Stage 2 thickening, which involves a high rate of
injection of vacancy row defects, proceeds a t the slower rate (Figure 19C)
where B1in eq. (42) is replaced by6s68
Bz
2.303 kT/(2ga2/a,
+ Ello)
(44)
where lo is 1.27 X lop8 em. for the carbon skeleton polymer and E is the
energy required to form a row vacancy per -Cunit. Bulk polyethylene
is known t o thicken in the two-stage rnanne~-ll*~~
depicted in Figure 19D.
Up to the present time, only the second stage has been seen in single crystal
mats, so that these crystals may be formed initially with the chain ends
220
DEFBT
REGIONS
&-A
near the surfaces (Pig. 19B). Either way, extcnsivc thickening cannol
occur in chain-folded single crystals or chain-folded lamellae in a bulk
polymer without injection of the type of defects illustrated in Figure 19C.
Evidence also exists that bulk PCTFE thickens markedly on annealing.lg
The transport of chain ends through the chain-folded crystal by the thickening process has been predicted to be accompanied by the formation of
edge dislocations of the type shown in Figure 19E.6 These dislocations
have been observed by Holland'O in polyethylene single crystals. Importantly, the number of them increases greatly with annealing. This
partially supports our contention that defects involving rows of vacancies
are injected into chain-folded crystals as they are annealed. The increase
of concentration of these vacancy rows will be used to explain the increase
of intensity of the y c - A process on annealing.
The model for y. - A is shown in Figure 20. A chain in the defect
region is subject to a greatly reduced barrier to reorientation from site 1 to
site 2 (Fig. 20) because of lowered repulsion. Any of the chains adjacent
to the defect can undergo turning, or turning and twisting, motions. It is
assumed for simplicity that the barrier system is such that the chain has
two sites 180" opposed (site 1 and 2 ) . We assume further that a simple
kink, similar perhaps to a Reneker
with an activation energy
AWd* allows an anguIar displacement of 180" to take place. The rest of
the chain then rotates, or attempts to turn, each -CHZunit adding a
free energy of activation barrier AWCH2* in the rigid-rod approximation.
The case for the rigid-rod
We consider first the calculation of T,,,.
approximation is given first. The free energy barrier resistling reorientntion between site 1 and site 2 is given by
AW,*(n)
AWd* -I- n A W c a 2 *
(45)
where AWd* is the free energy of activation associated with the kink
defect, and A T V ~ H ~is* the free energy of activation per -CHzgroup.
Breaking the free energy of activation into its entropy and enthalpy contributions gives
(46)
4-nA8cH20,*
(47)
and
A s , , ~ ) * ( n ) = A&"
a, p,
AND
RETAAXATIONS
221
- A) [(c
+ n)/(d + n)I
(50)
The above equation is similar in form to those obtained for aC - A,
ac - B, and ae - C, in the rigid-rod approximation, but somewhat different
values of TOare to be expected, and in general c # a and d # b. Because
of the looseness of the hole in which the chain reorients in the yc process
compared t o the ace, we must expect AHcH2(,)*to be considerably less than
aHCHz*
for the ac process.
The corrections for chain twisting can easily be made using the WilliamsLauritzen model. The heat of activation becomes
= To(yc
AHyC(,,*(n)= AHd"
+ A ~ c r r 2 ~ , ,[S(E,,Ez)
*2~
I
(51)
+~~AHcH~(~)*
222
vacaiicies, and ( p c ) the resolved dipole moment of the chain (or chains) of
length Zd in the defect region. The factor l/n, acting alone would cause
T,
na t o fall with increasing lamellar thickness, but the increase in ?%a
caused by injection of chain ends leading to vacancy rows should for a
time be the dominant effect, leading I , to increase with increasing lamellar
thickness. (HollandO has found that the number of dislocations in polyethylene single crystals increases by 103 on annealing.) This is consistent
with our suggestion that I , will increase with isothermal annealing.
- X-A
-.-
y-A
( r i g i d rod)
(rod w i t h
twist)
E
I-
/low
f,
LOG n
LOG f/f,,,
Note that we have not predicted that thick lamellae will always have a
larger yc effect than thin lamellae. Our prediction specifically applies to
new lamellae that have begun to thicken, where the original lamellae were
all produced under the same crystallization conditions. If lamellae of
different thicknesses are prepared by varying the crystallization conditions,
the behavior of the y c absorption with respect to thickness might be quite
different. Note also that after sufficient thickening that nd will tend to
level off, possibly allowing the l/?zc term t o predominate.
The mechanical absorption will vary approximately as (C1Cz/N2)nd,
with Cz = C1 exp { -AW,/lcT}, where AWd is the equilibrium energy
difference associated with the kink-type chain defect, Equation (52)
assumes for simplicity that the two sites associated with the intermolecular
forces for the chain itself have equivalent equilibrium energies.
Perhaps the most striking feature of the y c process is the broad and
asymmetric distribution of relaxation times that it exhibits. This can be
explained directly from the model shown for ye - A in Figure 20. Some
defects will contain short chains such as nl in Figure 20, and others will
contain larger ones such as nz. T o a, good approximation, the active part
of the chains in the defects will possess lengths that vary uniformly between
zero and n,. This gives
(53)
LY,
p, AND
RELAXArIONS
223
where
T(n) =
Toe
AWA*(?L)/~T
(54)
and
AWA*(n) = AWd*
+ ~~TZAWCH,,,,*[J(E~,EZ)I
(55)
224
Trnax(7)=
160[(25
+ n>/(50 + n)J
(56)
a, p,
AND
RELAXATIONS
n-PARAFFINS
tn-PARAFFINS
LOG,,
225
POLYMERS +
t-
POLYMERS +
(SEQUENCE
2n
LENGTH)
3
.
0
(b)
Fig. 22. The temperature T,, of maximum mechanical loss for the y o process i n
single crystal mats of p0lyethylene.~5 Data for low temperature process observed for
%-paraffinsin polystyrene matrix39shown for comparison: (a)T,, versus loglo n where
n is taken to be the number of -Catoms for the n-paraffins, and the number of
-Catoms in a fold period for the single crystals; ( b ) T,,, versus loglo (sequence
number). The sequence number is taken to be n for the n-paraffins and (n / 2 ) for the
single crystals. Dashed line on nght-hand side shows effect of cham twlstmg for case
% = 50.
T,,,,,
300 [55
(37)
is shown.
I n eq. (57) the effect of twisting is taken into account as was clone in
eq. (30), and f i was taken to be 50. It is seen in Figure 22 that eq. (57)
gives a satisfactory fit t o the paraffin data, but a discrepancy exists hctween the calculated and the experimental curve for the polymers. This
discrepancy is readily explained in terms of the modcl for the y c - A
process in which a distribution of active chain lengths is considered. The
effective ialue of n in the rigid rod approximation is (n/2), whcrc n is
the number of -Catoms in the fold period. Therefore, the polyiner
data in Figiirc 22 should be shifted 0.3 decades of log 7% t o the left, and
226
inspection of Figure 22 shows that if this is done (filled squares, Fig. 22b),
the polymer data fall satisfactorily on the calculated curve. An important
will depend upon
fcature of eq. (57) is that it predicts that [lim (Tmax)]n-+a
the frequency of measurement in the manner prescribed by the experiments. For example, for very high frequencies (In ArTnN 0), eq. (57)
becomes in the limit of large chain lengths
lim (T,,,),,,
300(255/200)
380K.
(58)
It is interesting that Starkweatherso has in the case of low-density polyethylene arrived at a value of about 380K. as the maximum tempcrature
at which the. y relaxation in polyethylene can be observed.
A further feature of eq. (57) is that the quantity ASCH,~,,* may be
obtained both from TOand from the constant d = 200 in eq. (57). For
AH,* = 12 kcal./mole from the mechanical studies50, AHcH~,,,* = 60
cnl./mole for m = 40, and AScHao,* = 60/300 = 0.20 e.u. from To =
300K. Alternatively, taking log A = 12 then ASCE,,~,* = 4.6 log A/d =
0.27 e.u. The agreement between the AXCH~,,,* values is satisfactory.
Therefore we conclude that the fit of the calculated curve [eq. (56)] is
probably fortuitous and that eq. (57) gives a more satisfactory account of
the yc relaxation in the single crystal mats of polyethylene. The fit of
eq. (57) to the paraffin data is also quite satisfactory. This implies that
the mechanism operative in the polymer crystals is related to that in the
n-paraffins, but, as previously noted, it is difficult to see how any appropriate variant of our y c - A model can account for the y process in the
n-paraffins. Final acceptance of the connection between the paraffin data
and polymer data implied by the fit obtained with eq. (57) must be delayed
until a satisfactory model for the y process in paraffins is advanced, and
until methods other than the mechanical veriiy and give information on
this process in the paraffins.
We turn now to a further consideration of the mechanical relaxation data
on polyethylene single crystal mats. I n Sinnotts data, the absorption
intensity of the yc peak definitely begins to increase as soon as the lamellae
start to thicken. The yc - A model predicts this result. Sinnotts
data also imply a broad distribution of relaxation times: the G versus T
peak at 1 Ha. is quite broad. These observations are consistent with the
yG - A model.
Ishida et al.72have clearly demonstrated the existence of a yc process
in single crystal mats of poly(ethy1ene oxide) by dielectric studies. The
observed activation energy is 9 kcal./mole. The yc loss peaks on an E
versus log j plot has a half-width of approximately 3.5 decades, which is
consistent with the large distribution of relaxation times produced by
model yc - A (see below).
The y c process appears prominently in bulk polyethylene. Some of this
effcct is a result of chain-end induced defects of the type proposed in model
yc - A, since T,,, appears in the same tcmperature region as it does in
single crystal mats. An extended-chain component giving a low-tempera-
a, p,
AND
RELAXATIONS
227
--f
228
.06
LOG,,f
I
12.2 k c d /mole
AH (y, )
yc
EXPERIMENTAL
I
10
(Hz)
I
50
THEORETICAL
I
(CALC)
-6
LOGlo
-2
-4
y,
I
wr.
Fig. 23. Experimental and calculated plots of the dielectric loss factor for the yc
process as a function of frequency a t two temperatures for PCTFE. (Experimental
data of Scott' as aiialyzed in Fig. 18.)
was calculated at 300 and 400K. and the corresponding values for
AWCH*(~)*
and m were evaluated as outIined above. These values are
indicated in Figure 23, together with A H C X ~ ( and
~ ) * AXCX~,,,*.
Figure 23 shows the plots of 'E against log W T O calculated numerically by
using eq. (53) together with the A W C H ~ (and
~ , * in values derived above.
It is seen that the calculated curves have the required shape, and lead t o a
shift of E" (max) with temperature that come reasonably close to reproducing the experimental activation energy. The comparison between
theory and experiment seems satisfactory.
The above analysis implies a To of about 800K. Because of the error in
the estimate of ASCxz,,,*, this value is undoubtedly no closer than 200 or
300K. to the true value. However, it can be shown that experimental
value of TO is quite high, and not inconsistent with the theoretical value.
In Figure 17, it is seen that the y process-the data shown are largely yGpersists up t o at least 200C. or 473K. The actual value of 7'0 is therefore probably near or above TTm"
= 494K.
The absorption intensity of the y e process as observed in dielectric
measurements evidently increases as the temperature is increased (Fig. 17).
a,
0,AND
RELAXATIONS
229
230
the motions is proposed as the basic cause for the observed overlapping of
the ya and yeprocesses shown in Figure 18.
The value of AH*(ya) slightly exceeds AH*(y,), and this point requirw
comment. Both AWd* and AWCX,,,,* involve intermolecular and intramolecular contributions. We would expect the intramolecular contributions to AWd* and AWcxP,,* in the y a and y G relaxations t o be rather
similar. However, the intermolecular forces will be somewhat different
because the packing of the molecules is different in the glassy state and in
the vicinity of a chain end defect in a crystal. One measure of this effect
is the local specific volume. I n the glassy state, this is about 0.475 ~ m . ~ / g .
in the temperature range of the y relaxation (Fig. 1). The free chain in an
idealized hole in an hexagonal lattice in PCTFE has associatcd with it a
local specific volume of 0.453 X (6/5) or 0.543 ~ m . ~ / g .Thus, a chain in a
defect such as that shown in Figure 20 could on the average meet less
resistance from neighbors as it forms a kink and reorients than would be
encountered by a similar motion in the glassy state. This would lead to
the observed fact that AH*(yc) is slightly less than A H * ( y J .
The distribution of relaxation times exhibited by the -ya process is extremely large, and exceeds that of the y c process (half-width of 4.3 decades
compared to 3.2 at 23C.). Considerations based on the properties of
kinks and related simple and localized chain distortions do not ordinarily
lead to such broad distributions, and it is believed that propagation of
twist over various lengths of chain, and correlations of movement along
the chain, are probably involved in addition to the simple motions.
1 / ( 2 ' 1 ~ f ~=
~ , )(h/kT)e*"*'"'
(59)
a, p,
AND
RELAXATIONS
231
peaks are possibly to be identified with the one we have called 6 in the E
versus log f plot in Figures 17 and 18. At least in the case of PVC, it is
clear that the 6 process cannot be due t o rotatable side groups. The same
is true of PCTFE. Nevertheless, the possibility that the 6 relaxation is in
some polymers associated with the rotation of side groups cannot be discounted.
The 6 relaxation in P C T F E evidently is a property associated with the
crystalline phase, as is apparent from Figure 17. I n previous discussions,l
the contribution Aecrystal of the 6 relaxation process (then called the highfrequency crystal relaxation) to the dielectric increment tS - E, was
estimated on the basis that the y relaxation process had a symmetrical loss
curve 011 an E versus log f plot. Actually, the y c process has a large highfrequency tail, and the intensity of the 6 process as estimated by using a
symmetrical y c process is probably high by a factor of perhaps two or three.
Thus, the 6 relaxation is not as intense as was originally proposed by
Scott et al.
With few exceptions, the 6 relaxation appears to be most active in chains
that exhibit a helical conformation. For instance, PCTFE, PVC, poly-4methylpentene-1, and isotactic polypropylene exhibit a 6 relaxation, while
polyethylene and nylon 66 do not.
I-lencc 6U
6U1 =
A10
6U2 =
X2W
(XI - Xz)a.
w120
=
2
~ 1 2 ~ [ l
w12
(6Cil/kil)] =
arid
wl
~ 1 2 [ 1-
in the presence of
(Xia/kT)]
(61)
WZlO[l
(Xaa/kT)]
(62)
232
where
N 1 = NP
+ rb
Nz =
-n
N20
= N10
N2O
N10and Nzo are the occupation numbers in sites 1 and 2 respectively in the
absence of the stress, and N1 and N2 are the corresponding quantities in the
presence of the applied stress. Substitution of eqs. (61), (62), and (64)
into eq. (63), with ( W ~ ~ ~ / W ~=~ ON2/N10,
)
and retaining linear terms, gives
dn/dl
n(w1z0
W Z I ' ) = Niow12O[(X1 -
XZ)/ICT]U
(65)
Now let
0') =
a' = (wrio
and
~ 2 1 ~ )
(67)
= w/w'
(68)
CJT
Insertion of eq. (68) into the real part of eq. (67) gives
=
ATei("t-$.)/(l+ w 2 T 2 ) ' / 2
Amiwt/(l i w ~ )
(69)
Y,
+ en
(7 1)
where ymis the instantaneous (elastic) deformation and c is a proportionality constant, the complex compliance J * = ( y / u ) is given by
J*
Here J ,
= y m / u , and
(-10Since
Jm)
(uYL"/u~IO)
J,
+ [(Jo - Jm)/(l+
iWT)I
( J o - Jm)
is given by
(72)
(73)
a, p,
AND y RELAXATIONS
233
W a ~ h t m a nhas
? ~ shown that c 0: (XI - X2)/v, where v is the volugne containing N relaxing species. Hence,
E,)
r 4 ~ n a= 4 T
number-active species
cm.3
(76)
7
References
1. A. T-T. Scott, D. J. Scheiber, A. J. Curtis, J. I. Lauritzen, Jr., and J. D. Hoffman,
J . 1Zm. Nall. Bur. Std., 66A, 269 (1962).
2. S. I. Reynolds, V. G. Thomas, A. 11. Sharbaugh, and R. M. FILOSS,
J . Am. Chem.
Soc., 73, 3714 (1951).
3. G . P. Mikhailov and B. I. Sazhin, Soviet Phys. Tech. Phys., 1, 1670 (1957).
4. L. Hartshorn, J. V. L.Parry, and E. Rushton, J . I . E. E., 100, Pt. IIA, No. 3
(1953).
5 . J. D. Hoffman and J. J. Weeks, J . Res. Natl. Bur. Std., 60, 465 (1958).
6. J. D. Hoffman, S P E Trans., 4, No. 4, 315 (1964).
7. J. D. Hoffman and J. J. Weeks, J. Chem. Phys., 37, 1723 (1962).
8. P. H. Geil, Polymer Single Crystals, Interscience, New York, 1963.
9. J. I. Lauritzen and J. D. Hoffman, J. Res. Natl. Bur. Std., 64A, 73 (1960).
10. J . D. Hoffman and J. I. Lauritzen, Jr., J . Res. Natl. Bur. Std., 65A, 297 (1961).
11. J. 11, Hoffman and J. J. Weeks, J . Chenz. Phys., 42, 4301 (1965).
234,
234,