Reversal of Recovery Direction During Creep Recovery of Polymer Blends

Reversal of recovery direction during creep recovery of
polymer blends
H. Gramespacher'v and J. Meissner
Swiss Federal Institute of Technology (ETHZj, Institute of Polymers,

CH·8092 Zurich, Switzerland
(Received 8 July 1994; accepted 28 September 1994)
Synopsis
At small stresses or strains, polymeric liquids show a linear viscoelastic behavior. This can be
demonstrated in creep followed by creep recovery. If the creep period 0 < t < t 1 is long enough,
the elastic portion J e(t) of the shear creep compliance is equal to the recovered creep compliance
J,(t'), the latter follows from the recovery of the shear strain for t > t1 with the new time scale
t' = t tl . Both functions are monotonously increasing. Such a behavior, at least approximately,
r:
is shown in this paper for melts of polystyrene (PS) and poly(methylmethacrylate) (PMMA).
However, when blends of these polymers are made with the PS dispersed in the continuous phase
of PMMA, the relation JeCt) = J,Ct/) is no longer valid. Unexpectedly, the recovered creep
compliance shows a maximum at which the recovery direction is reversed. The height of the
maxima increases with the PS concentration. We attribute this surprising phenomenon to the action
of the interfacial tension and the different retardation times of the PS and PMMA melts. When the
PMMA is dispersed in the continuous phase of PS, such a reversal of the recovery direction is not
observed. © 1995 Society of Rheology.
INTRODUCTION
When a creep test is performed with a linear viscoelastic liquid, the material response
is a deformation that consists of an instantaneous elastic deformation ro- a delayed
elastic portion Ye(t), and a viscous flow term tl Tlo that increases linearly with time. For
the case of shear, with Tlo as the zero shear viscosity, the total shear strain is
}(t) = Yo+ ye(t) +P21(0)tIT/o. (1)
P21 (0) is the shear stress that is kept constant during the creep test. After a sufficiently
long creep time tl , i.e., tl > 7' with T' as the maximum retardation time of the polymer
melt under test, the elastic portion of the strain achieves its equilibrium value
YE = Yo+lim t -. 00 Ye(t) = const. When at t > tl the stress is removed, the creep
recovery test is performed with the total stress history
P21(t) = P21(0)[h(t)-h(t-tl)], (2)
where het) is the unit step function
{~
(t < 0)
het) = (3)
(t> 0).
a)Present address: RAYCHEM GmbH. D-85521 Ottobrunn, Germany.
© 1995 by The Society of Rheology, Inc.

I. Rheol. 39(1), JanuarylFebruary 1995 o148-6055/95/39(1)/151/10/$7.00 151
Redistribution subject to SOR license or copyright; see http://scitation.aip.org/content/sor/journal/jor2/info/about. Downloaded to IP: 183.173.42.187 On: Sun, 31 May 2015
00:27:42
152 GRAMESPACHER AND MEISSNER
P21
t=0 t1
y
r(t')
y(t')
t =0 1
tI .. t' = t - t1
FIG. 1. Stress history for a shear creep test followed by recovery and the resulting shear strain for a linear
viscoelastic material. The creep period ends at t I ; for the recovered shear strain r(t'), a new time scale is
introduced: t I = t - t I .
The response to the stress release of the material is a recovery of the strain such that for
t> tl
y(t) = y(tl)-[YO+ye(t-tl)] tt > tl)' (4)

In other words, for sufficiently long times t I the recovery of the shear strain is symmetric
to the elastic portion of the strain during the creep period, t < t I. Compared with the
other terms in Eqs. (I) and (4) for polymeric liquids the instantaneous portion 1'0 is very
small and can be neglected. Following Schwarzl (1990) we denote the recovered strain by
the letter r and obtain with a new time scale, t' = t - t 1 ' for linear viscoelastic liquids
and sufficiently large t 1
ye(t) = r(t/) (t> tl)' (5)
Figure 1 schematically shows the stress excitation and the resulting strain response
with the used notations.
When the shear strain, Eq. (1), is related to the magnitude of the shear stress PZI (0),
the resulting linear viscoelastic material function is the creep compliance
l(t) = y(t)/P21(O) = 10+lit)+tIT/o. (6)

As for yo, the instantaneous compliance 10 can be neglected here. Hence leU) repre-
sents the elastic portion of the creep compliance. Analogously, the recovered creep com-
pliance is defined by
lr(t') = r(t' )lPZl (0). (7)

For the linear viscoelastic case it follows from Eq. (5) and these definitions that
l/t') = lit). (8)
00:27:42
UNUSUAL CREEP RECOVERY OF POLYMER BLENDS 153
For polymer solutions and melts such a linear viscoelastic behavior has been well docu-
mented, e.g., by Ferry (1980). This behavior is characterized by Eq, (8) and by the fact
that the quantities on each side of this relation are monotonously increasing until the
equilibrium value is achieved. It will be shown in this paper that such a behavior exists
also for melts of polystyrene (PS) and poly(methylmethacrylate) (PMMA). But when
these two polymers were mixed, e.g., for our studies on the influence of the interfacial
tension in melts of polymer blends, as described by Gramespacher (1993) and published
by Gramespacher and Meissner (1992) and Meissner (1992), it was surprisingly found
that r(t') and J r(t') do not always increase monotonously, but instead can go through a
maximum followed by a decrease, reflecting a reversal of the recovery direction. We are
convinced that this unexpected behavior is caused by the action of the interfacial tension
between the two immiscible blend components.
EXPERIMENTAL
The components of the blends were commercial grades of PMMA (PLEXIGLAS 5N
of Rohm GmbH, Darmstadt, Germany) and PS (POLYSTYROL 158K of BASF Aktien-
gesellschaft, Ludwigshafen am Rhein, Germany). The molecular mass averages of these
polymers and their zero shear viscosities are given in Table 1. These components were
mixed in a twin screw laboratory extruder (Collin GmbH, Miinchen, Germany) at a
temperature of 200 QC with the following weight fractions of PS in PMMA: 8%, 12%,
16%,20%, and 84%. In these blends the component with the lower weight fraction forms
small droplets in the matrix of the other component. The diameter average of the dis-
persed droplets is approximately I J.tm. Gramespacher (1993) has described the details of
its measurement: cutting the sample in thin layers of 0,5 mm thickness by a microtome,
phase contrast optical microscopy, particle size distribution determined by image analy-
sis, consideration of the systematic error due to the fact that often not a complete PS
sphere was cut and measured, but only a cutoff.
In order to establish the same thermal and rheological history for all the samples to be
tested, the pure components were extruded under equal extrusion conditions. The prop-
erties of the components including their rheological characterization and the preparation
of the samples have been described by Gramespacher and Meissner (1992), and in more
detail by Gramespacher (1993),
The creep and creep recovery experiments were performed with a commercial stress
rheometer (RHEOMETRICS STRESS RHEOMETER RSR 8600, Rheometries, Inc., Pis-
cataway, NJ, USA) the heating system of which has been modified, The modification is
similar to that described by Meissner et al. (1989). All experiments were performed in
cone-and-plate geometry (cone angle: 0.1 rad) at a temperature of T = 170 QC. To pre-
vent any chemical reaction at test temperature and hence any alteration of the molecular
weight of the material during such a measurement, all tests were performed in nitrogen
atmosphere. The shear stress for all experiments was P2l = P21 (0) = 150 N/m 2 , The
creep duration t1 was at least 1500 s. This time is longer than the maximum retardation
time of PS and PMMA at the test temperature.
TABLE I. Number and weight molecular mass averages, and the zero
shear viscosity Tlo at a temperature of 170 QC.
M Il (g/mol) u; (g/mol) Tlo (Ns/m 2)
PS III DOO 3140DO 1.78 X 105

PMMA 47 DOO 830DO 1.22 X 105
00:27:42
2.0
1.5
;>-
e
'(;j
....
'(;j 1.0
...
(Ij
'l)
..c
'"
0.5
o
o 1500 3000 4500 6000 7500
t[s]
FIG. 2. Shear strain of the polystyrene melt during creep and creep recovery with a creep period of t[ 1500 s
and a creep stress of P21 (0) = ISO N/m 2 Test temperature T = 170°C.
RESULTS
We begin the presentation of the experimental facts with results for the pure compo-
nents of the blends. As an example for the "raw curve" of a test result, Fig. 2 shows the
total strain y(t) for the polystyrene melt during the creep period of 1500 s and the
following recovery period of an additional 6000 s. The stress during the creep period is
very small (PZl = 150 N/mz) such that we can expect the material behavior to be in the
linear viscoelastic range.
In order to determine the elastic portion Je(t) of the creep compliance the mean
straight line tl '70 was subtracted from J(t); for more details, see Gramespacher (1993).
The recovered creep compliance, defined by Eq. (7), follows from r(t'). Both quantities,
Je(t) and fr(t'), were determined from the curve of Fig. 2 and are given in Fig. 3. For
the PMMA melt, these functions are shown in Fig. 4.
For each blend component, the two functions Je ( t) and f r ( t') fall sufficiently to-
gether, apart from small differences that may be attributed to the subtraction of tl 7/0 from
the total compliance J(t). Another reason for the differences could be that the range of
linear viscoelasticity is already slightly exceeded. The coincidence of Je(t) and fret')
reflects the linear viscoelastic response and proves that in spite of the very long total test
period of 7500 s there is no noticeable change of the molecular structure, e.g., by deg-
radation, of these samples under the test conditions chosen. However, the time response
of the melts and the magnitude of the elastic compliances of the two components are
different. The PS melt reaches the equilibrium values of the elastic compliances
lim, ~ fe(t) = le = J R = lim.. ~ 70 Jr(t') after 500 s, the PMMA melt already after
)C
SO s. The values of hand JR are given in Table 11. There are also values for Je that were
calculated from oscillatory data using the well-known relation given, e.g., by Ferry
(1980):
00:27:42
~
'"
..,.E 2 I- Je(t)
6
~
\
\
~IV
.,
-.
Jr(t')
0
0 500 woo 1500
t, t' [s]
FIG. 3. Elastic creep compliance and recovered compliance le(l) and Ir(t'), respectively, for the polystyrene
melt obtained from the raw curve of Fig. 2.
le = lim C' (w)/[C"(w)]2. (9)

w-tO
However, when a blend is investigated with PS dispersed as droplets in the continuous

phase of the PMMA melt, there is a remarkable difference between fe(t) and fret ").
Figure 5 shows both functions for a blend with 16 wt % PS in PMMA. We notice that at
the onset up to approximately t = t' = 300 s, both functions coincide. But then, fe(t)
increases to its equilibrium value Je = 27xlO- 5 m 2/N , whereas fr(t') shows a maxi-
mum followed by a decay down to the equilibrium value fR = 15X 10-5 m2/N , which is
3
,.......,
~
'"
..,.E 2
-6
~t
Je(t) Jr(t')
\ -- \
0
0 500 1000 1500
t, t' [s]
FIG. 4. Elastic creep compliance and recovered compliance I,(t) and 1,(1'), respectively, for the melt of
poly(methylmethacrylate). Test conditions are the same as for Fig. 2.
00:27:42
TABLE 11. Equilibrium values of the elastic compliance J E and the re-
coverable shear compliance J R at 170 QC of the blend components PS and
PMMA.
J E(m2/N) 2
J R(m /N ) J E(m
2/N)
Method creep creep recovery shear oscillations
PS IS X 10- 5 15 X 10- 5 IS X 10- 5

PMMA 3,7 X 10- 5 3.6 X 10- 5 3,6 X 10- 5
the JR value given in Table II for the pure PS. It should be pointed out that the maximum
of Jr ( (') reflects a remarkable and unexpected reversal of the recovery direction: before
the maximum, the total shear strain decreases whereas at the maximum there is a reversal
to an increasing total shear strain.
For all the blends investigated so far with 8, 12, 16, and 20 wt % PS, Fig. 6 gives such
unexpected and very different results. All these curves have a maximum that increases
with the PS content and slightly increases its position from t' = 300 to 1000 s. Notice
also that the equilibrium values JR increase from 8XIO- 5 (for 8% and 12% PS) to
30X 10- 5 m 2/N (for 20% PS); the latter value is twice the result for the pure PS (Table
II). The maxima demonstrate that the observed phenomenon, never described in literature
so far, viz. a reversal of the recovery direction, is more obvious with higher polystyrene
concentration in these blends.
In order to confirm this finding, we repeated the measurements using a different sensor
for the angular deflection representing the shear strain signal. In fact, the measurement of
the angular deflection by using the reflection of a laser beam, gave the same result. In
Z
ri'-
e 2
6
-....."""'
......
..........
....
...
"""'
.......'"
.....
o
o 2000 4000 6000 8000
r. t' [s]
FIG. 5. Elastic portion of the creep compliance J,(t) and the recovered creep compliance Jr(t'), for a blend
with 16% PS in PMMA, Test conditions are the same as for Fig. 2.
00:27:42
4
Z
.......
'"E 3
'<t
-......
6
r--
:t:,
2
-....
1 ~ ~8%PS
I ~
0
0.1 1 101 102 103 1()4
time of recovery [s]
FIG. 6. Recovered creep compliance J ,(I') of the blends with different concentrations of the polystyrene
component. Test conditions are the same as for Fig. 2. For each PS concentration the results of two different
samples are shown.
addition, these tests were repeated in a different instrument and at another place
(BOHLIN RHEOLOGI GmbH, Miihlacker, Germany). Again the same curves of Fig. 6
were obtained. The appearance of the maximum in JR is not changed if the creep period
is extended, as the coincidence of the results of Fig. 7 shows for two creep tests with two
different durations of creep, tl = 1500 and 2700 s. Furthermore, there is no influence of
the residence time at test temperature on the height and position of the maximum. When,
with the same sample, two consecutive tests were performed, the first with t1 = 1500 s
and a recovery time of 8000 s followed by a second creep test of again t 1 = 1500 s,
practically the same J,( t') curve is obtained, as is demonstrated in Fig. 8.
When the PSIPMMA ratio is converted, i.e., the PMMA forms the droplets dispersed
in the continuous PS melt, which is the case at a 84% PS content, no maximum appears
in the recovered creep compliance J r( t' ). This is demonstrated in Fig. 9.
DISCUSSION
The main result of this paper is the appearance of a maximum in the recovered shear
compliance J,(t') of melts in which PS is dispersed in PMMA. This maximum means
that during shear recovery the shear strain does not decrease continuously to an equilib-
rium value but that in contrast it reaches a minimum at which the recovery direction is
reversed and the shear strain increases again until the equilibrium value is reached. This
experimental result is a beautiful demonstration that polymer blends of that kind cannot
be treated as linear viscoelastic liquids, even at the small stresses applied in our experi-
ments.
When in a very simplified way, each pure component is characterized by an individual
Voigt-Kelvin element, its retardation time follows from the instant at which the recov-
erable compliance fe(t) or (better because of experimental problems) the recovered
00:27:42
Z
N- 3
E
"'1"
-.....
6
C"'
~
2
..,""
o
0.1 101 102 103 1()4
time of recovery Cs]
FIG. 7. Influence of creep duration I, on the elastic recovery, expressed by Jr(t'), for the blend with 20 wt %
PS, Results for two tests with t I = 1500 and 2700 s. Stress and temperature are the same as for Fig. 2.
Z
N-
E 3
--....
"'1"
6
---. 2
'-'
..,""
o
0.1 10 1 102 103 1()4
time of recovery Cs]
FIG. 8. Influence of residence time on Jr(t') for the 20% PS blend. Two consecutive creep recovery tests
performed with the same sample. each test with I, = 1500 s, separated by a rest period of 8000 s after the first
test. Stress and temperature are the same as for Fig. 2.
00:27:42
3
~
Je(t)
N
?: ____ I
~
s 2
6
......
~
~.I f
..., Jr(t')
2
...,0)
0
0 500 1000 1500
t, r [5]
FIG. 9. Elastic creep compliance Je(t) and recovered creep compliance J,(t') of a blend with 16 wt % PMMA
in PS. Test conditions as for Fig. 2.
compliance Jr(t') has a magnitude of 63% of the equilibrium value. From the curves of
Figs. 3 and 4 we obtain the respective average retardation times T' = 70 s for the PS melt
and T' = 7 s for the PMMA melt. In the blends, the maxima of Jr(t') occur at much
larger times, increasing with increasing PS content, viz., from 300 s for the blend with
8% PS content to 1000 s for 20% PS content. This is already an indication that a much
slower process must be the reason for the observed phenomenon. Gramespacher and
Meissner (I992) have shown that in shear oscillations the influence of the interfacial
tension can be described by a Maxwell model with a relaxation time of T = 240 s, and
this is also much longer than the main relaxation times of the pure melts of PS or PMMA.
At present there is no satisfying explanation for the reversal of the recovery direction
described above and the observed dependence on time and polystyrene concentration.
The first qualitative proposal made by the authors has been--eorrectly--eritisized by one
of the referees who himself offered another explanation that, in turn, does not please the
authors. This situation demonstrates that there is no valid explanation presently. But for a
future discussion it may be helpful and stimulating to briefly describe in the following the
basic ideas of both attempts for explaining the phenomenon found:
The first attempt starts with the differences in the transient reactions of the three
contributions to the viscoelastic behavior, viz. the two melts PS and PMMA and as third
contributor the interfacial tension. When at the end of the creep test the shear stress is
released at t I , the following constrained recovery, measured by the mutual angular mo-
tion of the cone-and-plate system, is connected with a quick recovery of the PMMA
matrix and a slower recovery in the PS droplets. But when the stress within the PS
droplets is completely relaxed, these droplets have not yet reached their equilibrium
spherical shape. The interfacial tension, driving the droplets to this final shape, leads to an
additional shear within the droplets that is of opposite sign to the previous shear during
the creep period, t < tl . Hence the corresponding shear stress, induced by the recovery
of the shape of the droplets into its final spherical form, causes a recovery in the opposite
direction as soon as the shape of the droplets is close to or has reached that of spheres.
Because of the fact that the PMMA has a much shorter retardation time than that caused
00:27:42
by the interfacial tension, the observed reversal of the recovery direction can only be
found if the PS is dispersed in the PMMA, and not the other way around.
This simple explanation has severe drawbacks. One of the referees pointed out that the
shear rate during the first recovery period is approximately 7.5 X 10- 5 S-I. With the
retardation time of the polystyrene (70 s) the reversed part of the total recovery should be
of the order of 0.005 shear units only, whereas a much greater reversed shear strain has
been measured (0.03 for the 20% PS sample). The referee proposes that the reversed
recoil is caused by a distribution of droplet shapes and sizes leading to differently elon-
gated droplets during the shear period. During the following recovery the less elongated
droplets may become deformed in the opposite direction due to the recovery of the more
elongated droplets. This may drive the reversal of the recoil and explains, at least, the
very long time scales of the reversed recoil phenomenon. However, the increase of the
recovery time at which the maximum of the recovered compliance is located with in-
creasing PS concentration cannot be explained. Not explained by this concept either is the
result that no reversal of the recovery direction was found with the PMMA forming the
dispersed droplets in the PS matrix.
The present discussion shows that only by a more detailed study of this
phenomenon-including the morphology of the sample during the creep and recovery
periods-the speculations above can be replaced by explanation.
Finally, we want to refer to recovery measurements with the same blends after melt
elongation performed by Gramespacher (1993) and prepublished by Meissner (1992). A
reversal of the recovery direction as described here has not been found in elongation. This
may be due to the fact that the elastic recovery after melt elongation has been very large:
at 20% PS content and after a total elongation of 3.5 Hencky strain units (stretch ratio
A = 33), reached at a strain rate of 0.1 s -I, the total recovered stretch was Ar = 15 after
a recovery time t' = 4000 s. Unfortunately, at this time the tests were terminated; there-
fore a small additional reversal of the recovery direction after that period cannot be
excluded. For a more detailed discussion concerning the recovery after shear and elon-
gational flow, it has to be taken into account that in shear we have constrained recovery
whereas in elongation there is free recovery.
ACKNOWLEDGMENTS
We express our thanks to Professor H. C. Ottinger for many discussions, to the refer-
ees for their helpful criticism, furthermore to Rohm AG, Darmstadt, Germany, and BASF
AG, Ludwigshafen am Rhein, Germany, for the donation of the test material. The support
by the Swiss National Foundation for Scientific Research (Project No. 21-29890.90) is
gratefully acknowledged.
References
Ferry, J. D" Viscoelastic Properties of Polymers, 3rd ed. (Wiley, New York, 1980).
Gramespacher, H., "Einfluss der Grenzflachenspannung auf das rheologische Verhalten von Schmelzen aus
Polystyrol!Polymetllylmethacrylat-Mischungen in Dehn-und Scherstromungen," Ph. D. dissertation ETH
Zurich No. 10179, 1993.
Gramespacher, H. and J. Meissner, "Interfacial tension between polymer melts measured by shear oscillations
of their blends," J. Rheol. 36, 1127-1141 (1992).
Meissner, L, R. W. Garbella, and J. Hostettler, "Measuring normal stress differences in polymer melt shear
flow," J. Rheol. 33, 843-864 (1989).
Meissner, L, "Experimental problems and recent results in polymer melt rheometry," Macromol. Chem. Mac-
romol. Symp. 56, 25 (1992).
Schwarzl, F. R., Polymermechanik (Springer, Berlin, 1990).
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Reversal of recovery direction during creep recovery of

H. Gramespacher'v and J. Meissner

Swiss Federal Institute of Technology (ETHZj, Institute of Polymers,

(Received 8 July 1994; accepted 28 September 1994)

}(t) = Yo+ ye(t) +P21(0)tIT/o. (1)

P21(t) = P21(0)[h(t)-h(t-tl)], (2)

where het) is the unit step function

a)Present address: RAYCHEM GmbH. D-85521 Ottobrunn, Germany.

© 1995 by The Society of Rheology, Inc.

y(t) = y(tl)-[YO+ye(t-tl)] tt > tl)' (4)

l(t) = y(t)/P21(O) = 10+lit)+tIT/o. (6)

lr(t') = r(t' )lPZl (0). (7)

M Il (g/mol) u; (g/mol) Tlo (Ns/m 2)

PS III DOO 3140DO 1.78 X 105

le = lim C' (w)/[C"(w)]2. (9)

However, when a blend is investigated with PS dispersed as droplets in the continuous

PS IS X 10- 5 15 X 10- 5 IS X 10- 5

time of recovery [s]

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