Physical Aging Kinetics of Syndiotactic Polystyrene

as Determined From Creep Behavior

JORG BECKMANN and GREGORY B. MCKENNA*

Polymers Division
National Institute of Standards and Technology
Gaithersburg, Maryland 20899
and
BRIAN G. LANDES, DAVID H. BANK, and ROBERT A. BUBECK

Dow Chemical Company

Midland, Michigan 48674

Creep experiments in uniaxial extension have been performed to explore the

kinetics of the physical aging process in semicrystalline syndiotactic polystyrene
(sPS) having two processing histories. Classical time-aging time superposition be-
havior was found for both materials at temperatures from 70 to 95°C, with the shift
rate m decreasing as temperature was increased. Virtually no aging was seen at
95°C, the DSC determined glass transition, Tg. This behavior was atypical for a
semicrystalline polymer and reminiscent of the behavior of glassy amorphous
thermoplastics. Some evidence for a separate crystalline aging mechanism . Tg,
which manifests itself as only vertical shifts without timescale shifts, is seen in
experiments at T . 100°C. Finally, the two different materials age differently,
suggesting that some control of aging can be obtained by altering processing
conditions or morphology.

INTRODUCTION of the amorphous phase being constrained by the

presence of the crystalline regions, hence having a
he cooling of an amorphous polymer through the
T glass transition Tg results in a non-equilibrium
glassy state that then proceeds to spontaneously
decreased mobility and correspondingly increased Tg.
This model is also consistent with concepts of a “rigid”
amorphous phase in semicrystalline polymers, but
evolve towards a temporally distant equilibrium (1, 2).
does not agree with the small changes in glass tran-
Associated with the evolution of the state variables of,
sition observed upon large deformation of, e.g., rub-
e.g., volume or enthalpy, are observable changes of
ber. Another complicating feature of the problem is
macroscopic properties such as viscoelastic response,
the fact that recrystallization phenomena are possi-
yield strength, impact resistance, etc. (3), which has
ble .Tg. Here we report on studies of the physical
come to be referred to as physical aging. One antici-
aging process in syndiotactic polystyrene, for which
pates similar behavior for the glassy response of semi-
the amorphous and crystalline phases have similar
crystalline polymers. However, it has been observed
densities (9), and one might consequently expect that
that for semicrystalline polymers physical aging per-
constraints on the amorphous phase would be less
sists even above the glass transition temperature (3–
than those found in other semicrystalline polymers
8). A partial explanation for this behavior was offered
where amorphous/crystalline densities are signifi-
by Struik (3– 8). His argument is based on the obser-
cantly different. As shown below, we find qualitatively
vation that in constant frequency experiments, in
different aging behavior for the sPS from that exhib-
which the temperature is ramped from below to above
ited by other semicrystalline polymers.
the Tg, the loss factor (tan d) of the semicrystalline
polymers is broadened and appears to extend well
TIME-AGING TIME SUPERPOSITION
above the Tg range of the equivalent amorphous poly-
mer. Struik interpreted such behavior in terms of part Typically, after quenching glass forming materials
from .Tg to the aging temperature, the evolution of the
viscoelastic response with increasing aging time can
* Corresponding author. be represented by a time-aging time superposition

POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 1997, Vol. 37, No. 9 1459
 Jorg Beckmann et al.

Table 1. Description of Injection Molded Samples of Syndiotactic Polystyrene.

Sample Designation Mold Temperature Sample Thickness, inch (mm) Visual Appearance
SPS140 140°F to 150°F (60°C to 66°C) 18⁄ (3.2) clear surface with a turbid core
SPS300F 285°F to 295°F (141°C to 146°C) ⁄ (3.2)
18 turbid
SPSA or SPS140A — ⁄ (1.6)
1 16 clear surface with a turbid core
SPSB — 1⁄16 (1.6) turbid

principle similar to time-temperature superposition.
We can examine this by considering the following:
assume that the creep behavior at each aging time can
be represented using a Kohlrausch-Williams-Watts
(KWW) function (10, 11):
D ( t ) 5 D 0 exp@ t/ t 0 # b
where t0(te) is the value of t0 in Eq 2 at aging time te and
t0(tref ) its value at the reference aging time. Having
obtained the values of ate, these are then analyzed in
the conventional manner of making double logarith-
mic plots of log(ate) vs. log(te), the gradient of which has
been defined by Struik (3) as:
(1)

where D(t), the creep compliance, 5 e/s where e is the
measured strain and s is the applied stress, t0 is a
characteristic retardation time and b a shape param-
eter for each creep curve. D0 is a fitting parameter. For
a given temperature and strain, and assuming that b
is independent of aging time, it is possible to perform
time-aging time superposition of the data by reducing
the curves to a reference aging time via a horizontal
shift along time axis. The aging time shift factor ate is
then defined from the KWW function as:
log@ a te # 5 log @ t 0 ( t e ) / t 0 ( t ref )#
m 5 d log( a te ) /d log( t e ) , (3)
where m is often referred to as the shift rate.
In general, if the shape of the creep curve is unal-
tered as aging time progresses, we consider that time-
aging time superposition (TAS) can apply. Hence, the
TAS is not limited to the KWW type of creep function,
but any function that describes the data can be used.
Finally, it is normally found that slight shifts in the
magnitude of the creep compliance are often needed to
superimpose the data. These vertical shifts represent
(2) a change in the strength of the retardation (creep)

Fig. 1. Double logarithmic representation of creep compliance vs. time for samples of syndiotactic polystyrene (SPS300F) “normalized”
at 160°C and quenched to 70°C where “sequential” aging tests were performed. Aging times were: (h) 1800 s; (E) 3600 s; (‚) 7200 s;
() 14,400 s; ({) 28,800 s; (1) 57,600 s; (3) 115,600 s; (✳) 230,400 s. Reduced curve produced by combination of vertical and
horizontal shifts is shown displaced arbitrarily for clarity. Applied stress 5 5 MPa.

1460 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 1997, Vol. 37, No. 9
 Physical Aging Kinetics of Syndiotactic Polystyrene

Fig. 2. Double logarithmic representation of creep compliance vs. time for samples of syndiotactic polystyrene (SPS300F) “normalized”
at 160°C and quenched to 90°C where “sequential” aging tests were performed. Aging times were: (h) 1800 s; (E) 3600 s; (‚) 7200 s;
(ƒ) 14,400 s; ({) 28,800 s; (1) 57,600 s; (3) 115,600 s; (✳) 230,400 s. Reduced curve produced by combination of vertical and
horizontal shifts is shown displaced arbitrarily for clarity. Applied stress 5 5 MPa.

process, and, in the context of the KWW function, can
be written as:
b te 5 D 0 ( t e ) /D 0 ( t e,ref )
These will be found to be particularly important .Tg.
EXPERIMENTS
Materials
Four samples of syndiotactic polystyrene were pro-
vided to NIST by Dow in the form of dumbbell- shaped
specimens produced by injection molding (12). Their
designations and some comments describing their vi-
sual appearances are presented in Table 1. Two of
these samples were used in the physical aging exper-
iments: The SPS300F, which was injected into a hot
mold (300°F; 149°C) and contained a nucleating
agent, and the SPSA, which was injected into a mold
held at 140°F (60°C) and contained no nucleating
agent. All samples were “normalized” for 1 h at 160°C
before quenching to the aging (testing) temperature
because of possible effects cold crystallization could
have on the physical aging measurements that would
lead to difficulty in experimental reproducibility.
Creep Tests
The mechanical tests were carried out in uniaxial
extension in creep conditions. The mechanical tests
were performed in load control using a computer-con-
trolled servo-hydraulic testing machine (Instron
model 132.25), equipped with an oven specially de-
signed for a rigorous temperature control. The tem-
(4) perature was controlled using a Cole Parmer Digi-
Sense Model 2186-20 temperature controller. Oven
stability was 6 0.2°C during each experiment. The
temperature gradient over the gauge length of the
sample was 6 0.2°C as determined from thermocou-
ple measurements. Sample strain was measured with
an extensometer Instron (12) Model 2620-259 at-
tached to the sample.
Aging Tests
The aging experiments were carried out by first an-
nealing the specimens at 160°C for 1 h. They were
then placed in the test machine at the aging test tem-
perature, and the sequence of aging “probe” stresses
in creep was applied. Experiments were performed at
aging test temperatures of 60, 70, 80, 82.5, 85, 90, 95,
100, 110, and 120°C. The experimental temperature
range encompasses region 1, region 2, and the very
lower end of region 3 of the four characteristic tem-
perature regions defined by Struik (4 – 8).
The loading history applied to the sample after the
quench, followed the protocol developed by Struik:
after quenching the samples to the aging test temper-
ature, the creep tests were started sequentially at in-
creasing aging times, te. The duration of the load ap-
plication, t l, was also increased to keep the ratio tl/te

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 Jorg Beckmann et al.

Fig. 3. Double logarithmic representation of creep compliance vs. time for samples of syndiotactic polystyrene (SPS300F) “normalized”
at 160°C and quenched to 95°C where “sequential” aging tests were performed. Aging times were: (h) 1800 s; (E) 3600 s; (‚) 7200 s;
(ƒ) 14,400 s; ({) 28,800 s; (1) 57,600 s; (3) 115,600 s; (✳) 230,400 s. Time-aging time superposition was not possible for these data.
Applied stress 5 5 MPa.

Fig. 4. Double logarithmic representation of creep compliance vs. time for samples of syndiotactic polystyrene (SPS300F) “normalized”
at 160°C and quenched to 110°C where “sequential” aging tests were performed. Aging times were: (h) 1800 s; (E) 3600 s; (‚) 7200 s;
(ƒ) 14,400 s; ({) 28,800 s; (1) 57,600 s; (3) 115,600 s; (✳) 230,400 s. Reduced curve produced by (primarily) vertical shifts is shown
displaced arbitrarily for clarity. Applied stress 5 5 MPa.

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 Physical Aging Kinetics of Syndiotactic Polystyrene

Fig. 5. Double logarithmic representation of creep compliance vs. time for samples of syndiotactic polystyrene (SPS300F) “normalized”
at 160°C and quenched to 120°C where “sequential” aging tests were performed. Aging times were: (h) 1800 s; (E) 3600 s; (‚) 7200 s;
(ƒ) 14,400 s; ({) 28,800 s; (1) 57,600 s; (3) 115,600 s; (✳) 230,400 s. Reduced curve produced by (primarily) vertical shifts is shown
displaced arbitrarily for clarity. Applied stress 5 5 MPa.

Table 2. Vertical Shift Factors bte Required to Superimpose was observed for these temperatures. Furthermore
the Creep Curves at Different Aging Times and at 110 and the curve shape can be described with the KWW Eq 1.
120°C for Samples SPS300F and SPS140A.
Many amorphous polymers have been found to follow
SPS 140A SPS300F SPS 140A SPS 300F Eq 1 with a value of b 5 1⁄3 and, for the sPS at 60, 70
T 5 120°C T 5 120°C T 5 110°C T 5 110°C and 80°C, we also find b 5 1⁄3. Figure 1 also shows the
te/S bte bte bte bte “offset” “master curve,” which is the result of the su-
1800 0.99 0.90 0.87 0.94 perimposed creep curves measured at different aging
3600 0.95 0.89 0.90 0.95 times shifted horizontally on the logarithmic timescale.
7200 0.95 0.91 0.92 0.95 In experiments at 82.5, 85 and 90°C, we found that
14,400 0.96 0.92 0.94 0.95
28,800 0.96 0.93 0.96 0.96 the KWW function did not fit the full range of the data.
57,600 0.98 0.95 0.97 0.98 At 82.5°C, the KWW function describes the creep re-
115,200 0.99 0.98 0.98 1.00 sponse only up to ;4000 sec and the exponent b
230,400 1.00 1.00 1.00 1.00 decreases slightly to 0.28 in the short time interval.
The deviation of the creep response from the KWW
behavior is more pronounced at 85 and 90°C. At 85°C,
constant at 0.1. An engineering stress of 5 MPa was the KWW function can only fit the creep behavior up to
applied to the samples. The zero aging time was cho- 500 sec with an exponent of b 5 0.1. Above this time
sen to be the time at which the samples attained the a constant double logarithmic creep rate m 5 0.2 was
testing (aging) temperature. observed (power law response). Despite these factors,
the individual curves at each of these temperatures,
RESULTS while not represented by the KWW function, are still
superimposable to create a master curve, as depicted
300F Polymer: Time-Aging Time Superposition in Fig. 2 for the 90°C data.
In this section we present the results from aging At 95°C (Fig. 3) we see that the short time creep
experiments in which the material was “probed” using responses are virtually independent of aging time and
sequential creep tests (13). Figure 1 shows the aging of the double logarithmic creep rate at long creep times
the SPS300F at 70°C. Similar behavior was observed decreases with increasing aging time. The opposite
at both 60 and 80°C. The typical aging as seen in Fig. behavior was observed for the responses at 100 and
1 as a shift of the creep behavior towards longer times 105°C. The creep curves are different in the short

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 Jorg Beckmann et al.

Fig. 6. Double logarithmic representation of the aging time shift factor ate vs. aging time te for syndiotactic polystyrene (SPS300F) at
the temperatures indicated. Data not shown at 95°C and 100°C because time-aging time superposition could not be performed on data
from these temperatures.

timescale but tend towards a common plateau value which may be due to increasing crystallinity. The ver-
as the aging time is increased. The change of shape of tical shifts for 110 and 120°C are presented in Table 2.
the creep responses at different aging times does not To characterize the aging in detail for the different
allow a master curve construction. Hence, time-aging regions the double logarithmic aging rate m (Eq. 3) can
time superposition in the range 95 to 105°C is not be determined from aging time shift factors ate ob-
possible. tained in producing the master curves in the temper-
Figures 4 and 5 show the creep behavior of sPS for ature regions where time-aging time superposition is
different aging times at 110 and 120°C, well above the applicable. Figure 6 shows how the aging of the
Tg of the sPS. Interestingly, master curves could be SPS300F depends on temperature for the creep data
constructed for the creep responses depicted in Figs. 4 described in the preceding paragraphs. We readily see
and 5 using only vertical shift factors with no horizon- that the slopes of the curves decrease as the aging
tal shift. This implies a stiffening of the material with- temperature increases and that at 110 and 120°C the
out any change in the viscoelastic response itself, aging (of the viscoelastic response) ceases. The reader
is cautioned to recall that between 95 and 105°C time-
Table 3. Initial Value of Double Logarithmic Shift Rate m for aging time superposition could not be applied, al-
sPS 300F and 140A Materials at Different Temperatures. though the responses did not change dramatically
with aging time in that region. In Table 3 are gathered
Temperature m 5 d log(ate)/d log(te) m 5 d log(ate)/d log(te)
(°C) for 300F Material for 140A Material
the shift rates m at different temperatures, calculated
from the initial slope of the curves shown in Fig. 6.
60 0.89 not measured Importantly, Fig. 6 and Table 3 indicate a pronounced
70 0.87 0.95
80 0.68 0.82
temperature dependence of m at temperatures be-
82.5 0.37 0.79 tween Tg – 25°C and Tg 1 25°C.
85 0.35 0.73
90 0.32 no superposition 140A Polymer: Time-Aging Time Superposition
95 no superposition no superposition
100 no superposition no superposition This section describes the results of the physical
110 0 0 aging characterization of the 140A material. The over-
120 0 0
all behavior is similar to that of the SPS300F material

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 Physical Aging Kinetics of Syndiotactic Polystyrene

Fig. 7. Double logarithmic representation of creep compliance vs. time for samples of syndiotactic polystyrene (SPS140A) “normalized”
at 160°C and quenched to 70°C where “sequential” aging tests were performed. Aging times were: (h) 1800 s; (E) 3600 s; (‚) 7200 s;
(ƒ) 14,400 s; ({) 28,800 s; (1) 57,600 s; (3) 115,600 s; (✳) 230,400 s. Reduced curve produced by combination of vertical and
horizontal shifts is shown displaced arbitrarily for clarity. Applied stress 5 5 MPa.

Fig. 8. Double logarithmic representation of creep compliance vs. time for samples of syndiotactic polystyrene (SPS140A) “normalized”
at 160°C and quenched to 85°C where “sequential” aging tests were performed. Aging times were: (h) 1800 s; (E) 3600 s; (‚) 7200 s;
(ƒ) 14,400 s; ({) 28,800 s; (1) 57,600 s; (3) 115,600 s; (✳) 230,400 s. Reduced curve produced by combination of vertical and
horizontal shifts is shown displaced arbitrarily for clarity. Applied stress 5 5 MPa.

POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 1997, Vol. 37, No. 9 1465
 Jorg Beckmann et al.

Fig. 9. Double logarithmic representation of creep compliance vs. time for samples of syndiotactic polystyrene (SPS300F) “normalized”
at 160°C and quenched to 90°C where “sequential” aging tests were performed. Aging times were: (h) 1800 s; (E) 3600 s; (‚) 7200 s;
(ƒ) 14,400 s; ({) 28,800 s; (1) 57,600 s; (3) 115,600 s; (✳) 230,400 s. Time-aging time superposition was not possible for these data.
Applied stress 5 5 MPa.

described previously. Even though a 160°C normal-
ization was performed prior to the aging experiments,
there are subtle differences in detail that indicate an
influence of the processing conditions on the aging
process.
Figure 7 depicts the aging response at 70°C for the
140A material. As in the case of the 300F material,
time aging time superposition holds for this material
and at the temperatures investigated up to 80°C, a
KWW function with constant b ' 1⁄3 fits the data. In
measurements at 82.5 through 85°C the behavior is
no longer systematically KWW in nature, but the
curves can still be superimposed by a combination of
vertical and horizontal shifts (see Fig. 8). In Fig. 9 we
show the creep responses at different aging times for
90°C. Non-superposability is observed for the different
aging times in the 90°C experiments as well as those
carried out at 95 and 100°C, a result that is somewhat
different from what was observed for the 300F mate-
rial where superposability was possible up to 95°C.
Figure 10 shows the aging response at 120°C. In
this data set, as well as that at 110°C, the superpos-
ability of the creep responses at different aging times
is primarily performed by vertical shifting, indicating
no significant change in the retardation times due to
aging at these temperatures. Rather, vertical shifts
indicate a change in the intensity of the retardation
processes. As discussed later, this behavior is atypical
of semicrystalline polymers. The vertical shift factors
for the SPS140A material are presented in Table 2.
Figure 11 summarizes the aging data for the 140A
material in a plot of log (ate) vs. log (te). We note that the
aging rates [slopes of the log (ate) vs. log (te) curves]
differ subtly from the data of Fig. 6 for the 300F ma-
terial. In effect, at 85°C the aging rate for the 140A
material is somewhat higher than for the 300F mate-
rial at the same temperature. Because the curves at
90 to 100°C and 95 to 100°C are non-superposable,
the comparison of the aging rates is not so straight-
forward. Close examination of the data, however, sug-
gests that the 300F material is more stable at these
temperatures than is the 140A material. The aging
shift rates m for both the 140A and 300F materials are
compared in Table 3.
DISCUSSION AND IMPLICATIONS
The aging of sPS, as measured by sequential creep
experiments subsequent to a quench from a “normal-
ization” temperature of 160°C is significantly different
from that observed in most semicrystalline polymers.
The experimental observations suggest that the sPS
behaves much like an amorphous polymer below Tg,
while above Tg the response is unlike either amor-
phous materials or other semicrystalline polymers.
These are discussed point by point below.
Behavior Below Tg: The creep compliance behavior
of the sPS at different aging times is similar to those
observed for amorphous polymers in general, viz., the
viscoelastic response can be represented by a time-

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 Physical Aging Kinetics of Syndiotactic Polystyrene

Fig. 10. Double logarithmic representation of creep compliance vs. time for samples of syndiotactic polystyrene (SPS140A) “normal-
ized” at 160°C and quenched to 120°C where “sequential” aging tests were performed. Aging times were: (h) 1800 s; (E) 3600 s; (‚)
7200 s; (ƒ) 14,400 s; ({) 28,800 s; (1) 57,600 s; (3) 115,600 s; (✳) 230,400 s. Reduced curve produced by (primarily) vertical shifts
is shown displaced arbitrarily for clarity. Applied stress 5 5 MPa.

aging time superposition and the double logarithmic
shift rate m is near to unity well below Tg and decreases
to zero as temperature increases to and above Tg.
Behavior Near Tg: Near the Tg (95 to 105°C) the creep
behavior does change as aging time increases. While
the changes in creep are small, time-aging time su-
perposition can still not be applied to the results. In
this temperature range, there is little volume recovery
response. The observed behavior in this range is dif-
ferent from that in other semicrystalline polymers (cf.,
Refs. 4 – 8). In other semicrystalline materials the ag-
ing of the viscoelastic response continues as strongly
as (sometimes more strongly than) well below Tg.
Behavior Above Tg: For creep compliance response
changes upon aging, however, there is no apparent
change in the characteristic viscoelastic retardation
time. Rather, all of the changes can be expressed as a
simple increase in the material stiffness, which is pre-
sumably due to changes in the crystalline phase, e.g.,
degree of crystallinity, crystallite size distribution or
secondary recrystallization. Such a response is differ-
ent from either that of the amorphous material or
other semicrystalline materials. For the former, phys-
ical aging of any sort ceases, while for the latter, aging
effects seem to be stronger above Tg (see, e.g., Ref. 8.)
than below it.
Implications: The above picture presents an inter-
esting set of possibilities for the sPS. While the
changes in viscoelastic properties below Tg are similar
to those associated with aging in both amorphous and
semicrystalline polymers, the behavior above Tg is dif-
ferent. Upon aging, only the stiffness increases, while
the viscoelastic component of the response remains
the same. Consequently, the viscoelastic dissipation
in the material remains constant and one might an-
ticipate less embrittlement upon aging at high temper-
atures than might be otherwise anticipated, although
fracture toughness investigations have not been a part
of this study.
Effects of Molding History: Finally, we note that the
two different materials investigated here exhibited
somewhat different aging behaviors. In particular, the
140A material showed a more rapid change in the
viscoelastic response with increasing aging time in the
vicinity of Tg. The reasons for this are unclear at this
time. The differences in the morphologies have not
been investigated systematically. However, it should
be noted that the 140A material did not contain a
nucleating agent, while the 300F material did. Fur-
thermore, the as-received materials were visually dif-
ferent. The 140A material had a clear surface with a
turbid core, while the 300F material was completely
turbid. The differences in aging are subtle, but sug-
gest that either a) the material with the nucleating
agent resists aging in the vicinity of Tg better than does
the sample with no nucleating agent or b) molding at a
temperature . Tg (300F material) results in a more
stable material than molding , Tg (140A material).

POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 1997, Vol. 37, No. 9 1467
 Jorg Beckmann et al.

Fig. 11. Double logarithmic representation of the aging time shift factor ate vs. aging time te for syndiotactic polystyrene (SPS300F) at
the temperatures indicated. Data not shown at 90°C, 95°C and 100°C because time-aging time superposition could not be performed
on data from these temperatures.

ACKNOWLEDGMENTS 7. L. C. E. Struik, Polymer, 30, 815 (1989).

This work was sponsored, in part, through a Coop-
erative Research and Development Agreement be-
tween the Dow Chemical Company and the National
Institute of Standards and Technology. Dr. Beckmann
thanks the University of Potsdam, Potsdam, Ger-
many, which also provided partial support for his stay
at NIST. The authors would also like to thank Dr.
Craig Carriere of the Dow Chemical Company for
many stimulating discussions during the course of
this work.
REFERENCES
1. A. J. Kovacs, Fortsch. Hochpolymer Forschung, 3, 394
(1963).
2. G. B. McKenna, in Comprehensive Polymer Science. Vol.
2, Polymer Properties, p. 311, C. Booth and C. Price, eds.,
Pergamon, Oxford, England (1989).
3. L. C. E. Struik, Physical Aging in Amorphous Polymers
and Other Materials Elsevier, Amsterdam (1978).
4. L. C. E. Struik, Polymer, 28, 1521 (1987).
5. L. C. E. Struik, Polymer, 28, 1534 (1987).
6. L. C. E. Struik, Polymer, 30, 799 (1989).
8. I. Spinu and G. B. McKenna, Polym. Eng. Sci., 34, 1808
(1994).
9. Dow Chemical Company internal data.
10. F. Kohlrausch, Pogg. Ann. Phys., 12, 393 (1847).
11. G. Williams and D. C. Watts, Trans. Faraday Soc., 66,
80 (1970).
12. Certain commercial materials and equipment are iden-
tified in this paper to specify adequately the experimen-
tal procedure. In no case does such identification imply
recommendation or endorsement by the National Insti-
tute of Standards and Technology, nor does it imply
necessarily that the product is the best available for the
purpose.
13. The creep and aging data reported here are typical of
those obtained by us (8, 14) and others (4 –7) on similar
equipment and with similar methods. Typically the creep
compliance measurements and the ability to determine
superposability are limited by the machine capabilities
and temperature stability of the measurement and the
resulting aging time shift factors are reliable to within
about 0.1 log10 units in isothermal measurements. Sta-
tistical estimates of the fitting parameters to the KWW
function are less meaningful because the parameters are
interdependent (not orthogonal in parameter space) and
we refrain from putting uncertainty estimates on them.
14. A. Lee and G. B. McKenna, Polymer, 29, 1812 (1988).

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