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

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

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

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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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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.

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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- Figure 11 summarizes the aging data for the 140A
ization was performed prior to the aging experiments, material in a plot of log (ate) vs. log (te). We note that the
there are subtle differences in detail that indicate an aging rates [slopes of the log (ate) vs. log (te) curves]
influence of the processing conditions on the aging differ subtly from the data of Fig. 6 for the 300F ma-
process. terial. In effect, at 85°C the aging rate for the 140A
Figure 7 depicts the aging response at 70°C for the material is somewhat higher than for the 300F mate-
140A material. As in the case of the 300F material, rial at the same temperature. Because the curves at
time aging time superposition holds for this material 90 to 100°C and 95 to 100°C are non-superposable,
and at the temperatures investigated up to 80°C, a the comparison of the aging rates is not so straight-
KWW function with constant b ' 1⁄3 fits the data. In forward. Close examination of the data, however, sug-
measurements at 82.5 through 85°C the behavior is gests that the 300F material is more stable at these
no longer systematically KWW in nature, but the temperatures than is the 140A material. The aging
curves can still be superimposed by a combination of shift rates m for both the 140A and 300F materials are
vertical and horizontal shifts (see Fig. 8). In Fig. 9 we compared in Table 3.
show the creep responses at different aging times for
90°C. Non-superposability is observed for the different
DISCUSSION AND IMPLICATIONS
aging times in the 90°C experiments as well as those
carried out at 95 and 100°C, a result that is somewhat The aging of sPS, as measured by sequential creep
different from what was observed for the 300F mate- experiments subsequent to a quench from a “normal-
rial where superposability was possible up to 95°C. ization” temperature of 160°C is significantly different
Figure 10 shows the aging response at 120°C. In from that observed in most semicrystalline polymers.
this data set, as well as that at 110°C, the superpos- The experimental observations suggest that the sPS
ability of the creep responses at different aging times behaves much like an amorphous polymer below Tg,
is primarily performed by vertical shifting, indicating while above Tg the response is unlike either amor-
no significant change in the retardation times due to phous materials or other semicrystalline polymers.
aging at these temperatures. Rather, vertical shifts These are discussed point by point below.
indicate a change in the intensity of the retardation Behavior Below Tg: The creep compliance behavior
processes. As discussed later, this behavior is atypical of the sPS at different aging times is similar to those
of semicrystalline polymers. The vertical shift factors observed for amorphous polymers in general, viz., the
for the SPS140A material are presented in Table 2. 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 to those associated with aging in both amorphous and
shift rate m is near to unity well below Tg and decreases semicrystalline polymers, the behavior above Tg is dif-
to zero as temperature increases to and above Tg. ferent. Upon aging, only the stiffness increases, while
Behavior Near Tg: Near the Tg (95 to 105°C) the creep the viscoelastic component of the response remains
behavior does change as aging time increases. While the same. Consequently, the viscoelastic dissipation
the changes in creep are small, time-aging time su- in the material remains constant and one might an-
perposition can still not be applied to the results. In ticipate less embrittlement upon aging at high temper-
this temperature range, there is little volume recovery atures than might be otherwise anticipated, although
response. The observed behavior in this range is dif- fracture toughness investigations have not been a part
ferent from that in other semicrystalline polymers (cf., of this study.
Refs. 4 – 8). In other semicrystalline materials the ag- Effects of Molding History: Finally, we note that the
ing of the viscoelastic response continues as strongly two different materials investigated here exhibited
as (sometimes more strongly than) well below Tg. somewhat different aging behaviors. In particular, the
Behavior Above Tg: For creep compliance response 140A material showed a more rapid change in the
changes upon aging, however, there is no apparent viscoelastic response with increasing aging time in the
change in the characteristic viscoelastic retardation vicinity of Tg. The reasons for this are unclear at this
time. Rather, all of the changes can be expressed as a time. The differences in the morphologies have not
simple increase in the material stiffness, which is pre- been investigated systematically. However, it should
sumably due to changes in the crystalline phase, e.g., be noted that the 140A material did not contain a
degree of crystallinity, crystallite size distribution or nucleating agent, while the 300F material did. Fur-
secondary recrystallization. Such a response is differ- thermore, the as-received materials were visually dif-
ent from either that of the amorphous material or ferent. The 140A material had a clear surface with a
other semicrystalline materials. For the former, phys- turbid core, while the 300F material was completely
ical aging of any sort ceases, while for the latter, aging turbid. The differences in aging are subtle, but sug-
effects seem to be stronger above Tg (see, e.g., Ref. 8.) gest that either a) the material with the nucleating
than below it. agent resists aging in the vicinity of Tg better than does
Implications: The above picture presents an inter- the sample with no nucleating agent or b) molding at a
esting set of possibilities for the sPS. While the temperature . Tg (300F material) results in a more
changes in viscoelastic properties below Tg are similar stable material than molding , Tg (140A material).

POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 1997, Vol. 37, No. 9 1467
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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).
8. I. Spinu and G. B. McKenna, Polym. Eng. Sci., 34, 1808
This work was sponsored, in part, through a Coop- (1994).
erative Research and Development Agreement be- 9. Dow Chemical Company internal data.
10. F. Kohlrausch, Pogg. Ann. Phys., 12, 393 (1847).
tween the Dow Chemical Company and the National 11. G. Williams and D. C. Watts, Trans. Faraday Soc., 66,
Institute of Standards and Technology. Dr. Beckmann 80 (1970).
thanks the University of Potsdam, Potsdam, Ger- 12. Certain commercial materials and equipment are iden-
many, which also provided partial support for his stay tified in this paper to specify adequately the experimen-
at NIST. The authors would also like to thank Dr. tal procedure. In no case does such identification imply
recommendation or endorsement by the National Insti-
Craig Carriere of the Dow Chemical Company for tute of Standards and Technology, nor does it imply
many stimulating discussions during the course of necessarily that the product is the best available for the
this work. purpose.
13. The creep and aging data reported here are typical of
REFERENCES those obtained by us (8, 14) and others (4 –7) on similar
equipment and with similar methods. Typically the creep
1. A. J. Kovacs, Fortsch. Hochpolymer Forschung, 3, 394 compliance measurements and the ability to determine
(1963). superposability are limited by the machine capabilities
2. G. B. McKenna, in Comprehensive Polymer Science. Vol. and temperature stability of the measurement and the
2, Polymer Properties, p. 311, C. Booth and C. Price, eds., resulting aging time shift factors are reliable to within
Pergamon, Oxford, England (1989). about 0.1 log10 units in isothermal measurements. Sta-
3. L. C. E. Struik, Physical Aging in Amorphous Polymers tistical estimates of the fitting parameters to the KWW
and Other Materials Elsevier, Amsterdam (1978). function are less meaningful because the parameters are
4. L. C. E. Struik, Polymer, 28, 1521 (1987). interdependent (not orthogonal in parameter space) and
5. L. C. E. Struik, Polymer, 28, 1534 (1987). we refrain from putting uncertainty estimates on them.
6. L. C. E. Struik, Polymer, 30, 799 (1989). 14. A. Lee and G. B. McKenna, Polymer, 29, 1812 (1988).

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