Polymer Degradation and Stability 90 (2005) 395e404

www.elsevier.com/locate/polydegstab

Review article

Accelerated aging and lifetime prediction: Review of

non-Arrhenius behaviour due to two competing processes
M. Celina*,1, K.T. Gillen, R.A. Assink
Sandia National Laboratories, PO Box 5800, MS 1411, Department 1811, Albuquerque, NM 87185-1411, USA
Received 12 April 2005; accepted 12 May 2005
Available online 5 July 2005

Abstract

Lifetime prediction of polymeric materials often requires extrapolation of accelerated aging data with the suitability and
confidence in such approaches being subject to ongoing discussions. This paper reviews the evidence of non-Arrhenius
behaviour (curvature) instead of linear extrapolations in polymer degradation studies. Several studies have emphasized
mechanistic variations in the degradation mechanism and demonstrated changes in activation energies but often data have not
been fully quantified. To improve predictive capabilities a simple approach for dealing with curvature in Arrhenius plots is
examined on a basis of two competing reactions. This allows for excellent fitting of experimental data as shown for some
elastomers, does not require complex kinetic modelling, and individual activation energies are easily determined. Reviewing
literature data for the thermal degradation of polypropylene a crossover temperature (temperature at which the two processes
equally contribute) of w83
C was determined, with the high temperature process having a considerably higher activation
energy (107e156 kJ/mol) than the low temperature process (35e50 kJ/mol). Since low activation energy processes can dominate
at low temperatures and longer extrapolations result in larger uncertainties in lifetime predictions, experiments focused on
estimating Ea values at the lowest possible temperature instead of assuming straight line extrapolations will lead to more
confident lifetime estimates.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Accelerated aging; Polymer; Aging; Thermal degradation; Lifetime prediction; Extrapolation; Performance; Material selection; Arrhenius;
Curvature

1. Introduction
Lifetime prediction studies on polymeric materials
rely heavily on the use of accelerated thermal aging
exposures. Failure times or degradation rates are
determined at elevated temperatures and these data are
used to extrapolate material performance to ambient
conditions. The most important methodology for such
extrapolations that is applied in polymer aging studies
* Corresponding author. Tel.: C1 505 8453551; fax: C1 505
8449781.
E-mail address: mccelin@sandia.gov (M. Celina).
1
Under contract.
and has been used for decades is based on the Arrhenius
relationship. Arrhenius extrapolations assume that
a chemical degradation process is controlled by a re-
action rate k proportional to exp (Ea/RT ), where Ea is
the Arrhenius activation energy, R the gas constant
(8.314 J/mol-K), T the absolute temperature and A the
pre-exponential factor (Eq. (1)). Therefore, a log-plot
of reactions rates (k) or degradation times (1/k) versus
inverse temperature (1/T ) is expected to result in
a straight line, allowing simple extrapolations to lower
temperatures.
 
Ea Ea
kZA!exp or ln kZln AC ð1Þ
RT RT

0141-3910/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2005.05.004
396 M. Celina et al. / Polymer Degradation and Stability 90 (2005) 395e404
There have been some discussions whether a com-
plex thermal degradation process based on free radical
reaction sequences (basic auto-oxidation scheme) with
many individual reaction steps, first demonstrated in the
1940se1950s by Bolland, Bateman et al. [1e3], should
indeed follow simple Arrhenius behaviour [4]. Despite
such concerns, many studies have clearly demonstrated
that some degradation processes can be well described
by a simple linear Arrhenius relationship even if
individual rate constants within the overall process
may have their own temperature dependencies [5e8].
While perhaps not always consistent with a specific
detailed kinetic model, a simple Arrhenius relationship
most importantly should allow for empirical material
lifetime prediction [4,5].
Perhaps the key weakness in testing linear Arrhenius
behaviour is often the limited availability of experimen-
tal data [4]. Accelerated aging data may be available
within a time frame of days to a year, or at the best
several years. Often data spanning two or three orders of
magnitude must be extrapolated an additional one or
two orders of magnitude in order to address ambient
aging conditions that may involve decades of aging.
Such issues and intrinsic limitations for empirical
extrapolations will be discussed in more detail in
a separate publication. To enhance our confidence in
Arrhenius extrapolations, more comprehensive data sets
covering a larger temperature range and requiring high
dynamic experimental sensitivity are required [4].
Perhaps the best experimental method allowing for the
collection of more comprehensive data sets, is ultra-
sensitive oxygen uptake measuring thermal polymer
oxidation rates [4,5,8,9].
Over the years many of the more comprehensive
materials’ aging studies have resulted in unambiguous
support for complex aging phenomena where a linear
Arrhenius relationship is insufficient to match the
observed aging data [4,6e8,10e15]. In some instances
simple diffusion limited oxidation (DLO) effects at high
temperatures are responsible for curvature in Arrhenius
plots resulting in longer aging times than for nonDLO
conditions [6]. Some examples were discussed as pro-
viding evidence for mechanistic variations or limitations
in lifetime predictions, but not necessarily analysed to
yield individual activation energies [12e14]. It is obvious
that curvature towards lower activation energies when
approaching lower temperatures would lead to overly
optimistic lifetimes based on high temperature extra-
polation. In some of these studies it was therefore
attempted to distinguish between a dominant high and
low temperature degradation processes, justifying vary-
ing activation energies for different temperature ranges
[4,7,8,10,11,15]. Individual activation energies were then
determined via selective linear approximations over
a specific temperature range [4,7,8,10,11,15]. In other
instances, potential evidence of curvature in some data
sets was actually discarded or rather treated as
experimental noise to allow fitting with the ‘preferred
model’ of a linear Arrhenius relationship [16]. In some
alternative approaches for dealing with curvature,
modified Arrhenius-based mathematical models using
compensation effects and challenging traditional
Arrhenius treatment of data were suggested [17], or
more complex kinetic schemes were considered to better
explain some observations [14]. It is certainly surprising,
but there appears to be no evidence in any of these
studies that a simple mathematical treatment was
applied to the observed non-Arrhenius curvature.
This paper reviews the many instances in thermal
polymer aging studies where evidence of curvature in
Arrhenius plots has been observed. While perhaps not
complete the most important studies that emphasized
curvature and thus suggested important high and low
temperature mechanistic variations have been identified.
Using published data the non-Arrhenius behaviour is
then approximated in its simplest form as a combination
of two independent reactions with individual rate
constants, leading to the concept of one clearly defined
high and low temperature degradation process, and
allowing for individual Ea’s to be determined. This is
a first-order approximation and some material aging
undoubtedly may involve more than two processes. For
instance it may be found that a third process with an Ea
value higher than either of the other two Ea values enters
at even higher aging temperatures such as those probed
by traditional short-term exposures in TGA (thermo-
gravimetric analysis) or OIT (oxygen induction time)
experiments.
2. Discussion
2.1. Previous evidence for non-Arrhenius behaviour
or limitations in lifetime predictions
Over the last four decades many degradation studies
have dealt with the complexity of polymer lifetime
prediction and extrapolations, either by measuring
mechanical or similar degradation indicators over a large
temperature range, thereby establishing the basis for
predictions, or by focusing on limitations in straight line
Arrhenius extrapolations. It is interesting to note how
trends in these studies over the years reflect on the
evolution of more sensitive analytical techniques, better
stabilization of materials and an overall improved
understanding of polymer aging phenomena.
Perhaps the first to point out the limitations in
estimating the useful life of polypropylene (PP) com-
pounds based on elevated temperature tests carried out
between 70 and 160
C were Tamblyn and Newland in
1965 who discussed curvature in the Arrhenius plot of
induction times of unstabilised PP and crossover effects
 M. Celina et al. / Polymer Degradation and Stability 90 (2005) 395e404
in thermal performance of various stabilized compounds
[18]. They concluded that more sensitive techniques
would be required for improved predictions, but no
activation energies or details of curvature were dis-
cussed. Also for PP degradation (investigated between
75 and 140
C), Oswald and Turi argued for possible
overestimation of lifetimes by oxygen consumption
techniques and expressed caution for low temperature
extrapolations, particularly with respect to chain scis-
sion of tie molecules at the interlamellae regions leading
to early embrittlement [19]. In 1970, Richters presented
detailed data on the induction times of unstabilised PP
degradation using oxygen absorption over a larger
temperature range (50e150
C) [12]. There was clear
evidence of curvature in the Arrhenius plot towards
lower temperatures. No activation energy determination
was reported. Incidentally, Richters also discussed the
observation of localized aging phenomena with dark
spots originating around foreign particles (metal con-
tamination) well before the end of the induction period
seen in oxygen absorption.
Howard and Gilroy commented on accelerated aging
and lifetime prediction of some stabilized polyethylene
formulations between 120 and 180
C [20]. They
concluded that high temperature aging above the
melting point could be measured by either differential
thermal analysis (DTA) [21] or oxygen uptake [9]
probing the same degradation chemistry but that
caution should be applied to Arrhenius extrapolations
due to physical changes (stabilizer solubility and
morphology) in the material at lower temperatures.
Bernstein and Lee similarly probed high density poly-
ethylene cable materials using oven aging (between 105
and 190
C) and OITeDSC (between 170 and 205
C)
[22]. They showed a discontinuity in the Arrhenius
plot at the melting point (w130
C) between the DSC
data and oven aging, with importantly no correlation
between the two techniques. OIT data seemed to follow
a linear process with 156 kJ/mol and oven aging
displayed curvature at the higher temperatures with
a linear process of w100 kJ/mol for the low temperature
range (below w150
C). Billingham et al. in an excellent
review in 1981 critically evaluated the use of DTA and
thereby addressed the issue of fast high temperature
tests providing data for lifetime prediction [23]. They
emphasized that extrapolations below the melting point
are complicated by crystallization effects leading to
mechanistic changes, and also stressed that while an
attractive technique, extrapolation of DTA data to
predict polymer stability, or even the efficiency of
different stabilizers at RT, is inexact. Perhaps not
directly an example of accelerated aging tests, but
worthwhile to mention in this context are the early
failures observed in the 1980s of stabilized polyethylene
cable insulation due to stabilizer migration at lower
temperatures. This reflects on a mechanistic variation
397
that could not be adequately simulated by high temper-
ature accelerated aging due to changes in stabilizer
solubility, and demonstrated that extrapolations were
insufficient as a predictive tool [20,24e26].
Kramer and Koppelmann explored the use of iso-
thermal long-term differential thermal analysis (ILDTA)
to study the aging behaviour of polybutene and cross-
linked PE pipe materials [27]. The experiments covered
a temperature range of 120e240
C with remarkable
dynamic sensitivity of 5 orders of magnitude in the
maximum oxidation time measurements. The Arrhenius
plot for the XLPE showed curvature at w150
C with
activation energies quoted as 218 kJ/mol above and
144 kJ/mol below. For the polybutene data curvature
was observed at w180
C. Both cases demonstrated that
extrapolations from short-term experiments were not
possible. High temperature DTA experiments are most
likely subject to diffusion limited oxidation which would
explain the shorter response times at those conditions.
The authors did not stress this point but in some of the
figures it was implied that the lower temperature process
should linearly extrapolate to low temperatures. In
a second related study in 1987, Steiner and Koppelmann
used ILDTA and investigated the thermal degradation
of PP over a temperature range of 90e210
C covering
more than 4 orders of magnitude in experimental
duration [28]. Surprisingly, and in contrast to Bill-
ingham et al. [23] the data appeared to follow linear
Arrhenius behaviour with 212 kJ/mol for some stabi-
lized materials and 102 kJ/mol for the unstabilised PP.
A good correlation between DTA results and perfor-
mance at service conditions was implied. Gugumus
reviewed the use of accelerated aging tests for evaluation
of antioxidants and light stabilizers [29]. He concluded,
in agreement with Billingham [26] that DTA/DSC
experiments conducted in the melt were of little
predictive value for aging in the solid state, and further
that the problem of extrapolation of measurements
conducted in the solid at high temperatures had not
been solved satisfactorily.
Gijsman et al. studied the influence of catalyst
residues on the thermal degradation of unstabilised PP
at temperatures of 50e130
C [13]. They suggested
a temperature dependent hydroperoxide decomposition
mechanism responsible for initiation and controlling the
induction period via Ti catalysis at lower temperatures,
but purely thermal decomposition at higher tempera-
ture. No estimation of the Ea at the different tempera-
ture regimes was presented. In related studies they
commented on fast decomposing peracids and slow
decomposing hydroperoxides responsible for initiation
processes [30,31]. During the induction period these
hydroperoxides are initially formed with their decom-
position potentially catalysed by Ti residues. Langlois
et al. also in 1993 commented on mechanistic issues of
stabilizer consumption and lifetime prediction of XLPE
398 M. Celina et al. / Polymer Degradation and Stability 90 (2005) 395e404
[32]. Interestingly, they noted that an overall lifetime
could be regarded as the sum of individual processes,
where the sum of individual Arrhenian terms would be
non-Arrhenius (curvature), particularly important for
aging at lower temperatures. They also noted disconti-
nuities at the melting point with an offset in the
degradation rates but similar activation energy (i.e.
a multiplier in the pre-exponential factor). In an
intriguing study Achimsky et al. commented on
a transition temperature of w80
C for the thermal
degradation of polypropylene (studied between 50 and
150
C) with 101 kJ/mol above and 72 kJ/mol below
80
C [33]. Importantly, they demonstrated curvature
for the induction time, but not for a reasonably
stationary rate of carbonyl build-up data after the end
of the induction period. This led to the conclusion that
the underlying changes had to be related to the initiation
process. They also discussed the concept of competitive
processes, slow and fast decomposing hydroperoxides,
as well as a catalysed and non-catalysed initiation
processes to explain the existence of the two temperature
regimes.
Reviewing many data sets for polypropylene,
Gugumus presented a summary of various non-linear
Arrhenius aging behaviours for PP materials and PP
films including a ‘downward curvature’ at temperatures
below 80
C and an additional upward curvature for
some stabilized samples [14]. He explored the use of
better kinetic models to fit the data, but no activation
energies for individual temperature regimes were pro-
vided or a suitable kinetic scheme to fit the data could be
established [14]. This is not surprising considering the
complex temperature dependence that was shown for
some of these materials.
Gillen and co-workers in the mid 1990s were the first
group who utilized a GC based ultra-sensitive oxygen
consumption technique to probe the aging of polymers
by measuring oxidation rates over extended tempera-
ture ranges with the aim of gaining better confidence
for lifetime predictions [4e8,10,11,15,34e37]. As a
validation of the technique excellent correlations
were demonstrated between oxidation rates and time-
dependent changes in mechanical properties, as well as
experimentally observed oxidation profiles and pre-
dicted rate-dependent diffusion limited oxidation effects
[5,34e36]. For black nitrile and neoprene rubbers more
or less linear Arrhenius plots between 125
C e RT were
observed with activation energies of w88 kJ/mol and
w84 kJ/mol, respectively [5,35]. In 1997 Gillen et al.
showed significant curvature for the thermal degrada-
tion rates of a filled EPDM elastomer investigated from
52 to 170
C, and challenged traditional linear extrap-
olations when sufficient data are not available to show
curvature [4,38]. For this material activation energies of
w115 kJ/mol above, and w75 kJ/mol below w110
C
were provided, with the higher Ea process related to
increased production of CO2. This and several other
studies have provided evidence that CO2 formation is
related to a distinctly separate degradation process that
becomes more important at higher temperatures [10,15].
Celina and co-workers in 2000 [11,39,40] studied the
thermal degradation of an elastomeric polyurethane
binder over the temperature range of RT e 125
C.
Activation energies of 120 kJ/mol above, and 70 kJ/mol
below w70
C were determined. For a butyl elastomeric
seal material Gillen et al. demonstrated non-Arrhenius
behaviour with w100 kJ/mol above 80
C and 75 kJ/
mol below [7]. Recently Gillen et al. investigated two
polychloroprene cable jacket materials where they found
moderate drops in activation energies at low temper-
atures [15]. For one of the materials they compared
elongation results after 24 years of aging at 24
C with
earlier oven-aging results taken from 70
Ce131
C and
showed that the high temperature results had an Ea of
89 kJ/mol compared with the low temperature Ea of
71 kJ/mol (from 24
C to 70
C). For the second
material they found similar behaviour from oxygen
consumption results (96 kJ/mol at temperatures above
80
C versus 82 kJ/mol from 25
C to 80
C). In 2005
Gillen et al. also evaluated the thermal aging of various
chlorosulfonated polyethylene cable jacket materials
with evidence for curvature in mechanical properties
(elongation data) and oxidation rates for some of these
materials [10]. Activation energies were determined as
w102 kJ/mol for temperatures above 100
C and 88 kJ/mol
below.
2.2. Curvature in Arrhenius plots originating
from two individual processes
In many of the studies discussed above, temperature
dependent degradation time (tTi) or rate (kTi) data (Eq.
(2)) can be expressed most conveniently on the basis of
accelerative shift factors aTi describing the temperature
dependence of the degradation process, where shift
factors can be easily normalized to any temperature
desired (i.e. aTi Z 1 at the lowest temperature or RT ).
Any activation energy over a temperature range of
interest (T1eT2) can be determined via Eq. (3).
1
kTi Z faTi ð2Þ
tTi
a
RlnaTT1
E a Z 2
 ð3Þ
1 1
T2
 T1
In most of the examples for non-Arrhenius behaviour
discussed above, the key conclusion was that of
a mechanistic change with perhaps one process being
dominant over an elevated temperature regime and
 M. Celina et al. / Polymer Degradation and Stability 90 (2005) 395e404
a second process becoming more important towards
lower temperatures. Obviously, this assumption reflects
on an empirical approach, but a detailed kinetic model
describing curvature and providing possible data fits
based on individual reaction schemes and their temper-
ature dependencies has so far not been developed.
Perhaps a step in the direction of more sophisticated
modelling that may ultimately lead to more appropriate
kinetic modelling is the recent work by Audouin and co-
workers for better predicting degradation profiles [41].
In the simplest form, curvature in Arrhenius plots
will result from the combination of two competing
reactions (I and II) with individual rate determining
constants (k1 and k2) as shown in Eq. (4). This adds one
level of complexity to the traditional assumption that
aging data should be described by the temperature
dependence of only one rate constant. Alternatively, but
leading to a similar analysis, it has previously been
discussed that the overall effective rate constant in the
complex auto-oxidation scheme depends on individual
sub-reactions [4]. If changes in the relative importance of
some critical underlying reactions occur, the resulting
temperature dependence of the effective rate will be
affected and is expected to display non-Arrhenius
curvature. In its simplest form this would result in the
rate determining k1 changing into k2, but obviously
could also involve additional rate determining scenarios
with more than two temperature regimes.
Changes with temperature in the relative importance
of some underlying processes in a complex reaction
sequence should also result in product distribution
variations, consistent with reactions I and II leading to
different products. However, since polymer oxidation
involves many reactions and usually results in a broad
range of products, it is difficult to predict how kinetic
changes may relate to overall product distribution
variations. For example, changes in initiation efficiencies
could be rate controlling but most likely would not
affect product formation, while changes in relative
importance of propagation or termination steps should
result in some product variations. Both situations have
been discussed, i.e. as changes in initiation reactions
for polypropylene degradation [13,30] or oxidation prod-
uct variations observed for the degradation of
some elastomers [4,10,15]. There is some experimental
evidence that for many aging processes investigated,
higher degree oxidation products such as CO2 appear
to be predominantly produced at higher tempera-
tures [10,15,42]. Similarly, and consistent with curva-
ture, some product variations (i.e. hydroxyls) were also
observed in a solid polymer [42].
Whether the approach of two competing processes
should serve as the best model will no doubt remain
open for discussion. For instance, it may be found that
a third process with a higher Ea value becomes
important at even higher aging temperatures, but the
399
fact is at least two reactions with individual temperature
dependence of their rate constant can be used to model
curvature in the Arrhenius plot over a large temperature
range as demonstrated here. Both k1 and k2 will depend
on temperature with individual activation energies and
the combination of the two (Eq. (5)) will describe the
temperature dependence of the overall degradation
process. Eq. (5) allows for fitting of experimentally
observed accelerative shift factors or degradation rates
versus inverse temperature to determine two individual
activation energies (Ea1 and Ea2).
k1 k2
A /B A /C ð4Þ
reaction I II
  
Ea1 Ea2
ksum Zk1 Ck2 ZA1 !exp CA2 !exp
RT RT
ð5Þ
2.3. Experimental approaches to probe for
Arrhenius behaviour
It is obvious that in order to probe for Arrhenius
behaviour or curvature and thereby gain confidence
in predictions, degradation rates or accelerative shift
factors should be available over the largest temperature
range possible. Traditional techniques that were success-
ful and covered many orders of magnitude were based
on DTA/DSC [27,28] or long-term oven exposure
[12,14,33]. Recently a study showed curvature based
on changes in mechanical properties for a 24-year-old
sample aged at w24
C [15]. Ultra-sensitive oxygen
consumption introduced by Gillen and co-workers was
shown to be suitable for probing large temperature
ranges, allowing for a critical evaluation of lifetime
predictions and has provided numerous examples of
curvature [4e8,10,11,15,34,36,37]. The advantages and
straightforward application of this technique were
clearly demonstrated. NMR spectroscopy determining
relaxation times related to polymer mobility has been
successfully employed to probe fractional damage in
polymers similar to trends in mechanical property
changes, allowing in some cases degradation rate data
to be obtained prior to the end of the induction period,
but generally lacks high dynamic sensitivity [43e46]. No
matter which technique is best suitable, patience is
required to obtain meaningful aging data and establish
confidence in the extrapolation and lifetime prediction
based on accelerated aging studies [4,6e8,15].
2.4. Analysis of curvature for some elastomers
Several studies demonstrated non-Arrhenius behav-
iour for the thermal degradation of elastomers using
400 M. Celina et al. / Polymer Degradation and Stability 90 (2005) 395e404

ultra-sensitive oxygen consumption measurements over Table 1

large temperature ranges [4,6e8,10,11,15]. There was Two-process fitting results for some elastomers
clear evidence for curvature and some activation energies Ea HT Ea LT T crossover Regression
over specific temperature ranges were determined ac- (kJ/mol) (kJ/mol) (
C) (k1 Z k2) coefficient
cording to Eq. (3); a good example being that of the PU rubber 119 65 62 0.9993
thermal degradation of an elastomeric polyurethane [11] best fit
PU forced fit 125 60 65 0.9984
as shown in Fig. 1. It is obvious how a straight line PU forced fit 110 70 55 0.9980
extrapolation of the high temperature data would EPDM black 127 78 123 0.9975
predict an order of magnitude of lower degradation Butyl rubber 100 60 55 0.9976
rates at ambient conditions. To demonstrate the
suitability of simple curve fitting according to Eq. (5)
the accelerative shift factors were re-examined. The data activation energies obtained are consistent with those
can be fitted as shown in Fig. 1a and, clearly previously reported and are summarized in Table 1. The
in agreement with previous estimations, results in an changes from the high to low temperature process are
activation energy of w119 kJ/mol for high temperatures 54 kJ/mol lower for the PU, 49 kJ/mol for the EPDM
and w65 kJ/mol for low temperature conditions. The fit and 40 kJ/mol for the butyl elastomer.
is excellent, resulting in a high regression coefficient Any variation (error) in the determination of the two
(Table 1), and provides for an additional analysis of the activation energies depends on minimization of residuals
two processes (relative importance of a high temperature in the curve fitting routine and scatter in the experi-
(HT) and low temperature (LT) process dependent on mental data. The high temperature activation energy
temperature as shown in Fig. 1b). Apparent in Fig. 1 is for the polyurethane elastomer is reasonably well
the crossover temperature at 62
C where each process defined in this example because experimental data
contributes 50% of the overall reaction (i.e. k1 Z k2). points are available up to 125
C, which is sufficiently
When diverging from this temperature each individual above the crossover temperature. We estimate an error
process becomes quickly dominant (Fig. 1b). Similar fits of G10 kJ/mol for the high temperature activation
were accomplished for an EPDM [4,38] as shown in energy. The low temperature activation energy is more
Fig. 2 and a butyl elastomer [7] as shown in Fig. 3. The problematic, however, because there are fewer data

106
103
5
a) PU binder exp. data
10 EPDM exp. data
Two-process fit 102 127 kJ/mol
Two-process fit
Relative shift factor

104
Relative shift factor

119 kJ/mol 101 a)

103
100
102
10-1
101 78 kJ/mol
64.8 kJ/mol
10-2
100
10-3
200C 170C150C 120C 100C 80C 60C 40C 20C
-1
10 200C 170C150C 120C 100C 80C 60C 40C 20C
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 10-4
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6

100 100
Fraction of process [%]

Fraction of process [%]

b)
80 80 b)
60 60
HT process HT process
LT process LT process
40 40

20 20

0 0
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6
-1 -1
1000/T [K ] 1000/T [K ]

Fig. 1. (a) Curve fitting with two processes for a PU elastomer [11], (b) Fig. 2. (a) Curve fitting with two processes for an EPDM elastomer
relative contribution versus temperature. [4,38], (b) relative contribution versus temperature.
 M. Celina et al. / Polymer Degradation and Stability 90 (2005) 395e404 401

106 106

Butyl elastomer exp. data PU binder exp. data

105 a) 105 119 + 65 kJ/mol
Two-process fit 119 kJ/mol
125 + 60 kJ/mol
Relative shift factor

Relative shift factor

4
10 104 110 + 70 kJ/mol
100 kJ/mol

103 103

102 102

101 101
60 kJ/mol
65 kJ/mol
100 100
200C 170C150C 120C 100C 80C 60C 40C 20C 200C 170C150C 120C 100C 80C 60C 40C 20C
10-1 10-1
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6
-1
1000/T [K ]
100
Fraction of process [%]

Fig. 4. (a) Curve fitting with two processes for the PU elastomer [11]
80
b)
with different Ea combinations.

60 HT process
LT process
40 lead to non-fitting of the data, but it would again
suggest representing the PU data conservatively with
20
a combined high temperature process of for instance
0 119 G 10 kJ/mol and a low temperature process of
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 65 G 15 kJ/mol. Similar variances could be suitable for
-1
1000/T [K ] the curve fitting of other materials.
Fig. 3. (a) Curve fitting with two processes for a butyl elastomer [7],
(b) relative contribution versus temperature.
2.5. Analysis of curvature in literature
data for polypropylene

points below the crossover temperature to define the Some of the best data demonstrating curvature in
slope. As an example to estimate variations in the fitting, Arrhenius plots for thermal aging were observed for the
we intentionally varied the 25
C acceleration factor by classic polymer polypropylene, a material where degra-
G20% in order to examine the effect of experimental dation behaviour [47] and stabilization optimisation
uncertainties on the low temperature fit. An increase in [14,48,49] have been investigated extensively. We ana-
the 25
C acceleration factor decreased the low temper- lysed data from published figures, converted them into
ature activation energy from 65 to 47 kJ/mol, while relative accelerative shift factors, and fitted the data with
a decrease in the 25
C acceleration factor increased the a two-reaction regime process to determine individual
low temperature activation energy from 65 to 79 kJ/mol. activation energies. Data sets were those published by
These results imply that the low temperature activation Richters (Fig. 1 in ref. [12]), by Gijsman (lower curve in
energy should probably be conservatively estimated as Fig. 4 in ref. [13]), and Gugumus (where the data appear
65 G 15 kJ/mol. The curvature and crossover point for to have been published numerous times, Fig. 1.8 in [48],
the polyurethane is typical for many polymeric materials Fig. 3 (p. 58) in [50], Figs. 1 and 2 in ref. [14] for
that have been investigated in that there are more data unstabilised PP), and Gugumus for temperature shifted
above the crossover point than there are below. This stabilized PP (solid line, superposition average in Fig. 9
emphasizes the importance of acquiring sufficient low in ref. [14]).
temperature data by sensitive techniques such as oxygen All four examples could be fitted very well with
consumption. To further illustrate how slightly different the two processes. The data fits and individual process
activation energies would fit the data, the PU data were contributions are shown in Figs. 5e8 (a summary of the
also analysed with two potential processes, one changing fits is given in Table 2). Two aspects are immediately
from 125 to 60 kJ/mol and the second one changing captivating, the significant difference in activation
from 110 to 70 kJ/mol as shown in Fig. 4. It is obvious energies for the high and low temperature processes
that such fits would not be as good as the best fit of 119 and the virtually identical transition temperature of
and 65 kJ/mol, but would still describe the experimental 83 G 2
C. The LT process appears to have an Ea of
data reasonably well. Hence, small variations in the w35e50 kJ/mol, while the HT process has larger
activation energies would not be significant enough to variation with a value between w107 and 156 kJ/mol.
402 M. Celina et al. / Polymer Degradation and Stability 90 (2005) 395e404

105 104

PP exp. data a) PP exp. data

121 kJ/mol
104 Two-process fit Two-process fit
a) 103
Relative shift factor

Relative shift factor

107 kJ/mol
103
102

102
101
101
49 kJ/mol
100
100 41 kJ/mol

200C 170C150C 120C 100C 80C 60C 40C 20C 200C 170C150C 120C 100C 80C 60C 40C 20C
10-1 10-1
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6

100 100

Fraction of process [%]

b)
Fraction of process [%]

b) 80
80

60 60 HT process
HT process
LT process
LT process 40
40

20 20

0 0
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6
-1
-1 1000/T [K ]
1000/T [K ]
Fig. 7. (a) Curve fitting with two processes for PP [14], (b) relative
Fig. 5. (a) Curve fitting with two processes for PP [12], (b) relative
contribution versus temperature.
contribution versus temperature.

105 104
a) PP exp. data
a) PP exp. data
104
Two-process fit 3 Two-process fit
10
Relative shift factor
Relative shift factor

3
10
156 kJ/mol 146 kJ/mol

2 102
10

101
101

100 36 kJ/mol
41 kJ/mol
100
10-1
200C 170C150C 120C 100C 80C 60C 40C 20C 200C 170C150C 120C 100C 80C 60C 40C 20C
10-2 10-1
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6

100 100
Fraction of process [%]

Fraction of process [%]

b) b)
80 80

60 60
HT process HT process
LT process LT process
40 40

20 20

0 0
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6
-1 -1
1000/T [K ] 1000/T [K ]

Fig. 6. (a) Curve fitting with two processes for PP [13], (b) relative Fig. 8. (a) Curve fitting with two processes for PP [14], (b) relative
contribution versus temperature. contribution versus temperature.
 M. Celina et al. / Polymer Degradation and Stability 90 (2005) 395e404
Table 2
Two-process fitting of PP data taken from the literature
PP literature data Ea HT Ea LT T crossover
(kJ/mol) (kJ/mol) (
C) (k1 Z k2) coefficient
Richter (Fig. 1, [12]) 107 41 83
Gijsman (Fig. 4, [13]) 156 36 85
Gugumus (Fig. 2, [14]) 121 49 83
Gugumus (Fig. 9, [14]) 146 41 82
The larger variation in the HT process could be related
to considerably shorter aging times at high temperatures
with perhaps anomalies due to DLO effects, or may
simply reflect on some intrinsic material variations. It is
intriguing how the transition temperature matches that
of w80
C reported by Achimsky et al. [33] in another
long-term aging study (w3000 h at 50
C). However,
their estimated Ea’s of 101.5 and 72.5 kJ/mol for the
different regimes did not display the same dramatic
changes as could be established here for the other PP
examples. In any case, the excellent fits for the various
PP examples show how a simple competitive process
with two temperature dependent reactions has a suffi-
cient degree of freedom to match the experimental data
and can be used to adequately describe the observed
curvature.
3. Conclusion
The evidence of non-Arrhenius behaviour (curvature)
in polymer degradation studies has been reviewed.
While many studies emphasized mechanistic variations
and its importance for changes in activation energies,
individual activation energies or a more detailed de-
scription of curvature were often not presented. To
enable analysis, a simple approach for dealing with
curvature is introduced, assuming two competing
reactions or two critical reactions with individual
temperature dependence within a more complex re-
action scheme. This allows for excellent fitting of many
experimental data sets as shown for the thermal
degradation rates of some elastomers, does not require
complex kinetic modelling and individual activation
energies are easily determined. Reviewing independent
data for the thermal degradation of PP a transition
temperature of w83
C was confirmed, with the high
temperature process having a considerable higher
activation energy (107e156 kJ/mol) than the low
temperature process (35e50 kJ/mol). Such examples
demonstrate the excellent fits that can be obtained by
introducing as a minimum two processes to address
curvature in Arrhenius plots. For accelerative aging
studies where evidence of some curvature exists but
limited data are available, better lifetime predictions
could be made by estimating a low temperature process
403
activation energy or allowing for a second rate de-
pendence instead of forcing a straight line extrapolation.
Regression
0.9994 Acknowledgements
0.9987
0.9997
0.9995 Sandia is a multiprogram laboratory operated by
Sandia Corporation, a Lockheed Martin Company, for
the United States Department of Energy’s National
Nuclear Security Administration under Contract DE-
AC04-94AL85000.
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