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Polymer Degradation and Stability xxx (2013) 1e11

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Polymer Degradation and Stability


journal homepage: www.elsevier.com/locate/polydegstab

Review article

Review of polymer oxidation and its relationship with materials


performance and lifetime prediction
Mathew C. Celina*
Sandia National Laboratories, Materials Characterization and Performance Dept. 1819, PO Box 5800, MS 1411, Albuquerque, NM 87185-1411, USA

a r t i c l e i n f o a b s t r a c t

Article history: All polymers are intrinsically susceptible to oxidation, which is the underlying process for thermally
Received 2 May 2013 driven materials degradation and of concern in various applications. There are many approaches for
Received in revised form predicting oxidative polymer degradation. Aging studies usually are meant to accelerate oxidation
12 June 2013
chemistry for predictive purposes. Kinetic models attempt to describe reaction mechanisms and derive
Accepted 14 June 2013
Available online xxx
rate constants, whereas rapid qualification tests should provide confidence for extended performance
during application, and similarly TGA tests are meant to provide rapid guidance for thermal degradation
features. What are the underlying commonalities or diverging trends and complications when we
Keywords:
Accelerated polymer aging
approach thermo-oxidative aging of polymers in such different ways? This review presents a brief status
Lifetime prediction report on the important aspects of polymer oxidation and focuses on the complexity of thermally
Thermal oxidation accelerated polymer aging phenomena. Thermal aging and lifetime prediction, the importance of DLO,
Polymer degradation property correlations, kinetic models, TGA approaches, and a framework for predictive aging models are
Arrhenius extrapolation briefly discussed. An overall perspective is provided showing the challenges associated with our un-
Diffusion limited oxidation derstanding of polymer oxidation as it relates to lifetime prediction requirements.
Published by Elsevier Ltd.

1. Introduction briefly highlight the evolving knowledge with regard to some


important aspects when we deal with thermo-oxidative degrada-
Long-term thermo-oxidative degradation is a concern for any tion. This also warrants some questions about the assumptions and
polymer under normal environmental conditions, unless sealed expected behavior which feed into predictive aging approaches.
systems or purposely introduced inert conditions apply. Therefore, Some of these challenges are: Can degradation chemistry be simply
a focal point in the field of ‘Polymer Degradation and Stability’ is accelerated? Under which conditions do accelerated aging experi-
thermally driven degradation. The other big field of course is UV ments lose their predictive value? How important are diffusion
induced photo-oxidation or radiation degradation, where much limited oxidation (DLO) complications? Can kinetic modeling pro-
overlap with thermal aging exists when the effects of temperature vide predictive capabilities, and if so, where are the limits? What
on degradation processes are considered. Understanding thermal are the ongoing issues that need to be addressed to enable this
aging processes, oxidation mechanisms, thermal acceleration research field to move forward?
behavior, activation energies, and the convoluted manner in which Therefore, to address such questions we will briefly review how
degradation pathways may present themselves, is an integral thermo-oxidative processes relate to different aspects of polymer
requirement of meaningful polymer aging studies. chemistry and physics. Further, we will discuss how reaction
The different methods that are used to evaluate thermo- chemistry has been correlated with mechanical property or molec-
oxidation may often yield diverging perspectives. It is not always ular weight changes. It is also important to consider the limits of
clear if or to what degree extrapolations have predictive value or kinetic models or the circumstances under which diffusion limited
what complications could be introduced by raising the tempera- oxidation (DLO) conditions affect accelerated aging experiments.
ture. Polymer oxidation depends on simultaneous chemical and This opens up a discussion about non-correlations between accel-
physical phenomena and accelerative conditions add complexity to erated and ambient aging conditions. A questionable approach, for
this relationship. This overview perspective is therefore intended to example, is the overexposure of polymers in fast thermo-gravimetric
analysis (TGA) degradation methods, which in the literature unfor-
tunately may be regarded as a quick substitute for more extended
* Tel.: þ1 505 8453551; fax: þ1 505 8449781. polymer aging studies. We hope to provide a few comments about
E-mail address: mccelin@sandia.gov. other intriguing developments and a perspective on how evolving

0141-3910/$ e see front matter Published by Elsevier Ltd.


http://dx.doi.org/10.1016/j.polymdegradstab.2013.06.024

Please cite this article in press as: Celina MC, Review of polymer oxidation and its relationship with materials performance and lifetime
prediction, Polymer Degradation and Stability (2013), http://dx.doi.org/10.1016/j.polymdegradstab.2013.06.024
2 M.C. Celina / Polymer Degradation and Stability xxx (2013) 1e11

material characterization approaches could aid more sophisticated 1000


spatially resolved degradation models in the future. Slower bulk degradation at higher T

Relative shift factor aT


2. Discussion 260°C

2.1. Thermal polymer degradation and lifetime prediction 100 150°C


Mechanistic changes Linear behavior for
Temperature coupled with oxygen is the most commonly used DLO
some T range
accelerative condition for polymer degradation as it is easy to apply.
100°C
It is also an integral part of most other exposure conditions (i.e. 10
photo-oxidation), as is schematically shown in Fig. 1. Materials
which do not ‘age well’ are commonly exposed to hotter temper- 25°C
atures until they may ‘fall apart.’ The best example for this approach
Mechanistic changes
is given by ramped temperature TGA, since TGA will not ‘fail’ to
induce thermal decomposition of organic polymers. In more 1 Faster degradation at lower T
commonly used accelerated aging studies, temperature and time 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4
are perhaps selected based on project constraints, funding avail- -3 -1
ability or even the need to have Ph.D. students publish within a 1/T [10 K ]
three year timeframe. Whatever the reason, temperature is used for
Fig. 2. Most accelerated aging studies use some convenient temperature range where
a common purpose, namely to accelerate the underlying ‘degra- linear Arrhenius behavior may be observed over a limited temperature range. How-
dation chemistry.’ But is it sensible to use accelerated chemistry ever, non-linearity may be seen when a larger temperature range is examined.
from a TGA experiment to provide guidance for long term perfor-
mance of polymers under ambient conditions? It is clear that limits
associated with mechanistic changes in dominant chemistry over a
in acceleration factors need to be considered if the resulting
large temperature range are at the core of accelerated aging and
accelerated degradation pathways are to be representative.
lifetime predictions [1,5,6,8]. It is therefore imperative that for any
There are many indications that chemical processes which
accelerated thermal aging study all relevant parallel processes be
govern polymer oxidation often follow the ‘holy grail’ of kinetics,
considered which could add complexity to the analysis of degra-
which is Arrhenius behavior, as long as moderate conditions and
dation rates and definition of mechanistic reaction schemes. Such
perhaps limited temperature intervals are applied. But significant
issues are evident when dealing with DLO behavior and surface
evidence has also been collected when larger temperature regimes
versus bulk degradation phenomena [9e14], heterogeneous versus
are examined, that many materials show curvature in an Arrhenius
homogenous aging processes [15e23], liquid state versus solid state
plot of oxidation rates [1]. Oxidation rates measured over a large
kinetic frameworks [19,24,25], or complex TGA signatures [26]; all
temperature range are an excellent indicator for the relative
which affect the interpretation of thermal polymer oxidation.
importance of oxidative processes with temperature and underlying
Thermo-oxidative aging and lifetime prediction are also intrin-
activation energies [1e7]. Textbook chemistry does not always apply
sically linked with the action mechanism and behavior of polymer
and reaction kinetics competes with other processes which induce
stabilizers or additives. Much emphasis of applied polymer testing
non-linearity. A schematic of deviations from linear Arrhenius
and aging studies relates to the effectiveness of additives or com-
behavior over a large temperature range due to mechanistic changes
binations thereof. It is not the intention of this review to go into
and DLO is shown in Fig. 2. It shows an Arrhenius plot of relative
details here, since sufficient knowledge and excellent overview
degradation rate data, which are often called shift factors when
literature in this area exists [27e31]. Further, the concerns associ-
obtained from a timeetemperature aging data superposition
ated with evaluating stabilizers when using short term high tem-
analysis and may be normalized to a particular temperature. Shift
perature or similar exposure have been discussed before [20,21,32e
factors are proportional to rate and inversely proportional to aging
34]. Correlations between high temperature and low temperature
time for a particular aging state. It is common to observe linear
action of stabilizers can be non-existent, because crossover effects
Arrhenius behavior over a limited temperature range, but non-
exist which project the opposite rating from highly accelerated
linearity may evolve when a larger temperature range is examined
tests than observed at slower aging conditions [32e34]. The chal-
due to mechanistic variations in the aging process. The challenges
lenges of truly understanding stabilizer performance and their
behavior under accelerated conditions are very similar to the ex-
• Polymers are often exposed to a multitude of environments amination of materials for lifetime prediction purposes. It is also
• Materials can display particular sensitivities important to remember that thermo-oxidative degradation will
• Temperature, oxygen, hydrolysis, UV may act in combination
proceed despite the presence of antioxidants. Obviously rates will
O2 be much lower for stabilized materials, but significant degradation
Radiation
H 2O γ, e-beam, particles can occur even when high levels of antioxidant are present [35], or
UV, vac-UV in space when oxidation induction time (OIT) data may suggest a suffi-
ciently stabilized material [36]. In such situations significant ma-
H+, OH-, ions
terial degradation at lower temperatures is not necessarily
Polymer material Temperature
inhibited until all antioxidant is consumed, which suggests the
Metal contaminants participation of localized non-inhibited reaction zones [17,24,35].
Mechanical load
Other sensitivities Stress, creep
Microbial, solvents, surfactants etc 2.2. Correlation of degradation chemistry and mechanical
properties
Major differences between oxidative and inert conditions

Fig. 1. Various exposure conditions result in polymer degradation where oxygen and Materials performance is usually associated with expected
temperature are important aging parameters. mechanical properties or similar desired attributes (elasticity,

Please cite this article in press as: Celina MC, Review of polymer oxidation and its relationship with materials performance and lifetime
prediction, Polymer Degradation and Stability (2013), http://dx.doi.org/10.1016/j.polymdegradstab.2013.06.024
M.C. Celina / Polymer Degradation and Stability xxx (2013) 1e11 3

toughness, adhesion, impact fracture resistance etc.). Aging studies Oxidation [%]
are intended to accelerate the degradation chemistry and the
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
resulting degradation state is often monitored with supporting
400
chemical analyses, such as IR signatures, discoloration, crosslink
state, molecular weight analysis, melting behavior, or morpholog-
Superposed tensile elongation data at 80°C
ical characterization. Of course, aging trends are commonly also

Tensile elongation [%]


average oxidation rate 4*10-11 mols/g-s
monitored using tensile elongation, modulus analysis, fracture 300
50% elongation corresponds to ~ 1.8% oxidation
sensitivity or similar mechanical tests. However, in many acceler-
ated aging situations material characterization may be limited to
small specimens or it is often more convenient to consider sub- 200
gram samples for chemical diagnostics, since mechanical tests
may not always be feasible. This then requires appropriate corre-
lations between ‘oxidative chemical state’ and ‘mechanical or
physical state.’ Our understanding and description of oxidative 100
polymer degradation processes depend strongly on well-described
cross-correlations between properties measured with diverging
methodologies. 0
In addition to our discussion in Section 2.1., as part of predictive 0 50 100 150 200 250 300 350
oxidative aging studies, the value of using oxidation rate mea-
surements over large temperature regimes has been demonstrated Aging time [d]
repeatedly [1e7,37]. This is advantageous for two reasons, namely
Fig. 3. Correlation between oxidation level and tensile elongation properties for an
that steady oxidation rates can be easily extrapolated in time and HTPB elastomer aged at 80  C. Data from Ref. [2].
integrated to yield predicted oxidation levels, and that a super-
position analysis of oxidation rates and subsequent Arrhenius plot
of the underlying shift factors allows for an overview of whether conditions (i.e. very high temperatures), stress cracking and
linear or curved Arrhenius behavior may apply, and to what degree oxidative damage are severe and commonly observed [46e49].
the corresponding activation energies may differ between high and Similarly, under aggressive thermal or radiation-thermal oxidative
low temperatures. Since the use of oxidation rates allows for pre- conditions measurable chemical changes can be detected [50e52],
diction of oxidative state (degradation level) with time, and further yet numbers for exact percent-oxidation level are usually not
since DLO behavior describes and predicts oxidation levels with provided. Interestingly, under photo-oxidative conditions epoxies
depth, such approaches require knowledge of oxidation levels can show strongly heterogeneous oxidation behavior when
versus mechanical properties to be of broader value. examined by AFM [53]. Also, for photo-oxidation of a range of
Cross-correlations can be established for many polymers; thermo-set coatings, a good correlation between carbonyl growth
however, experimentally this is not always easy. In general, poly- and AFM micro-hardness was observed [54e56]. Not knowing
olefins are the most challenging materials, as they are most sensi- exact molar absorptivities and homogeneity of the degraded films,
tive to localized oxidative damage, because of their semi-crystalline it remains challenging to establish chemical oxidation levels. To
morphology and dependence on tie-molecules which are address this issue, we have recently succeeded to measure oxida-
compromised by oxidative chain scission. Little oxidation is tion rates for two epoxy systems over a large temperature range.
required to result in stress cracking of semi-crystalline polyolefins. Coupled with extended accelerated thermal oxidation experiments,
The work by Billingham et al. throughout the 1970se1980s enabled we concluded that epoxies are more reactive than anticipated [57],
much progress in the understanding of these phenomena but that they can also accommodate significant oxidation levels
[15,16,25,38e40], followed by ongoing work in the 1990s which (>10%) before any cracking may develop (so far unpublished).
dealt with the heterogeneity of oxidative aging [17,18,24,41e43]. In order to establish meaningful oxidation level to mechanical
Recent unpublished data combining chemiluminescence (CL) with property correlations, significantly aged specimens are normally
oxuptake for PP suggest on the order of 0.01% oxidation to result in
beginning embrittlement for PP; similar numbers are obtained
when comparing bulk carbonyl-index with the earliest observa-
tions of brittle features as discussed later [44].
In comparison, oxidation of elastomers nearly always affects
their elastic modulus, mostly via oxidative crosslinking. Most
elastomers harden as part of oxidative aging which facilitates stress
cracking and loss of desirable properties. It is well known that in-
tegrated oxidation rates (i.e. oxidation levels) coupled with tensile
elongation or modulus profiling data, allows for excellent correla-
tions to be established [2,3,37,45]. An example is shown in Fig. 3 for
thermal oxidation of a soft polyurethane rubber, and in Fig. 4 for
localized oxidation levels and modulus changes during aging of
neoprene. The predicted oxidation levels and localized modulus for
the neoprene rubber material are based on thermal DLO modeling
of relative localized oxidation rates for this specific geometry.
Thermo-set materials, such as highly crosslinked epoxies, bis-
maleimides, benzoxazines or phenolics, seem to accommodate
Fig. 4. Diffusion limited oxidation and its predicted correlation with localized modulus
significant oxidation levels. So far exact numbers for oxidation for a neoprene elastomer specimen under highly accelerated thermal aging conditions
levels in correlation with modulus or other property changes for of 15 days at 125  C. It shows the absence of oxidative damage and therefore soft
these materials do not exist. Under highly oxidative pyrolytic material in the center. Model input data taken from Ref. [3].

Please cite this article in press as: Celina MC, Review of polymer oxidation and its relationship with materials performance and lifetime
prediction, Polymer Degradation and Stability (2013), http://dx.doi.org/10.1016/j.polymdegradstab.2013.06.024
4 M.C. Celina / Polymer Degradation and Stability xxx (2013) 1e11

required. Oxidation rates can be determined with short term 0.024% oxidation. Such approximate numbers are consistent with
thermal exposure [58,59]. However, if high oxidation levels are the essentially non-detectable carbonyl absorption when this
required so that measurable moduli changes or significant loss of transition occurs (see Fig. 1 in Ref. [44]). A detection limit of
tensile elongation develop, then extended exposure and strongly 0.005 mol/kg carbonyl groups equals w1.3 carbonyl groups for Mw
accelerative aging environments are needed [2e4,37]. Therefore, of 270 kDa, the equivalent of 0.016% oxidation. In comparison, a
while oxidation rates can be measured for low oxidation levels at Nylon material undergoing degradation from Mw of 50e20 kDa via
ambient temperature, higher oxidation levels depend on acceler- CeN scission chemistry will require a minimum of w0.16% oxida-
ated aging; hence, oxygen consumption experiments often run in tion for the relevant scission to occur. The required chain scissions
parallel with aging studies. Surface modulus and modulus profiling depend on the initial molecular weight and Mw associated with
analyses, when combined with local oxidation state from DLO ap- failure and do not require much oxidative ‘chemistry,’ yet can
proximations/predictions, can also help to extract the degree to significantly change toughness and tensile properties.
which chemical oxidation affects elastic properties [3,12,37]. This situation is further complicated when heterogeneity as-
pects in thermo-oxidation are considered. More localized reactions
2.3. Molecular weight changes as part of oxidative degradation can create more volatiles and small molecular weight fragments,
perhaps increasing oxidation chemistry yields. One such contro-
Another polymer oxidation characterization approach which versy arises when the chemical variety of volatile species produced
provides significant mechanistic insight is linking oxidative during oxidation of PP or Nylon is considered, as analyzed with
degradation with molecular weight changes. It is well known that sensitive mass spectrometry methods (MS) [78e82]. Unfortunately,
degradation will proceed via scission or crosslinking reactions. MS analysis does not easily quantify total amounts of volatiles per
Unfortunately, it is not always possible to predict how specific sample weight and exposure condition, and without a clear un-
polymers will behave. For example, it is generally accepted that derstanding of percent oxidation level associated with the type and
polyolefins show predominantly scission behavior under oxidative absolute amounts of chain scission products, the underlying reac-
conditions as evidenced by reduced molecular weight, but more tion dynamics cannot be established. However, it is clear that each
crosslinking characteristics under inert (non-oxidative) degrada- small fragment originates from two scission events; further, it is
tion which develops during g-irradiation under N2 or under high unlikely that for example one Nylon molecule only produces one X
temperature DLO conditions. However, morphology, crystallinity volatile product and another molecule only one Y product to
and the aging temperature are important parameters which affect maintain limited chain scission, while at the same time producing a
this process. For example, crosslinked polyolefins with low crys- large range of degradation species [79,83]. Hence, the balance be-
tallinity seem to crosslink further under thermo-oxidative condi- tween total volatile yield and at the same time maintaining critical
tions at high temperatures where partial crystalline melting average molecular weights as evidenced by ongoing ductile prop-
becomes active [60], but related materials show strong scission erties holds the key to the discussion of average homogeneous ki-
behavior under photo-oxidative low temperature conditions [61]. netics versus localized ‘chemistry amplification,’ here resulting in
In comparison, most elastomeric materials tend to crosslink under higher scission yields with many different volatiles. Mechanical
oxidative conditions, leading to increased modulus and hardening properties and therefore critical Mw values were maintained,
with embrittlement [2,3,12,37,58,62e65]. Thermo-set materials despite the identification of a large number of volatile products in
tend to also crosslink under thermo-oxidative conditions with the corresponding experiments [79,83]. This cannot be explained with
modulus increasing in parallel [46,48,54e56,66]. a model of a few localized average chain scission events. Instead, it
A systematic review of how molecular weight changes are is clear evidence for the participation of heterogeneous oxidation
coupled with brittle behavior and oxidation as measured by domains which are not represented by current homogeneous ki-
carbonyl growth was conducted by Fayolle and co-workers for netic models [76].
polyolefins [44,67e70] and other polymers [71e76]. In particular,
the results summarized how a critical molecular weight exists 2.4. Kinetic modeling
which corresponds with a ductile to brittle transition during
oxidative polymer degradation [44,69,77]. For example critical Mw Kinetic modeling is a broad approach that is pursued by a
values (in kDa) were provided as 28 for PC, 40 for PPMA, 60 for PS, number of research groups to help in the interpretation of polymer
70 for PE, 200 for PP, or 130 for PP fibers, 70 for POM, 200 for PTFE oxidation, the evaluation of the underlying reaction mechanisms
[71], or 17 for PA 6,6 [76]. Mechanistically, chain scission, followed and for the development of kinetic data extrapolation strategies
by a decrease in molecular weight and chemi-crystallization, was [84e88]. Kinetic models of oxidation pathways are built on detailed
then discussed as affecting tie molecules and interlamellar spacing mechanistic degradation chemistry, yet they do not easily embrace
and ultimately leading to brittle sensitivity. Interestingly, embrit- the physical constraints of localized solid state reactions and
tlement is seen as occurring before significant damage in the mechanistic variations with temperature, perhaps based on
entanglement network, at higher than expected Mw. Because of the morphology and reactivity zones. Reactive transport models which
involvement of tie molecules and critical interlamellar domains, address DLO are often grouped together with kinetic modeling
chain scission damage is essentially amplified to result in brittle approaches, but are actually quite separate approaches, as the more
features [77]. physical competitive process of localized diffusive oxygen reagent
Considering the relatively high remaining Mw when brittle supply and consumption terms are not necessarily dependent on
failure occurs and the limited reduction in average Mw from the the exact chemical reaction mechanism. It is not intended here to
original material, it is clear that from a chemistry point of view very present a critique of kinetic modeling, but nevertheless caution
little oxidation is required. For example, to discuss a few basic should be taken for a number of reasons. Some of the outstanding
numbers, if PP with an initial MW of 400 kDa oxidatively cleaves challenges associated with kinetic modeling of thermal polymer
and the critical Mw is on the order of 200 kDa, then ideally only one degradation are:
effective scission in the middle of the chain is required to transition
the material from ductile to brittle. In this case only 0.008%  The determination of rate constants from accelerated degra-
oxidation would be required. Three perfect scission events in this dation depends on the kinetic scheme that is being applied.
simplistic example would drop Mw to 100 kDa and only require Parameters are often extracted based on data fits with initial

Please cite this article in press as: Celina MC, Review of polymer oxidation and its relationship with materials performance and lifetime
prediction, Polymer Degradation and Stability (2013), http://dx.doi.org/10.1016/j.polymdegradstab.2013.06.024
M.C. Celina / Polymer Degradation and Stability xxx (2013) 1e11 5

mechanistic assumptions, but may then be discussed to justify As discussed before, kinetic models which rely on data obtained
the underlying mechanism. Suitable fits may evolve for a under DLO conditions lack predictive value for non-DLO conditions.
particular kinetic pathway, but other mechanisms may provide
correlations of similar quality. Correlations between kinetic 2.5. Importance of diffusion limited oxidation (DLO)
models and experiments which are meant to provide rate
constants are encouraging, but the models should be regarded Whenever dealing with highly accelerated thermal degradation
with some caution as they may not be exclusive. Models can of polymers and larger sample specimens, the complicating effects
provide guidance, but obviously can be no better than the as- of diffusion limited oxidation (DLO) must be considered. This sit-
sumptions applied to derive the underlying model input pa- uation applies when degradative acceleration does not only result
rameters (rate constants and activation energies). in much faster chemistry (as intended for predictive studies), but
 Kinetic parameters (rate constants) are often only available also leads to the introduction of competing physical phenomena as
when sufficiently fast degradation processes can be experi- part of the degradation process. Fig. 5 shows schematically that
mentally observed, i.e. when conducting classic accelerated DLO can occur in many different accelerated aging scenarios. Of
aging studies to derive model input parameters. Long-term course for very large specimens DLO may already exist at ambient
aging behaviors where complicating physical processes may temperatures [2]. Most polymer degradation pathways evolve
evolve over large temperature differences are not easily around competition between oxidative versus inert degradation
accommodated (as with any limited accelerated aging study) processes, i.e. when oxygen supply is diffusion limited because of
and the applied models can therefore not confidently predict too much reactive consumption within the material and spatially
them. dependent degradation zones evolve. Under accelerated condi-
 Extrapolation is associated with assumptions of the prevailing tions, depending on geometry and specific material properties, any
activation energy and perhaps Arrhenius linearity. For many oxidative aging process has the potential to transition from ho-
materials it has been shown that linearity may not apply and mogeneous aging into a heterogeneous oxidation process, perhaps
therefore combinations of rate constants do not necessarily better defined as bulk versus surface dominated degradation. If the
follow basic model assumptions with temperature. Most ki- exact oxygen supply and consumption rates are known under
netic models do not establish Arrhenius behavior for extended thermal conditions, it is then possible to develop a spatially
temperature regimes, but rather assume it to be valid for lower dependent degradation model which couples the O2 supply with
temperatures as part of extrapolations [76]. consumption chemistry, for example applied under thermal only
 Many of the kinetic models which have been proposed rely on [2,3,11,12,37], or under thermal-g-radiative conditions [93,94].
initial hydroperoxide levels to trigger follow-up reactions [46e Diffusion limited oxidation (DLO) predictions describe spatially
48]. For high temperature polymer degradation, it is ques- dependent degradation chemistry based on competition between
tionable whether such hydroperoxide based approaches are oxygen supply (physics) and consumption (chemistry). Such
always appropriate, since there are limits to chemical forma- models explain spatially dependent changes in modulus, i.e. sur-
tion and thermal stability of hydroperoxides. Another issue is face degradation versus bulk property changes, and generally can
associated with initial hydroperoxide level assumptions. For predict the magnitude of chemical degradation as a function of
example, it is difficult to comprehend how a kinetic model depth. For larger specimens the ingress of oxygen from the surface
describing the thermo-oxidation of Nylon accommodates an becomes a self-limiting maximum flux, i.e. when the decreasing
oxidation level of only 0.0056 mol/l carbonyl scission products partial reactivity is integrated with depth, and further depth does
(0.016% oxidation) for mechanical failure, but requires not contribute additional chemical oxidation reactivity (i.e. when
0.05 mol/l of initial hydroperoxides (i.e. a significant pre- more material is added beyond the reactive zone). DLO models
oxidation level of 0.14%) [76,89]. These hydroperoxides which can predict localized chemistry have shown excellent cor-
should decompose and result in scission and follow-up relation with spatial variations in mechanical properties of
chemistry; therefore additional oxidative scission events may degraded polymers [2,3,12,37].
occur. Further, the correlation between oxidation level and DLO complications are one of the most important components
effective scission required for failure should also depend on the of accelerated polymer aging. They apply to thermally driven, UV
morphology and initial Mw condition. photo-oxidation and radiation oxidative processes (see Fig. 5), as
 Current kinetic models also do not accommodate heterogene- well as many severely accelerated polymer testing approaches
ity aspects in solid polymer degradation. There are significant where oxygen is involved, such as oxidation induction time (OIT)
challenges associated with the more localized reactions and
reactivity zones encountered in solid polymer degradation
than covered by the widely-used description based on solution
Stress variable DLO conditions
chemistry reaction kinetics.
Temperature excessive T
One example where high temperature and highly accelerated (high temperature
polymer degradation, and for that manner any kinetic model fitting O2 oven, TGA or similar)
such data, fails to predict long-term aging, is in situations where
UV exposure strong dose rate
‘inverse temperature effects’ are observed. Such phenomena evolve
(high dose rate
when effective degradation levels may change with temperature or O2 Polymer sample
wheatherometer)
depend on morphology, hence where the underlying assumption of
any kinetic model of equal ‘chemistry’ for equal physical property O2 Radiation high dose rate
changes is no longer valid. For example, this was observed for (intense gamma,
e-beam, ion beam)
combined thermal radiation oxidative degradation of semi-
crystalline cable insulation materials [90,91]. Another example is Mechanical severe load
stress surface cracking
given when rapid accelerated qualification testing of polymers
excludes the participation of oxidative processes, but when Fig. 5. DLO situations may arise during severely accelerated polymer degradation, all
oxidation will be the dominant long-term degradation process [92]. resulting in preferential surface versus bulk degradation phenomena.

Please cite this article in press as: Celina MC, Review of polymer oxidation and its relationship with materials performance and lifetime
prediction, Polymer Degradation and Stability (2013), http://dx.doi.org/10.1016/j.polymdegradstab.2013.06.024
6 M.C. Celina / Polymer Degradation and Stability xxx (2013) 1e11

or TGA pyrolysis. Fig. 6 emphasizes that a significant increase in dose rate is sufficiently high, meaning that for a particular thick-
temperature not only accelerates chemistry, but eventually in- ness non-oxidative photochemistry processes commence and
troduces additional physical processes. High temperature total polymer degradation yields will no longer be proportional
methods, such as severely accelerated thermal aging (high tem- with dose.
perature ovens), oxidation induction time (OIT) or thermo- DLO is at the core of an unresolved discrepancy between the
gravimetric analysis (TGA) measurements are often subject to complexity of polymer degradation and knowledge gained in the
DLO, even when small samples are used. Such techniques may field of ‘polymer aging’, and the more engineering-based testing
offer avenues for stability comparison of nearly identical material approaches incorporated into standardized methods for lifetime
formulations, but generally lack extrapolative value as discussed prediction purposes of many polymeric materials. Limited highly
later [32e34,36,95e97]. In some studies OIT data have been an accelerated testing methods using a few data points and relying on
attractive approach to resolve stabilizer diffusion and depletion linear Arrhenius-type extrapolations do not always reproduce
aspects in polyolefins [98,99] or stabilizer profiles associated with homogeneous degradation processes and do not accommodate
heterogeneous aging in PE nano-composites [100]. mechanistic changes and non-linear temperature dependencies.
If the complicating phenomena of DLO are poorly understood, it DLO behavior is a key contributor to divergence between acceler-
is clear that a non-correlation between ambient oxidative aging ated thermal aging and actual aging behavior under use condi-
and predictive aging under partially or mostly inert conditions can tions. A comprehensive understanding and prediction of DLO
quickly develop. As long as only surface properties are of interest, requires two terms, namely the O2 permeation [101] and oxidation
DLO is not important. In contrast, whenever accelerated aging is rate as a material property (O2 consumption) which has been
focused on uniform sample degradation or bulk property assess- published on numerous occasions [1,3,4,37,58,59,102,103]. Com-
ments, then DLO is an important component of accelerated expo- putations then allow for spatially dependent oxidation chemistry
sure and must be considered. This means that there are intrinsic to be described, as shown for example in Fig. 4, which shows inert
limits for maximum temperatures, as long as temperature accel- degradation in the center and oxidatively dominated thermal
erates the oxidation rate, coupled with a maximum thickness or degradation toward the exterior for a particular geometry. DLO
volume for specimens for which homogeneous aging will apply. models can also help establish the amount of material in a spec-
Similarly, under UV or g-radiation exposure there is a limit in imen that actively oxidizes. Under homogeneous conditions the
thickness and dose rate for homogenous oxidative processes to material oxidizes throughout, whereas under heterogeneous
occur. DLO is one reason that high dose rate exposure (mostly for conditions only a small fraction of the material oxidizes at all. Fig. 7
sterilization purposes) results in surface polymer degradation, shows such transitions for an XLPO material of different thick-
whereas the bulk of the material experiences non-oxidative nesses with increasing temperature. With integration of localized
conditions. rates over the predicted degradation profile it is possible to
Rapid qualification testing of polymers for performance pre- determine the amount of material that oxidizes at the equivalent
dictive purposes in engineering applications, where highly surface oxidation rate.
accelerated conditions are applied based on significant tempera-
tures coupled perhaps with high UV or gamma dose rates, may 2.6. High temperature TGA approaches
give a sense of tremendous over-exposure and hence the
perception of performance margins. However, unless very thin Based on the evolving literature and perhaps driven by needs
films are used under such conditions, DLO effects will induce inert originating from the standards community for more rapid testing
dominated degradation, and those will most likely not correlate approaches as part of material qualification, there appears to be a
with the use application, where oxidative conditions are normally desire to embrace ramped TGA as one technique for rapid thermal
expected to be much more important. The situation described aging and as a kinetic evaluation tool with the potential to deliver
here will apply to the qualification testing of cable assemblies activation energies. Obviously such approaches are appealing
[92], to O-rings and seals and related materials. Similarly, DLO is because of speed and available mathematical data interpretation
one reason that the reciprocity law (equal damage for equal dose) tools. While ramped TGA can certainly deliver data for pyrolytic
under highly accelerated UV exposure cannot apply when the volatilization processes, for lifetime prediction purposes or more

OIT-T (DSC temperature ramp) TGA (Temperature ramp) High temp ovens Physics
In some instances these techniques may provide relative comparisons
OIT (Oxidation Induction Time) DLO TGA (isothermal) DTA, DMA
Isothermal DSC (220-160°C)
Temperature

Moderate temp ovens


Moderately accelerated aging
Monitor chemistry and
mechanical/physical changes Moderate UV exposure

Non-DLO Ambient aging processes

Goal: Representative test with predictive


capability for specific application Chemistry

DLO is the most important complication in highly accelerated oxidative degradation


Similar issues could occur for moisture diffusion and hydrolysis when significant rates are involved
Goal: Conduct aging under non-DLO to understand material behavior and chemistry

Fig. 6. Extensive temperature exposure transitions polymer oxidation from accelerated chemistry to include physics based anomalies. Diffusion limited oxidation can affect any
rapid high temperature characterization and aging methods.

Please cite this article in press as: Celina MC, Review of polymer oxidation and its relationship with materials performance and lifetime
prediction, Polymer Degradation and Stability (2013), http://dx.doi.org/10.1016/j.polymdegradstab.2013.06.024
M.C. Celina / Polymer Degradation and Stability xxx (2013) 1e11 7

Very thin specimens will oxidize homogenously


even at very high T (high rates)
0.1mm
Homogeneous 1.0

Material fraction
At very low temperatures
0.8 thick materials will oxidize
homogenously
0.6 1mm

XLPO insulation
0.4 10mm material
0.2 100mm
Thick materials do not fully
0.0 oxidize at mid temperatures
Heterogeneous Significant DLO effects
250°C 170°C 100°C 60°C 25°C

1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6

1000/T [1/K]
Fig. 7. Example of DLO modeling for a crosslinked polyolefin material which can predict the equivalent fraction of material oxidizing at the surface oxidation rate. Any thickness will
transition to heterogeneous aging with increasing temperature. Even small 1 mm sized sample specimens for TGA experiments can be subject to DLO effects.

moderate oxidative aging processes TGA is questionable and should  Modern TGA instruments may include software assisted data
be approached with caution for a number of reasons: analysis options. There is no limit to what can be done with
non-isothermal weight loss curves in terms of fitting differ-
 For many polymers thermo-oxidative degradation is associated ential equations from various mathematical models that
with a weight increase due to incorporation of oxygen. In describe degradation conditions at different scanning rates.
contrast, TGA forces volatilization of the material and as such However, it does not mean that the computational power
represents a process that is often not encountered during provided itself validates a particular mathematical treatment
polymer aging. or the resulting Ea and data analysis employed. Many studies
 TGA yields Ea values in a high temperature regime that is far seem to lack a critical perspective on what the computational
removed from use temperatures. TGA is outside the framework output justifies and the challenges in the meaning of such
to deliver meaningful Ea for long-term polymer aging processes numbers for the material properties.
and often yields Ea data that are much higher than observed in
other studies. Many polymers show curvature in Arrhenius In principle, ramped TGA can provide kinetic data (i.e. Ea) when
plots toward lower Ea values [1e3,5,6]. the decomposition associated with weight loss involves well-
 Even for small samples, TGA under oxidative conditions is defined steps, and chemical conversion can be established to then
subject to DLO effects. This method can therefore not easily be examined with any of the existing mathematical treatments
provide information for overall sample representative oxida- [104e108]. These interpretations have the identical goal of extract-
tion kinetics and is greatly affected by diffusion of oxygen into ing Ea from ramped temperature experiments under different
the material, and likewise volatile diffusion and desorption scanning rates, but resolve the rate equation with different ap-
from the sample surface. TGA polymer behavior can be very proximations for the determination of the kinetic triplet (functional
different depending on whether a single sample (i.e. 10 mg) or form of conversion, Ea and frequency factor). The CoatseRedfern
finely cut sample pieces are analyzed. Even isothermal TGA approach uses defined reaction orders (i.e. first or second) [107],
measurements can be convoluted by DLO effects, which pro- whereas Friedman and Vyazovkin rely on iso-conversional
duce variability in activation energies extracted from such data
(see Fig. 8 for an EPDM material under oxygen). The results 10000
shown in Fig. 8 from 210  C to 170  C imply that timeetem- 4% loss
perature superposition of the weight loss versus aging time 3% loss
2% loss
curves is impossible. The relatively faster drop-off in weight 1% loss
loss at 170  C is also indicative of the pronounced induction- Ind time
1000
time behavior found for many EPR/EPDM materials during
Time [min]

4% 82 KJ/mol
oven aging. While an Ea of 160 kJ/mol is observed for the in-
3% 72 KJ/mol
duction time and 1% weight loss data over the 170e210  C 2% 71 KJ/mol 4% 124 KJ/mol
temperature range, this material has yielded an Ea of 113 kJ/mol 1% 74 KJ/mol 3% 132 KJ/mol
tind. 73 KJ/mol 2% 147 KJ/mol
for loss in tensile elongation between 170 and 110  C and even 100
1% 160 KJ/mol
lower values with oxidation rate measurements toward 52  C tind. 160 KJ/mol
[103]. This is an example of the non-correlation in Ea that can
exist between lower temperature extended thermal aging and
a rapid TGA approach. 10 240°C 230°C 220°C 210°C 200°C 190°C 180°C 170°C

 TGA curves need to be thoroughly deconvoluted to yield


kinetic insight and activation energies, This requires actual 1.9 2.0 2.1 2.2 2.3
chemical conversion with temperature/time for clearly 1/T [10-3K-1]
defined decomposition steps. If multi-step reactions are
Fig. 8. Time data for equivalent weight loss levels taken from primary TGA curves from
involved they should consist of clearly separated single-stage isothermal analysis of an EPDM material under oxygen. It shows the effect of DLO
steps, as mentioned in standards such as ISO 11358 and resulting in curved Arrhenius behavior and the dependence of Ea on temperature and
ISO 11358-2. extent of weight loss.

Please cite this article in press as: Celina MC, Review of polymer oxidation and its relationship with materials performance and lifetime
prediction, Polymer Degradation and Stability (2013), http://dx.doi.org/10.1016/j.polymdegradstab.2013.06.024
8 M.C. Celina / Polymer Degradation and Stability xxx (2013) 1e11

treatment of the rate equation [106,108]. The Ozawa and FlynneWall UV exposure conditions [121,122]. All this has to be considered
iso-conversional approach utilizes a linear approximation in the with the goal of true biodegradation, which appears to be
integrated rate constant with respect to inverse temperature in a dependent on the interaction of fine polymer particulate degra-
narrow range of Ea/RT [104,105]. Such models are mathematically dation products with moisture based on relative surface area,
correct as long as exact conversion can be derived from weight loss versus just ‘bio-fragmentation’ leaving undesirable polymer trash
curves for a particular decomposition step; and this represents the in the environment.
key challenge with ramped TGA.
Ramped TGA data interpretation is intrinsically complicated or
2.8. Research strategy for better predictive models
often impossible because polymer degradation rarely proceeds
with well resolved individual decomposition steps. Weight loss
There is a need for broad polymer reliability models which can
curves often show multiple parallel degradation steps, and hence
predict changes in polymer performance associated with specific
the activation energies when ‘brute-force’ mathematics are applied
physical properties based on an understanding of time-dependent
to weight loss data as perceived conversion, do not replicate a
and spatially resolved degradation chemistry. One such application,
particular mechanistic step that may govern long-term aging under
for example, can be found in photovoltaic (PV) modules where a
limited weight loss conditions. Ramped TGA experiments tend to
number of polymers are used as critical components and multiple
focus on degradation chemistry pathways that for most polymers
parallel degradation pathways are encountered. Long-term reli-
are too far removed from the mechanisms that are relevant for the
ability is a key demand, as is an understanding of the kinetics and
usual application conditions. Unless thermal pyrolytic decomposi-
mechanisms that reduce power outcome with time. If the pro-
tion behavior is the focus of a particular study, ramped TGA pre-
gression of spatially resolved chemistry is known as a function of
sents a high risk approach and introduces significant uncertainty
exposure conditions (for PV systems these are temperature, UV
for any polymer lifetime prediction purposes.
doses, ingress of oxygen and moisture), and cross-correlations with
physical property are available as model input, then very powerful
2.7. Other current developments predictive models can be developed. For example, oxidatively
driven degradation could be modeled for both thermo and photo-
This review also requires a few comments on some related oxidative processes subject to diffusion limited oxidation (DLO)
encouraging research trends relevant to heterogeneity and conditions (see a visual example in Fig. 9). Input parameters would
controlled degradation. There has long been a need to better be oxygen supply based on permeation through a number of
visualize heterogeneous thermo-oxidative degradation processes polymers, as well as thermal and photo-oxidation rates. For the
before they appear as visible cracks. Chemiluminescence (CL) latter, rates would need to be available in consumed oxygen mol/g s
originally provided direct evidence for interaction between and not only in produced carbonyl absorption versus deposited
degrading PP particles [18] and spreading phenomena in solid dose as is usually reported. Subsequently, these models could be
film samples [109e112], with ‘infectious degradation’ even improved by coupling oxidative degradation with parallel hydro-
observed between different polymers [113] and likely carried by lytic degradation processes, as long as moisture ingress parameters,
low molecular weight peroxidic species [114]. The usefulness of CL the kinetics of hydrolysis with temperature and localized water
has been greatly expanded with the advent of pro-fluorescent concentration, and cross-correlation with the most important
nitroxide reagents which allow monitoring the in-situ formation physical property changes can be established. In the future the
of free radicals during thermo-oxidative [115e117] or even during evolving knowledge of polymer degradation processes coupled
processing conditions [118]. Such avenues will greatly improve with more easily available computational tools will allow for the
diagnostic tools and will enable more insight into heterogeneous development of complex finite element (FE) DLO models to predict
polymer degradation aspects. It is equally important that a better the progression of spatially resolved property changes in polymers.
understanding of the effects of nano-particles on polymer A generic approach for such a potential target is given below:
degradation behavior be developed [119,120], since nano-
particulate fillers can also affect degradation pathways and  Characterization of oxygen permeation through relevant
rates. This plays into the accelerated environmental degradation polymers as a function of temperature. Measurement of
behavior of polymers (mostly polyolefins) where UV degradation permeability and its activation energy as material properties.
needs to be balanced with catalytically enhanced thermo- Derive numbers for oxygen solubility for all polymers involved.
oxidative processes, which for example can be facilitated by the  Characterization of thermo-oxidative polymer degradation.
incorporation of pro-degradants. It is clear that optimized mate- Measurements of intrinsic thermal oxidation rates and their
rials with on demand stability under environmental conditions activation energies.
require a solid understanding of the competing behaviors be-  Estimations of oxidation rates under UV exposure from IR
tween stabilizers, pro-degradants, processing and thermal versus changes (carbonyl, hydroxyl, etc.) as a function of deposited

Fig. 9. Visual example of competing oxidative processes (thermal and UV) in a mock PV section showing oxidative degradation below the glass cover (UV) and under the inert cell
(thermal) due to O2 diffusion trapping in a thin film, but strong DLO behavior above the cell. The encapsulant above the cell center experiences non-oxidative photo-chemistry.

Please cite this article in press as: Celina MC, Review of polymer oxidation and its relationship with materials performance and lifetime
prediction, Polymer Degradation and Stability (2013), http://dx.doi.org/10.1016/j.polymdegradstab.2013.06.024
M.C. Celina / Polymer Degradation and Stability xxx (2013) 1e11 9

dose or alternative avenues to measure oxidation rates as an Polymer oxidation will never cease, but analytical methods will
intrinsic material property under photo-oxidative polymer continue to evolve, as will model capabilities. Kinetic models that
degradation conditions. perhaps embrace more heterogeneous pathways consistent with
 Define localized oxygen supply and consumption scenarios for solid state reactions, incorporation of non-linear Arrhenius
specific geometries. Use DLO model to predict spatially behavior and morphological contributions to the effectiveness of
dependent oxidation states with progressive temperature and oxidative damage, should be expected. Significant progress will
UV exposure under static and dynamic conditions. occur in applied DLO models that soon will combine thermal and
 Establish cross-correlation of ‘degradation chemistry’ with parallel photo-oxidative processes. With similar efforts dedicated
‘performance critical physical properties’ using classic polymer to acquiring critical material parameters as model input (i.e.
degradation approaches, i.e. linking %-oxidation with light diffusion and permeation constants, plus oxidation rates under
transmissivity, discoloration, adhesion, embrittlement or thermal and UV- and g-radiation), spatially dependent visualiza-
similar features. tion and prediction of polymer oxidation in complex assemblies
 Predict progressive material degradation and property changes and geometries under dynamic exposure conditions are within
under long-term exposure conditions. reach. With suitable model calibration parameters (i.e. oxidation
 Apply similar reaction DLO models to hydrolytic processes as state versus physical property correlations) made available we will
long as water ingress, solubility, permeation parameters, and be a significant step closer to our goal of predicting localized failure
consumption kinetics have been established. This would also in components based on ‘Polymer Oxidation.’
require cross-correlations between ‘hydrolysis state’ and rele-
vant physical properties.
Acknowledgments

This paper is an invited contribution based on a plenary address


3. Conclusion
given at the 2012 MODEST conference. All previous and current
collaborators, colleagues, mentors, technical staff and students are
This brief summary of the status and major trends in polymer
gratefully acknowledged. Adam Quintana is recognized for creative
oxidation, its measurements, modeling, and effects shows, that all
approaches to DLO modeling. Sandia National Laboratories is a
the intricate details which affect the oxidation of polymers and
multi-program laboratory managed and operated by Sandia Cor-
basic property changes are not easily addressed. Many researchers
poration, a wholly owned subsidiary of Lockheed Martin Corpora-
have contributed to the comprehensive understanding of degra-
tion, for the U.S. Department of Energy’s National Nuclear Security
dation phenomena, which has evolved in parallel with polymer
Administration under contract DE-AC04-94AL85000.
synthesis and processing over the last 60 years. Tremendous
progress has been achieved, considering the knowledge docu-
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Please cite this article in press as: Celina MC, Review of polymer oxidation and its relationship with materials performance and lifetime
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