INFLUENCE OF THE CROSSLINK STRUCTURE ON THE ACTIVATION

ENERGY CALCULATED UNDER THERMO-OXIDATIVE CONDITIONS

RICHARD J. PAZUR*, T. MENGISTU

POLYMER AND TEXTILE SCIENCE, QUALITY ENGINEERING TESTING ESTABLISHMENT (QETE), DEPARTMENT OF NATIONAL
DEFENSE, OTTAWA, ON K1A 0K2, CANADA

RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 1, pp. 205–224 (2018)

ABSTRACT
A series of six carbon black reinforced brominated poly(isobutylene-co-isoprene) (BIIR) compounds has been
developed varying only in cure system type: sulfur, sulfur donor, zinc oxide, peroxide, phenolic resin, and ionic. Compounds
were aged from room temperature up to 115 8C, and hardness, mechanical properties, and network chain density were
measured. Non-Arrhenius behavior was observed due to data curvature from 70 to 85 8C. The oxidation process was
adequately described by assigning low (23–85 8C) and high (85–115 8C) temperature regimes. Heterogeneous aging due to
diffusion limited oxygen (DLO) occurred for heat aging above 85 8C, and all measured responses except tensile strength were
strongly affected, causing lower activation energies. The activation energy for the high temperature oxidation process is in
the range of 107 to 133 kJ/mol in the following ascending order: zinc oxide, ionic, sulfur donor, sulfur, peroxide, and resin.
The midpoint of the high temperature activation energies is of the same order as the BIIR and poly(isobutylene) elastomers.
The low temperature activation energy is in the range of 55–60 kJ/mol and is likely due to a combination of oxidative chain
scission (crosslink density loss) and crosslinking recombination (network building) reactions. Apart from the crosslink
structure stability, the presence of unsaturation along the polymer chain after vulcanization affects the high temperature
activation energy. [doi:10.5254/rct-17-83714]

INTRODUCTION
Much work on lifetime prediction has been accomplished on commercially provided rubber
formulations. Such information is invaluable, as it provides useful service and/or shelf life data for
manufactured rubber articles under thermo-oxidative environments. However, it is well known that
such formulations can possess deviant Arrhenius behavior causing difficulty in data interpretation
and subsequent extrapolation to service temperatures.1 The lack of knowledge of the base elastomer
structure as well as the level and type of compounding ingredients (reinforcing/non-reinforcing
fillers, antioxidant, plasticizer, vulcanization system, etc.) prevents a thorough comprehension of
their effect on the activation energy measured through the Arrhenius approach.
Lifetime predictive studies involve heat aging a material under various temperatures and times
and then measuring compound property changes.2 Time–temperature superposition (T-TS) is used
to overlay the property data at a defined reference temperature Tref, by shifting the time through the
use of shift factors (aT), which are used to calculate the activation energy (Ea) for the thermo-
oxidative process via the Arrhenius equation (see Eq. 1) where R is the gas constant (8.314 J/K/
mol).
  
Ea 1 1
aT ¼ exp  ð1Þ
R Tref T
Ea represents an effective activation energy for the total mix of chemical reactions underlying the
compound degradation. A change in the relative mix of competing oxidative degradation reactions
as a function of temperature can lead to curvature in the Arrhenius plot. Diffusion limited oxygen
(DLO) can occur whenever the oxygen consumption rate is greater than the rate at which oxygen
can be resupplied by diffusion by the surrounding air, causing the production of heterogeneously

*Corresponding author. Email: richard.pazur@forces.gc.ca

205
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oxidized materials: high levels of oxidation on the surface and reduced or non-existent oxidation in
the interior regions.3 This phenomenon depends primarily on temperature and sample geometry
(i.e., sample thickness).
Our group has been interested in examining the thermal stability of isobutylene containing
polymers in thermo-oxidative environments in order to aid in the determination of reliable shelf
and/or service lives of butyl based articles. Base elastomers have been investigated in order to
mitigate any effects from the formulation, and thermo-oxidation after aging in the 40–100 8C
temperature range was followed using carbonyl growth measurements by transmission Fourier
transform infrared spectroscopy. Poly(isobutylene)(PIB) possesses Ea values from 116 to 125 kJ/
mol.4 The addition of isoprene in forming the poly(isobutylene-co-isoprene) (IIR) copolymer
caused the appearance of non-Arrhenius behavior due to competing oxidative degradation
reactions at high and low temperatures seen by the curvature in the Arrhenius plot in the vicinity of
70 8C. The high (80–100 8C) and low (23–70 8C) temperature oxidative processes possess
activation energies of 85–87 and 59 kJ/mol, respectively, and are both significantly lower than that
of the homopolymer.5 Isoprene incorporation levels of either 0.9 and 1.85 mol% did not affect the
activation energy. Upon halogenation of IIR to produce chlorinated (CIIR) and brominated (BIIR)
poly(isobutylene-co-isoprene), it was found that the activation energy increased in the high
temperature regime (114 and 121 kJ/mol) and decreased at lower temperatures (52 and 22 kJ/mol)
for CIIR and BIIR, respectively.6 The difference in the low temperature energy was explained
largely by the increased thermal stability of the C–Cl over the C–Br bond. The higher thermal
stability of halobutyls over IIR may be related to the unique array of halobutyl unsaturated
microstructures, which is dominated by the kinetically favored exomethylene group.
General vulcanization information pertaining to BIIR and its effect on compound properties
can be found in Harmsworth, Fath and Radar, and Fusco.7–9 The weak C–Br bond strength in BIIR
leads to cure sites on the polymer main chain that are inherently more reactive, resulting in faster
cures and better adhesion to unsaturated rubbers.10 In addition, it enables a greater cure versatility
by providing the possibility of using a wide range of curatives. Owing to the predominance of the
exomethylene structure in the base elastomer, it will be assumed that the majority of crosslinking is
taking place at this unit. Heat application at vulcanization temperatures causes its isomerization to
the bromomethyl structure, but it is understood that concurrent transformation to the more stable
endomethylene form and to conjugated dienes through loss of HBr is also taking place.11 These
unsaturated structures together with residual isoprene may also participate in additional
crosslinking through different mechanisms. A summary of the most plausible crosslink structures
investigated in this study is provided in Figure 1.
Sulfur curing normally provides relatively unstable polysulfidic crosslinks, while efficient
vulcanization (EV) systems use less total sulfur such as through the use of a sulfur donor system in
order to provide more stable crosslinking (mono and disulfide crosslinks) and enhanced heat
resistance. The dissociation energy increases in going from polysulfidic (142 kJ/mol), to disulfide
(226 kJ/mol), and to monsulfide (310 kJ/mol) crosslinks. Highly polysulfidic crosslinks are more
heat labile and may lead to reversion with a resulting loss of crosslinks during non-oxidative
thermal vulcanizate aging. BIIR is unique in its ability to be cured by sulfur alone due to the
weakness of the C–Br bond (Figure 1a.). Acid catalysis through the generation of HBr is known to
hasten the conversion of the polysulfidic crosslinks to shorter lengths albeit with a loss of crosslink
density.12 The first structure of Figure 1a is kinetically favored due to the isomerization of the
exomethylene to bromomethyl group at vulcanization temperatures.
The reaction of BIIR with a base such as zinc oxide is believed to progress through the
formation of zinc bromide, which then catalyzes the cationic crosslinking reaction. Stable carbon–
carbon bonds (335 kJ/mol) between adjacent chains are formed in conjunction with conjugated
 INFLUENCE OF CROSSLINK STRUCTURE ON ACTIVATION ENERGY 207

FIG. 1. — Summary of the crosslinking systems and their likely structures upon vulcanization with BIIR: (a) sulfur and EV,
(b) zinc oxide, (c) peroxide, (d) phenolic resin, and (e) ionic. Reaction products are primarily shown through reactions via the
highly reactive exomethylene (and bromomethyl) groups.

diene groups along the polymer backbone. The final structure of Figure 1b has been proposed by
Vukov.13
Radical curing of BIIR is feasible through the use of a peroxide, a coagent, or a combination of
both, producing vulcanizates possessing low compression set, high heat resistance, and improved
ozone resistance. Free radical curing of BIIR via a homolytic scission of the C–Br bond is the most
likely mechanism producing C–C crosslinks between adjacent chains through a coupling
termination reaction. This reaction, however, is in competition with the molecular weight
breakdown of the dominant isobutylene regions of the polymer, so it must proceed at a faster rate
than the latter in order to form a stable crosslink network. A series of plausible final radical induced
structures is depicted in Figure 1c.
Phenolic resin cure is known to provide outstanding heat/oxidation resistance to butyl
compounds due to the stability of the aromatic crosslinks.14–16 One plausible crosslinking structure
is shown in Figure 1d, where the resin chain ends have been shown to undergo 1,4 cycloaddition
onto the main chain saturation of the bromomethyl microstructure to generate a stable chroman ring.
An increase in resin content aids in favoring crosslinking reactions over degradation chain scission
upon thermo-oxidative aging.17
Through a post-polymerization functionalization by nucleophilic substitution, ionomeric type
structures can be generated as seen in Figure 1e. Ionic bonding can lead to improved green strength,
208 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 1, pp. 205–224 (2018)

adhesion, flex, and impact resistance of BIIR, but the ionic clusters are labile in nature and break
down at temperatures over 100 8C.18
It is possible to learn about the effect of thermo-oxidative aging on cure systems by
summarizing investigations that deal with both butyl rubber and BIIR due to their abilities to
vulcanize with similar systems. Edwards19 examined the degradation of unfilled butyl vulcanizates
cured with either sulfur, quinoid, or phenolic resin using equilibrium swelling in cyclohexane. For
varying levels of butyl unsaturation, the activation energies for the sulfur system varied from 112 to
132 kJ/mol for 149–177 8C, while the resin cure possessed values from 103 to 122 kJ/mol for 177–
204 8C. Increasing isoprene content led to an increase in the sulfur activation energy, while such
dependence was not seen for the resin. Results in comparing resin cured BIIR with IIR showed that
the latter was superior for heat aging resistance.15 Optimal heat resistance in BIIR was attained
through a zinc oxide activated sulfur donor cure system comprising of active magnesium oxide.15
Heat aging of a series of BIIR compounds differing only in cure system (conventional sulfur, semi-
EV, EV, bismaleimide/peroxide, phenolic resin/ZnO) was performed for up to 1 week at 150 8C.20
All sulfur containing systems exhibited poor heat resistance with loss of all tensile strength after 1
week aging. The bismaleimide/peroxide and phenolic resin/ZnO vulcanization systems provided
the best retention of crosslink density and heat aging resistance. Kannan et al.21 has investigated the
thermo-oxidative behavior of a sulfur cured BIIR nuclear, biological, chemical respiratory mask
and found that tensile strength loss reached 63% through aging at 80 and 100 8C. Surface cracking
developed at 120 8C. Elongation at break change values were chosen at 80, 100, and 120 8C for
lifetime prediction. The elongation at break data are seen to reach a limiting lower plateau at about
60% loss in the 80 and 100 8C temperature ranges.
Peroxide cured butyl compounds of thermally aged butyl-A and butyl-B O-rings were reported
to possess significantly different Arrhenius behavior through compressive stress relaxation and
ultra-sensitive oxygen consumption measurements.22–24 Linear Arrhenius behavior (82 kJ/mol)
was demonstrated by butyl-A, while butyl-B was best described as containing a high (100 kJ/mol)
and low temperature (60 kJ/mol) process. DLO concerns were minimized by using a smaller test
specimen size, and the deviant Arrhenius behavior of butyl-B was able to account for the dissimilar
service lives. Xiang et al.25 has reported Ea values of 127 and 59 kJ/mol for the high and low
temperature process of a silica filled and resin cured butyl compound using compression set
measurements. The effect of DLO on their high temperature testing results, however, cannot be
ruled out given the size of the compression disks (3 cm diameter 3 1.25 cm h). More work into
investigating the effect of cure systems in BIIR during thermo-oxidative aging would be a welcome
asset to rubber technology.
This investigation will examine the effect of the type of cure system and, therefore, crosslink
structure on the thermo-oxidative resistance in a series of carbon black filled BIIR compounds. Six
compounds have been devised varying in cure system type—sulfur, sulfur donor, zinc oxide,
peroxide, phenolic resin, and ionic—and then aged from room temperature up to 115 8C for various
times. Hardness, mechanical properties, and network chain density have been measured. In addition
to property change data, activation energies will be calculated through the Arrhenius approach in
order to assess the stability of the crosslink structures.

EXPERIMENTAL
Six BIIR rubber compounds of equal carbon black loading and differing only in their cure
system have been developed as illustrated in Table 1. Formulations were devised in order to
maximize as much as possible a single type of crosslinking. This led to the omission of zinc oxide
activation for both the sulfur and resin cures as well as a coagent for the peroxide based formulation.
Other details about the compounding ingredients are provided in the appendix (Table A1).
 INFLUENCE OF CROSSLINK STRUCTURE ON ACTIVATION ENERGY 209

TABLE 1
FORMULATIONS OF THE SIX BROMOBUTYL COMPOUNDSa

Ingredients Sulfur EV ZnO Peroxide Resin Ionic

Bromobutyl 1 100 70
Bromobutyl 2 0 30
Carbon black (N550) 50
Stearic acid 1
Zinc oxide 0 0 5 0 0 5
Sulfur 1.5 0 0 0 0 0
DPTT-70 0 2 0 0 0 0
ZDMC 0 0.2 0 0 0 0
Peroxide 0 0 0 1.5 0 0
Resin 0 0 0 0 2 0
Phrs 152.5 153.2 156 152.5 153 156
a
Each formulation will be designated by their cure type throughout the report. Further information about the compound
ingredients is provided in the Appendix.

Mixing took place on a Plasticorder internal mixer (Brabender) equipped with cam blades and a
420 cm3 mixing chamber per ASTM D3182. A two roll laboratory mill (Farrell) was used to refine
and to sheet out the compounds. Molded tensile slabs were prepared on a hydraulic compression
press (Wabash) set at 160 8C and using a pressure of 90 short tons.
Cure and rheological characteristics were measured on a moving die rheometer (MDR) 3000
Basic (MonTech) using a die temperature of 160 8C and an arc of 18.
Hardness measurements of the tensile sheets were carried out using a digital Type A tester
(Shimana) following ASTM D2240.
A universal tensile testing machine (TechPro) possessing a 500 N load cell was used to
measure physical properties. Testing was carried out following ASTM D412 guidelines, and a MET
D4482 die was employed to cut out the 2 mm thick samples. Samples were tested in triplicate and
median values reported.
A hot air circulating oven (Binder) was used to age the dumbbell samples according to the
method described in ASTM D573. The aging temperatures and times are provided in Table 2.
Eighteen data points were measured for each cure system.

TABLE 2
HEAT AGING MATRIX AS A FUNCTION OF TIME AND TEMPERATURE

t, wk

T, 8C 1 2 3 4 5 8 10 15 25 30 40 60

23 x x
40 x x
55 x x x
70 x x x
85 x x x
100 x x
115 x x x
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FIG. 2. — Compound curing behavior represented by the elastic component of the torque as a function of time as measured
by MDR at 160 8C.

The network chain density (n) was calculated through using the equilibrium solvent swelling
technique according to Eq. 2. For butyl based rubbers, cyclohexane was the preferred solvent, and a
value of 0.44 (ref. 26) was used for the Flory–Huggins interaction parameter (v). A phantom model
derived through use of crosslink point fluctuations was chosen, and a chain functionality of 4 was
assumed. Vs is the molar volume for cyclohexane, and mr is the volume fraction of rubber that was
corrected due to filler (carbon black and zinc oxide) content by the method of Kraus.27 Values of the
network chain density are presented in terms of percentage change with the assumption that the
level of physical interactions between the polymer chains and the carbon black remain constant
during the aging process.
n 1
lnð1  vr Þ þ vr þ vv2r ¼  Vs v3r ð2Þ
2

RESULTS AND DISCUSSION

The six compounds possess widely different rheological and vulcanization behavior
depending on the type of cure system (see Figure 2). The most rapid cures were provided by the
sulfur, EV, and peroxide systems followed by ZnO, while the resin and ionic systems required up to
2 hours of total cure time given the lack of activator or accelerator in their formulations. The sulfur
cure system demonstrates strong reversion due to changes in sulfur crosslink length distribution and
crosslink loss. This is good evidence that the system is polysulfidic in nature, as reversion was
 INFLUENCE OF CROSSLINK STRUCTURE ON ACTIVATION ENERGY 211

TABLE 3
SUMMARY OF INITIAL HARDNESS, MECHANICAL PROPERTIES, AND NETWORK CHAIN DENSITY MEASURED AT AMBIENT
TEMPERATURE

Type A Tensile
Cure hardness, strength, Elongation 50% tensile 100% tensile 300% tensile n 3 104,
system pts MPa at break, % stress, MPa stress, MPa stress, MPa mol/cm3

Sulfur 52 13.9 490 0.4 1.2 9.1 5.0

EV 51 14.6 500 0.3 0.8 8.8 3.8
ZnO 52 10.7 360 0.4 1.8 9.3 3.8
Peroxide 39 7.0 600 0.3 0.3 1.9 1.2
Resin 53 8.1 470 0.3 0.5 5.7 2.7
Ionic 54 9.3 440 0.4 1.3 7.3 1.6

limited in the EV or sulfur donor system. Using the maximum torque as an indication of state of
cure, the compounds from highest to lowest are in the order of sulfur, EV, ZnO, peroxide¼resin and
ionic. Given the time to 90% optimum cure values (i.e., tc90), tensile sheets were molded at 160 8C
for the following press times (in minutes): sulfur, 10; EV, 20; ZnO, 15; peroxide, 10; resin, 120;
ionic, 40.
Table 3 summarizes the unaged hardness, mechanical properties, and network chain density of
the six formulations, while their corresponding stress–strain curves are illustrated in Figure 3. Cure
system type has a significant effect on these properties in spite of the constant loading of reinforcing
carbon black. The peroxide cured material possesses the poorest combination of compound

FIG. 3. — Representative curves of the stress–strain properties measured at 23 8C of the unaged compounds.
212 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 1, pp. 205–224 (2018)

properties: lowest hardness, network chain density, and tensile strength and highest elongational
behavior. The absence of peroxide coagent in the formulation is the primary reason for the lack of
stiffness and chain network formation. Chain breaking reactions due to the radical nature of curing
at high temperatures would also contribute to lower overall stiffness. Lack of compound
stabilization may also play a part in lower hardness observed in using peroxide versus the other
compounds. The remaining compounds possess quite similar hardness (51–54 pts) values but differ
in their ultimate properties and network chain density. The sulfur based system possesses the
highest network chain density agreeing with the rheometry maximum torque behavior of Figure 2.
The EV and ZnO cured compounds possess the same network chain density. The higher ultimate
properties of the sulfur containing compounds are likely due to the ability of sulfur crosslinks to
break, rearrange, and recombine during tensile stretching in contrast to the stability of the C–C
bond. This may explain the lower elongation at break and tensile strength for the ZnO compound.
The reason for the discrepancy between rheological state of cure and network chain density between
the EV and ZnO cure systems is unknown. The lower network chain density and corresponding
state of cure observed in the ionic compound were likely due to the competition between the
carboxylate groups and the cationic crosslinking reaction for zinc oxide. The combination of ionic
bonding with less C–C bonds compared with the ZnO compound is likely responsible for the higher
elongational behavior. The resin cure system is in general agreement between its network chain
density and state of cure by rheology in relationship to the other compounds. Little distinction
between all the compounds is observed using the tensile stress at 50% elongation as a test criterion,
likely due to the softness of these compounds. The tensile stress response demonstrates compound
differentiation for elongations of 100% and beyond.
Figures 4–9 summarize the aging data following the heat aging matrix of Table 2 for the
percentage change in the five chosen responses: hardness, tensile strength, ultimate elongation,
50% tensile stress, and network chain density for the six BIIR compounds. The aging data in each
case were shifted assuming time–temperature superposition (T-TS) principles by a shift factor aT in
order to line up with the data points on the dashed master line, which has a reference temperature of
85 8C (i.e., aT ¼ 1). Some extra extrapolation of the data points was necessary, especially in the
lower temperature region.
In the case of the sulfur cured system of Figure 4, the hardness and 50% tensile stress change
data each clearly demonstrate that the samples stiffen with time. An appreciable increase of
hardness of about 15 points was measured. Tensile strength displays a slow rise to a maximum and
then abruptly decreases to values nearing 70%. Elongation at break slowly decreases with aging,
reaching values of60%. A 50% decline of either ultimate property is generally indicative of loss of
the material functionality. The network chain density displays a small drop in the beginning
followed by an increase to a maximum value before falling after aging for the longer shifted aging
times. Maximum property change was achieved through aging to 85 8C for the hardness,
elongation, and tensile stress. For these responses, aging at 100 and 115 8C caused an attenuated
value, which slowly increased, decreased, or stagnated as a function of aging time. We attribute this
unusual behavior to heterogeneous aging due to DLO. In this temperature range, oxidation is
causing hardening at the sample surface, hindering oxygen diffusion into the matrix. In the absence
of oxygen, heat induces a proliferation of chain scission reactions in the isobutylene sequences of
BIIR, causing a drop in network density. This is observed in the decrease of the crosslink density
data at 100 and 115 8C. Of the five responses tested, only the tensile strength appears to follow the
expected loss behavior, with values continuing to decrease at higher temperatures. DLO effects for
1–2 mm thick rubber specimens are expected for heat accelerated aging above 80 8C.1
The effect of accelerated aging on the sulfur donor or EV system is provided by the graphs
illustrated in Figure 5. This system is displaying behavior very similar to the property changes of the
responses in the sulfur system as a function of time and temperature. The tensile strength does not
 INFLUENCE OF CROSSLINK STRUCTURE ON ACTIVATION ENERGY 213

FIG. 4. — Aging and accompanying T-TS graphs for the five responses measured on the sulfur cured BIIR compound.
214 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 1, pp. 205–224 (2018)

FIG. 5. — Aging and accompanying T-TS graphs for the five responses measured on the sulfur donor cured BIIR compound.
 INFLUENCE OF CROSSLINK STRUCTURE ON ACTIVATION ENERGY 215

FIG. 6. — Aging and accompanying T-TS graphs for the five responses measured on the zinc oxide cured BIIR compound.
216 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 1, pp. 205–224 (2018)

FIG. 7. — Aging and accompanying T-TS graphs for the five responses measured on the peroxide cured BIIR compound.
 INFLUENCE OF CROSSLINK STRUCTURE ON ACTIVATION ENERGY 217

FIG. 8. — Aging and accompanying T-TS graphs for the five responses measured on the resin cured BIIR compound.
218 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 1, pp. 205–224 (2018)

FIG. 9. — Aging and accompanying T-TS graphs for the five responses measured on the ionic cured BIIR compound.
 INFLUENCE OF CROSSLINK STRUCTURE ON ACTIVATION ENERGY 219

proceed through a small maximum and reaches a loss beyond 60% for the longest shifted aging
time. The best fit of the network chain density T-TS did not go through a maximum but nevertheless
displayed maximum gains through the 85 8C aging data. The relative magnitude of property loss is
only slightly better than that of the straight sulfur system. More of an improvement was expected
due to the prevalence of mono and disulfide bridges in the EV system. Under mild aging conditions,
the sulfur system develops a similar crosslink structure to the EV system. DLO is affecting all the
responses beyond 85 8C except for the tensile strength.
Figure 6 summarizes the aging data along with the T-TS for the ZnO cure system.
Hardness change values increase with aging time up to a maximum of approximately 20 pts.
The surface hardening effect through thermo-oxidation appears to be more aggressive versus
the sulfur based systems. Tensile strength displays a slight drop in the beginning and then
goes through a maximum before falling to a 40% loss at the longest shifted aging time. The
elongation at break shows a small increase and then gradually decreases to a lowest value of
40%. The tensile stress at 50% elongation displays an increasing behavior with shifted
aging time similar to the hardness. The network change density decreases for low aging
times (20%) but then increases steadily to values up to 120%. The overall magnitude of
ultimate property of 40% is less than either the sulfur or EV system, demonstrating the
improved heat aging resistance of this cure system due to the heat stability of the C–C
crosslinks. As with the sulfur based cure systems, tensile strength is able to follow the loss
of properties in spite of DLO effects operating above 85 8C.
The peroxide cured compound aging data are summarized in Figure 7. This system stiffens
substantially with shifted aging time as seen by both the hardness (up to 25 pt increase) and 50%
tensile stress (400% increase). The tensile strength data show little change in the beginning but then
decrease down to values of 70%. Elongation at break values are stable and slowly decrease to
about60%. A network chain density loss of about30% is observed at short times, which quickly
increases up to 175% with the 85 8C aging data. Poorer T-TS was observed for the hardness and 50%
tensile stress data. Property loss in this system is generally worse than the ZnO cure and about equal
with the straight sulfur system. Furthermore, it is obvious that all responses are affected by DLO at
100 and 115 8C except for the tensile strength change.
The resin cured compound aging data are provided in Figure 8. This system possesses a much
lower surface stiffness rise compared with the previous systems with hardness increases limited to
10 pts. The tensile strength displays a slight rise and then abruptly decreases down to 60% for the
longest shifted aging time. The elongation at break change is positive at short times and then
decreases down to values around 40% for the longest shifted aging time. The network chain
density initially drops to 50% before slowly rising with aging time to about 60%. Except for the
minimal hardness rise upon aging, the magnitude of the losses (or gains) of the responses is similar
to the sulfur, EV, and ZnO systems.
Finally, the results of the aging for the ionic system are illustrated in Figure 9. This system
contains both C–C (due to the presence of zinc oxide) and ionic bonding. This formulation appears
to show exceptional heat aging resistance up to 100 8C where the hardness change is limited to
between 0 to 4 pts. At 115 8C, however, the hardness immediately jumped to values between 10 and
12 pts. The tensile strength shows a modest rise in value up to 30% before falling for the longest
aging time down to near 30%. The elongation at break slowly decreases with shift aging time
down to a maximum loss of 30%. The network chain density displays a small loss at lower times
followed by an increase to up to 150%. This particular combination of cure systems appears to
mitigate in particular the ultimate property losses. The abrupt increase in hardness is likely due to
the transition that destroys the ionic bonding above 100 8C.18 Upon cooling, the ionic clusters
reform into a tighter network. This is akin to a post-curing reaction, which has been proved to be
beneficial for other elastomers containing ionic bonding.28
220 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 1, pp. 205–224 (2018)

FIG. 10. — Arrhenius plots of the derived shift factors for (a) sulfur, (b) EV, (c) zinc oxide, (d) peroxide, (e) resin, and (f )
ionic cured compounds using Tref ¼ 85 8C.

The Arrhenius plots for all six compounds are summarized in Figure 10. In all cases, curvature
was observed in the 70–85 8C region, indicating that two competing oxidation processes are taking
place. T-TS was attempted at reference temperatures of 70 and 85 8C, and it was found that the latter
temperature permitted a more convenient separation between the high (85–115 8C) and the low
temperature (23–85 8C) processes. The tensile strength possesses the steepest slope in the high
temperature range independent of cure system in comparison to the other four responses. The latter
data have been deeply influenced by the onset of DLO effects as discussed earlier, bringing about a
lower slope to the Arrhenius plot. In contrast, the five responses are demonstrating similar linear
Arrhenius behavior in the low temperature region.
Activation energies and goodness of fit for the high temperature regions are summarized in
Table 4. The tensile strength response appears to amply describe the high temperature processes,
while the other responses present either much lower activation energies or lower linearity due to
DLO effects. Only the network chain density for the sulfur system shows some similarity to the
tensile strength activation value. The reasoning for this is unknown, but it may be related to the
 INFLUENCE OF CROSSLINK STRUCTURE ON ACTIVATION ENERGY 221

TABLE 4
ACTIVATION ENERGIES AND R2 COEFFICIENTS (IN PARENTHESES) CALCULATED FOR THE HIGH TEMPERATURE (85–115 8C)
THERMO-OXIDATION PROCESS

Property Sulfur EV ZnO Peroxide Resin Ionic

Hardness 37 (0.99) 24 (0.85) 83 (0.97) 43 (0.79) 27 (1) 61 (1)

Tensile strength 128 (0.99) 117 (0.98) 107 (0.99) 126 (1) 133 (0.97) 108 (0.96)
Elongation at break 58 (0.97) 64 (1) 67 (0.9) 27 (1) 37 (0.87) 69 (0.99)
50% tensile stress 28 (0.78) 42 (0.85) 59 (0.81) 40 (0.99) 15 (0.12) 56 (0.75)
Network chain density 120 (0.99) 33 (1) 65 (0.95) 50 (0.99) 43 (0.97) 82 (0.96)

extent of DLO effects on both the compound and property response. The activation energy for
tensile strength change is in the range of 107–133 kJ/mol across all six compounds. The highest
activation energies were calculated from the resin, sulfur, and peroxide cure systems. The ZnO and
ionic bonding systems possessed the lowest activation energy from tensile strength for the high
temperature process. Assuming curvature at 70 8C for the peroxide cure system, the 126 kJ/mol
result becomes 99 kJ/mol, which is in good agreement with the high temperature result of 101.5 kJ/
mol from 80 to 110 8C reported by Gillen et al.23 Our activation energy result of 133 kJ/mol for the
resin system is slightly higher than those reported for butyl rubber.19,25 The combination of either
high temperature testing or large specimen size can lead to DLO effects, which would consequently
lower calculated activation energies.
In comparison with the high temperature activation energy values for BIIR (121 kJ/mol) and
PIB (116–125 kJ/mol), the midpoint (120 kJ/mol) of the calculated activation energy range is in
excellent agreement. The sulfur, sulfur donor, and peroxide cures are closest to the base elastomer
values, whereas the resin and the zinc oxide based vulcanizations provided higher and lower
activation energies, respectively, in the high temperature region. Oxidative chain breaking
reactions are dominant in the isobutylene regions for temperatures above 85 8C and would be the
main contributor to the overall activation energy.4,29 Heat induced depolymerization causing
chain scission can also take place generating end chain radicals in the absence of oxygen.30
Assuming that the level of chain breaking reactions in the isobutylene regions is independent of
crosslinking system, similar activation energies would be expected. This was not the case, since
the differences seen can be linked to the stability of the crosslink and polymer chain at the
crosslinking point. The resin cure provided the most stable crosslinking due to its aromatic nature
and attachment to the polymer chain via the proposed chroman structure (Figure 1d), which
eliminates main chain unsaturation. On the other hand, the lower activation energy seen for the
ZnO cured system may be due to the chain unsaturation produced during vulcanization, since the
allylic sites may undergo hydrogen abstraction and additional oxidation reactions. Nonetheless,
these extra reactions appear to attenuate ultimate property loss providing a perceived improved
heat resistance. The addition of ionic crosslinking in combination with the ZnO cure did not
change the high temperature activation energy, but its addition does aid in reducing ultimate
property loss upon heat aging, likely due to the breaking and reforming of the ionic clusters during
tensile testing at ambient temperature. Finally, the sulfur, sulfur donor, and peroxide activation
energies were similar within error. As with the zinc oxide system, the degree of chain unsaturation
on the adjacent chains between crosslinks is a likely additional factor in contributing to chain
instability adjacent to the crosslinks.
The five responses showed much more similarity in activation energies for the low temperature
region as seen in Table 5 due to the absence of DLO. An averaged value of 55 6 10 kJ/mol is a good
approximation across all the responses for the sulfur, zinc oxide, peroxide, and resin cures. The
222 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 1, pp. 205–224 (2018)

TABLE 5
ACTIVATION ENERGIES AND R2 COEFFICIENTS (IN PARENTHESES) CALCULATED FOR THE LOW TEMPERATURE (23–85 8C)
THERMO-OXIDATION PROCESS

Property Sulfur EV ZnO Peroxide Resin Ionic

Hardness 61 (0.97) 63 (0.98) 44 (0.95) 47 (0.99) 57 (0.95) 50 (0.98)

Tensile strength 58 (0.99) 55 (0.96) 47 (0.94) 48 (0.95) 54 (0.99) 50 (0.98)
Elongation at break 56 (0.96) 63 (0.96) 61 (0.94) 59 (0.99) 59 (0.99) 57 (0.99)
50% tensile stress 53 (0.96) 54 (0.99) 48 (0.93) 41 (0.99) 47 (0.98) 55 (0.99)
Network chain density 53 (0.96) 65 (0.96) 61 (0.96) 57 (0.99) 59 (0.98) 69 (0.96)

sulfur donor and ionic systems possess an average activation energy of 60 6 10 kJ/mol. Owing to
the error involved, a difference in crosslink stability in this temperature range was not discerned.
Furthermore, more experimental values from the room temperature to 55 8C range would aid in
facilitating the drawing of the master curves during T-TS. Nevertheless, our results are in excellent
agreement with the reported values of 60 and 59 kJ/mol for the low temperature thermo-oxidation of
peroxide and resin cured butyl, respectively.23,25
All crosslinking systems underwent an initial network chain density loss during aging from
ambient to 40 8C and then slowly started to increase upon increasing both temperature and time.
Lack of an antioxidant system in the formulations may explain the drop in crosslink density. The
sulfur based systems can rearrange to a certain extent, causing a loss in sulfur crosslinking as readily
seen in the reversion of the rheological maximum torque of Figure 2. Low temperature oxidation
reactions commencing by hydrogen abstraction6 may be occurring at the numerous allylic positions
along the chain backbone for the crosslinked structures of Figure 1. These reactions can
conceivably lead to chain scission and a decrease in measured crosslink density. In fact, owing to
the potential of hydrogen abstraction, the carbon–carbon crosslinks of the ZnO (Figure 1b) and
peroxide (Figure 1c) are susceptible to direct oxidation, which can lead to crosslink breakage.
Assuming the crosslink structure of the resin cure of Figure 1d, hydrogen abstraction is favored at
the tertiary carbon of the chroman ring, leading to oxidation and chain scission reactions. The
increase in crosslink density can be explained by crosslinking reactions that start to predominate
through recombination reactions only at temperatures of 55 8C and above. The low temperature
oxidation chain scission and crosslinking reactions are likely adequately described by the low
temperature activation energy (55–60 kJ/mol).
Finally, the DLO process has an effect on property responses for the butyl rubber system. In
comparison with other elastomers, the oxygen permeation rate is inherently less in butyl due to the
enhanced packing density of the regularly spaced methyl units in the isobutylene zones. Above 85
8C, the development of a thin, hard surface layer additionally prevents oxygen diffusion into the
matrix. This contributes to the reduction in permeation behavior along with solubility effects after
thermo-oxidation.31 The interior of the sample softens and gradually loses tensile stress due to the
advent of chain scission reactions, which dominate upon increasing temperature. Depolymer-
ization reactions can take place in the absence of oxygen, further leading to loss of molecular
weight. Matrix softening is the most dominant contributor to the overall sample cross-section
stiffness in comparison with the thin, hardened surface layer, so it permits the tensile strength
response to adequately follow the overall degradative effects. This mechanism is contrary to
observations seen with nitrile rubber, which develops surface cracking that initiates elongational
failure at the hardened oxidized surface.2 Surface cracking was not observed in our high
temperature testing up to 115 8C, and thus elongation at break was not a good predicative response
for Arrhenius.
 INFLUENCE OF CROSSLINK STRUCTURE ON ACTIVATION ENERGY 223

CONCLUSIONS
Non-Arrhenius behavior during the thermo-oxidative aging of BIIR compounds was observed
from room temperature to 115 8C due to curvature in the 70–85 8C region. The oxidation process
was adequately described by defining low (23–85 8C) and high (85–115 8C) temperature regimes.
Heterogeneous aging due to DLO occurred for temperatures above 85 8C. All measured responses
except tensile strength were affected by DLO. The activation energy for the high temperature
process ranged from 107 to 133 kJ/mol depending on the cure system: zinc oxide, ionic, sulfur
donor, sulfur, peroxide, and resin going from lowest to highest. The low temperature activation
energy is in the accepted range of 55–60 kJ/mol and is likely due to a combination of oxidative chain
scission (crosslink density loss) and recombination (network building) reactions. In addition to
crosslink stability, the presence of residual unsaturation along the polymer chain after vulcanization
can influence the high temperature activation energies. Oxidative degradative studies are useful to
aid in the comprehension and/or confirmation of the nature of the crosslink itself including the
structure of the polymer chain.

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[Paper 86, presented at the Fall 190th Technical Meeting of the Rubber Division, ACS (Pittsburgh, PA), 10–12 October
2016]

[Received October 2016; Revised October 2016]

APPENDIX

TABLE A1
DETAILED INFORMATION ABOUT THE BASE ELASTOMER AND THE COMPOUNDING INGREDIENTS USED IN THE
FORMULATIONS

Chemical name Product name Characteristics Supplier

Bromobutyl 1 BB 2030 1.8 wt% Br, ML(1þ8) 125 8C) ¼ Arlanxeo Inc.
32 MU
Bromobutyl 2 X_Butyl I4565P ML(1þ8) 125 8C ) ¼ 56 MU, Arlanxeo Inc.
Ionomer ¼ 0.40 mol%, Br ¼
0.5 mol%, unsaturation ¼
0.6 mol%
Carbon black Sterling SSO N550, Iodine number ¼ 43 g/kg, Cabot Canada
DBP ¼ 122 mL/100g Ltd.
ZnO Zinc oxide Zinc oxide National Bureau
of Standards
(NBS)
Stearic acid Stearic acid Stearic acid NBS
Sulfur Sulfur Sulfur NBS
DPTT-70 Rhenogran 70% dipentamethylene thiuram Rhein Chemie
tetrasulfide/30% EPDM/EVA
þ dispersing agents
ZDMC Vulkacit L Zinc-N-dithiocarbamate Arlanxeo Inc.
Peroxide Dicup 40C Dicumyl peroxide (40% active Arkema Canada
on calcium carbonate carrier) Inc.
Resin SP 1045 Alkyl phenol-formaldehyde SI Group
resin, Methylol (%): 8–11