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Compounding and Mixing Methodology for Good

Performance of EPDM in Tire Sidewalls

Article in Tire Science and Technology · October 2018

DOI: 10.2346/tire.18.460408

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Philip Hough,1 Niels van der Aar,2 and Zhaoyao Qiu3

Compounding and Mixing Methodology for Good

Performance of EPDM in Tire Sidewalls

REFERENCE: Hough, P., van der Aar, N., and Qiu, Z., ‘‘Compounding and Mixing
Methodology for Good Performance of EPDM in Tire Sidewalls,’’ Tire Science and
Technology, TSTCA, Vol. 48, No. 1, January–March 2020, pp. 2–21.

ABSTRACT: Ethylene propylene diene terpolymer (EPDM), which is a terpolymer of ethylene,

propylene, and a diene, is characterized by having a fully saturated polymer backbone, resulting
in excellent ozone and oxidative aging resistance. By contrast, diene elastomers such as natural
rubber (NR) and polybutadiene rubber (BR) have high levels of unsaturation along their main
polymer backbones, increasing their susceptibility to chemical degradation by main chain
scission and therefore their need for a protection system. This is generally provided by adding
combinations of primary antioxidants and migrating waxes. Protective systems based on
paraphenylenediamines (PPDs) are very effective and are used extensively for the protection of
tire sidewalls, but because they function by preferentially reacting with ozone, their activity
becomes depleted over the service life of the tire. Other potential drawbacks are that PPDs form
a reaction product that discolors the surface of the sidewall, and they are considered to be
potentially hazardous to human health and the environment through contamination of water
systems. By contrast, it has been shown that the addition of EPDM to a conventional sidewall
compound can give a permanent high level of ozone protection that is nonhazardous and non-
discoloring. However, differences in polarity, solubility, and levels of unsaturation create
significant challenges for achieving successful blends of EPDM in typical NR/BR sidewall
compounds, leading to inferior physical and dynamic properties. This study shows that by
combining best practices for compound design and mixing methodology with optimum grades of
EPDM, it has been possible to produce tire sidewall compounds having full ozone protection as
well as physical and dynamic properties closely matching a typical sidewall compound.
Additionally, this study shows that the presence of EPDM leads to improved properties after heat
aging and vulcanized compounds having reduced energy dissipation behavior, which could lead
to tires having reduced rolling resistance.
KEY WORDS: EPDM, tire sidewall, ozone protection, mixing, heat aging, rolling resistance,
nonstaining, non-discoloring

Introduction

Exposure of tire sidewalls to demanding service conditions requires

compounds having excellent physical and dynamic properties and has generally
necessitated the use of rubber compounds based on blends of natural rubber
(NR) and polybutadiene rubber (BR) for most types of pneumatic tires.

1
Global M&S/TSAD, ARLANXEO Netherlands B.V., Urmonderbaan 24, 6167 RD, Geleen,
The Netherlands. Email: philip.hough@arlanxeo.com
2
Global M&S/TSAD, ARLANXEO Netherlands B.V., Urmonderbaan 24, 6167 RD, Geleen,
The Netherlands. Email: niels.vanderaar@arlanxeo.com
3
Corresponding author. Global M&S/TSAD, ARLANXEO USA LLC, 111 RIDC Park West
Drive, Pittsburgh, Pennsylvania 15243, USA. Email: Joe.qiu@arlanxeo.com

2
HOUGH ET AL. ON COMPOUNDING AND MIXING 3
METHODOLOGY FOR EPDM PERFORMANCE

However, both of these polydiene type elastomers have poor resistance to

environmental aging by oxygen and ozone due to the presence of double bonds
along the main polymer backbones. The mechanisms of oxidative aging and
ozone degradation are well described [1,2], but in summary, cleavage of the
double bonds by oxygen (oxidation) and ozone (ozonolysis) causes chain
scission along the polymer backbone, leading to surface cracks that can
propagate into the rubber under conditions of critical strain. This is particularly
well demonstrated with ozone degradation, which can be recognized as the
formation of cracks that run perpendicular to the direction of strain (Fig. 1). The
sidewall of an inflated tire is under constant strain, making it extremely
susceptible to ozone cracking. While this is largely a cosmetic issue, there is
some potential for cracks to propagate through the sidewall toward the tire
carcass, eventually leading to a reduced ability of the tire to retain air pressure,
and the possible exposure of ply reinforcement. In the case of steel cords,
exposure to the corrosive influence of the environment could seriously impair
the safety and service life of the tire. It is therefore necessary to include an
adequate protection system within the design of the tire sidewall formulation to
avoid such degradation through the normal lifetime of the tire.
The use of antiozonant systems that combine Class 1 (ASTM D4676)
paraphenylenediamines (PPDs) with paraffin and/or microcrystalline wax is
very effective and has become established as normal industry practice because it
offers both static and dynamic ozone protection to the tire sidewall. Class 1
PPDs are primary antioxidants that function as very effective chemical
antiozonants by migrating to the surface of the rubber and reacting directly
and preferentially with ozone, thereby protecting the double bonds along the
polymer backbone. A resulting reaction product also provides an inert
discoloring film over the surface of the sidewall. This mechanism provides
dynamic ozone protection and is effective until the supply of the migrating
antiozonant is exhausted. PPDs commonly used in the rubber industry fall into
three main groups; dialkyl, alkyl-aryl, and diaryl. Of these, the alkyl-aryl PPDs
tend to offer the best all round performance as antidegradants, offering excellent
antioxidant as well as both static and dynamic ozone protection. Examples of
the alkyl-aryl PPDs include N-phenyl-N 0 -isopropyl-p-phenylenediame (IPPD),
N-phenyl-N 0 -(1,3-dimethylbutyl)-p-phenylenediamine (6PPD), and N-octyl-N 0 -
phenyl-p-phenylenediamine (8PPD), with 6PPD being most commonly selected
for use in tires because of its reduced volatility, its low tendency to be leached
out in water, its minimal impact on cure safety, and its tendency to be less of a
skin sensitizer compared with other PPDs from the same group [1]. Waxes are
added because they rapidly migrate to the surface of the sidewall, producing a
continuous inert film that provides a physical barrier to ozone attack. The rate of
migration is dependent upon the solubility and mobility of the wax, while
variables such as the quantity added, cross-link density, and the time and
temperature of storage after curing will affect the amount of wax that blooms
4 TIRE SCIENCE AND TECHNOLOGY

FIG. 1 — Ozone cracking on a tire sidewall.

onto the rubber surface. An adequate and continuous wax bloom on the surface
of the sidewall will provide static ozone protection. It is also generally
understood that the wax acts as a carrier for the PPD, helping in its migration to
the rubber surface.

Issues with Current Antiozonant Systems

Perhaps the most obvious disadvantage of PPD protective systems is that
they are staining and discoloring. As already mentioned, the PPD migrates to
the surface of the rubber, where it reacts with ozone and forms a reaction
product that has the appearance of a brown film. This tendency makes PPDs
unsuitable for light colored rubber articles, while for black products and
particularly tires, the discoloration is often reluctantly accepted as a tradeoff for
good ozone resistance.
Concerns have been documented [3] that PPDs, including 6PPD, possess
properties that indicate a hazard to both human health (skin sensitization and
anemia) and to the environment, and recommendations that further studies are
carried out to evaluate the true nature and extent of the risk have been made. It
should be noted, however, that according to the Hazard Classification and
Labeling Instructions (August 9, 2017) provided by companies to the European
Chemicals Agency in REACH registrations, 6PPD ‘‘is very toxic to aquatic life,
HOUGH ET AL. ON COMPOUNDING AND MIXING 5
METHODOLOGY FOR EPDM PERFORMANCE

is very toxic to aquatic life with long lasting effects, is harmful if swallowed and
may cause an allergic skin reaction.’’ There is an expectation by industry
experts [4] that government regulation will impose an enforced ban on the use
of 6PPD and that the tire industry will need to find alternative methods for
ozone protection.
The ongoing protection provided by PPD necessarily means that the source
of PPD in the compound will become depleted over the lifetime of the tire as it
migrates to the surface of the rubber and reacts with ozone. This is not generally
an issue if the amount of PPD added to a sidewall compound is adequate to
ensure a sufficient reservoir for the normal lifetime of a tire, but where tires see
a longer than normal service life, there will be an increased risk that the level of
protection will become inadequate. Ozone cracking can also often be observed
on the sidewalls of retreaded truck tires, where the tire carcass is recycled by the
application of a new tread and sidewall. Although the new sidewall compound is
formulated with PPD protection, it is generally applied only as a thin veneer, so
the source of available PPD is often not sufficient to protect the tire throughout
its second service lifetime, particularly as the PPD migration can also be in the
direction of the depleted remaining sidewall on which the veneer is applied.
Waxes migrate to form a bloom on the tire sidewall, which provides an
inert physical barrier for static ozone protection. It is important, therefore, that
the bloom forms a continuous film over the surface of the sidewall, so damage
of the film during service, for example, by curb scuffing or washing with
detergents, will compromise the effectiveness of the wax. Also, because only a
finite amount of wax can be added to a sidewall compound, there is a risk that at
some point in the lifetime of the tire the supply of wax will become exhausted.

The Use of EPDM For Ozone Protection

In contrast to the polydiene type elastomers, ethylene propylene diene
terpolymer (EPDM) has a fully saturated polymer backbone (Fig. 2), giving it
an inherently high resistance to ozone and oxidative aging. Pendant unsaturation
is provided by the inclusion of a diene monomer, which allows for sulfur
vulcanization without compromising the stability of the polymer main chain.
The last three decades have seen a considerable number of studies aimed at
exploiting the excellent ozone resistance of EPDM in blends with polydiene
elastomers, and there has been a general recognition that dispersed blends of
about 30 to 40 parts per hundred of rubber (phr) of EPDM provide a level of
ozone resistance at least as good as PPD/wax protection.
Differences in the polarity and solubility behavior of EPDM versus NR and
BR lead to a thermodynamic incompatibility when the polymers are blended
together [5], resulting in interspersed heterogeneous polymer phases due to poor
miscibility. Andrews [6] teaches that the introduction of an ozone resistant
phase such as EPDM in the form of dispersed particles within the continuous
polydiene phase hinders the propagation of ozone cracks by raising the critical
6 TIRE SCIENCE AND TECHNOLOGY

FIG. 2 — EPDM structure.

stored energy needed to initiate macroscopic ozone cracking. The presence of

the dispersed ozone resistant particles also provides a physical barrier to hinder
crack propagation. The effectiveness of such a protection mechanism will be
influenced by the volume ratio of the ozone resistant polymer as well as the size
and distribution of its dispersed particles [5].
There are several benefits in using EPDM blends in tire sidewalls for ozone
protection; namely, EPDM is nonhazardous to humans and the environment,
and, because it is neither discoloring nor staining, it will allow the sidewall to
retain a black appearance throughout its service life. Furthermore, because
EPDM provides a physical rather than chemical protection, its effectiveness
does not become depleted but instead offers a consistent level of protection over
the lifetime of the tire.

Technical Challenges
Despite the mentioned benefits of blending EPDM into tire sidewalls for
ozone protection, the use of this technique has generally not been adopted by
the tire manufacturing industry. A lack of any legislation enforcing a ban on the
use of PPDs has limited the need to find alternative solutions, but there are also
significant technical challenges to be overcome when blending EPDM into
sidewall compounds if good physical and dynamic properties are to be retained.
Differences in unsaturation levels, polymer viscosities, solubility parameters,
and the polarity of EPDM compared with NR and BR all contribute to reducing
properties. Even EPDM grades that are regarded as fast curing, incorporating
high diene monomer levels (i.e., 8 to 11%), still have substantially lower
available unsaturation for cross-linking compared with polydienes such as NR
and BR. Such differences in unsaturation levels lead to a more rapid use of the
cross-linking system by the high diene NR and BR polymers, resulting in an
overcure of the polydiene phase, a low cross-link density of the EPDM phase,
and weak interfacial adhesion between the different polymer phases. This effect
is exacerbated by a preferential solubility of the cure system to the polydiene
HOUGH ET AL. ON COMPOUNDING AND MIXING 7
METHODOLOGY FOR EPDM PERFORMANCE

phase during mixing and curing, leading to a migration away from the EPDM
phase [7–9].
Further difficulties, which are created by polarity, levels of unsaturation,
and viscosity differences between the EPDM and polydiene phases leading to a
preference for the carbon black to mix into the more polar NR and BR phase,
can result in the EPDM phase having little, if any, filler reinforcement. Zhang et
al. [5] report that for reinforcing carbon blacks the preferential mixing effect
becomes greater as the surface area of the black increases, whereas for non-
reinforcing inert fillers, the relative molecular weight or viscosity of the
polymer phases determines the location of the filler. It has further been
suggested that the presence of an uneven filler distribution between the polymer
phases influences the cured compound properties to a greater extent than does
an uneven cross-link density [10].
Overcoming these technical issues to optimize the potential benefits of
blending dissimilar elastomers has stimulated a considerable amount of
academic interest over the years. A comprehensive description of many of the
more promising studies is given by Zhang et al. [5].

Experimental

The scope of this study is to confirm and combine certain best practice
methodologies selected from previous published works. Particular focus is
given to the following:
 NR/BR sidewall compounds incorporating 30 phr EPDM combining high
diene, high molecular weight, high ethylene, and oil extension for maximum
cross-link density, filler distribution [8,11], and viscosity compatibility.
Grades having lower ethylene and molecular weight were also used in
blends for improved processing and low temperature flexibility.
 Masterbatch (MB) mixing to ensure carbon black incorporation into the
EPDM phase prior to blending with NR and BR [10].
 Addition of the cure system to the EPDM phase prior to blending with NR
and BR.
 Reactive mixing to form polymer bound accelerator intermediates to the
EPDM phase to minimize migration of the cure system to the NR/BR phase
[5,9,12,13].

Materials
All formulations containing EPDM used commercially available Keltant
grades. Where there is no sensitivity regarding intellectual property, details of
the grades used are given (Table 1). All other rubbers, fillers, oils, additives, and
8 TIRE SCIENCE AND TECHNOLOGY

TABLE 1 — Properties of EPDM grades used.

Grade ML (1 þ 4) @ 125 8C Ethylene (wt%) ENB (wt%) Oil content (phr)

Keltant 4869C 48 62 8.7 100
Keltant 5470C 55 66 4.6 0
Keltant 9950C 60a 44 9 0
a
ML (1 þ 8) @ 150 8C.

vulcanization chemicals are commercially available and commonly used within

the rubber compounding industry.

Mixing
Depending on the experiment, mixing was carried out either on a 1.5 L
H&F Intermixer or a 5 L GK5 E Intermixer. Unless otherwise mentioned, the
following standard mixing conditions were used on both machines: 72% fill
factor, mixer starting temperature of 45 8C, and a rotor speed of 50 rpm. Where
the mixing procedure did not form a part of the experiment, a conventional
mixing sequence was used in which the polymer was first introduced to the
mixer and masticated for 30 seconds before adding all of the filler, oil, and other
additives, excluding the cure system. After 3 minutes the ram was raised and
swept, then lowered until completion of the mix at 5 minutes, typically giving a
batch temperature of approximately 105 8C at the end of the mixing cycle. The
compound was then transferred to a two-roll mill with rolls heated to 50 8C. The
batch temperature was reduced to approximately 80 8C, at which point the cure
system was added and final blending was completed. All compounds rested 24
hours before rheological testing and curing.

Vulcanization
For all compounds containing a vulcanization system, the curing
characteristics were determined using a moving die rheometer (MDR) at 160
8C, unless otherwise stated, and the time required to reach a 90% state of cure
(t90) was established. The compounds were then vulcanized in steel molds
under hydraulic pressure between steam heated platens at the MDR test
temperature. Cure times of t90 þ 10% were used for 2 mm thick test sheets and
t90 þ 25% for 6 mm thick test sheets.

Testing
Unvulcanized compound viscosity measurements were determined using an
Alpha Technologies Mooney viscometer according to ISO 289-1 to give
Mooney (1 þ 4) @ 100 8C data. Curing behavior was carried out on an Alpha
Technologies MDR for 30 minutes at 160 8C, unless otherwise stated, according
to ISO 6502. Where possible, all physical testing of cured test pieces was
carried out in accordance with the appropriate ISO standards; tensile strength to
HOUGH ET AL. ON COMPOUNDING AND MIXING 9
METHODOLOGY FOR EPDM PERFORMANCE

ISO 37 using a type 2 test piece, crescent tear (nicked) to ISO 34-1, Shore A
hardness to ISO 868, compression set to ISO 815, and static ozone resistance
according to ISO 1431. Non-ISO testing included hot air aging, which was
carried out using a circulating hot air oven according to DIN 53521, rebound
resilience according to DIN 53512, and Zwick abrasion to DIN 53516. Tear
analyzer fatigue testing was carried out using a Coesfeld instrument (Fig. 3)
according to an in-house (Lanxess) specification comprising a uniaxial stretch
with a pulse repetition rate of 4 Hz and a pulse speed (modulation) of 30 Hz.
The amplitude ranged between 5 and 40%. Test pieces were 1.5 mm thick and
15 mm wide with a 1 mm long perpendicular cut into one edge All tests were
conducted at 70 8C. The length of the cut is continuously monitored by use of a
camera, and failure is reached when the length of cut has grown to 10 mm. The
test is useful for measuring stress–strain behavior; differential cut growth rate;
cycles to failure; total, elastic, and dissipated energy densities; and the
consequent fraction of dissipated energy density (¼ dissipated energy density
Wdiss/total energy density Wtot). Optionally, De Mattia flex fatigue testing was
used according to DIN 53522. Adhesion properties were evaluated using an in-
house ‘‘T’’ peel test (Fig. 4) using 25 mm wide test pieces and a grip
separation speed of 100 mm/min. Where evaluated, compression set testing
was carried out according to ISO 815, Method B. Finally, static ozone
testing was carried out according to DIN 53509. Details of the specific test
conditions used are given in the text.

Evaluation of Masterbatch Mixing

As mentioned, differences in polarity, levels of unsaturation, and viscosity
between the EPDM and polydiene phases lead to a tendency for preferential
mixing of carbon black to the NR/BR phase. Therefore, in mixing processes
where NR, BR, and EPDM are added to the mixer together, the carbon black
will almost entirely mix into the NR and BR, leaving the EPDM phase with
very limited filler reinforcement. Masterbatch mixing of the EPDM with carbon
black prior to blending with NR and BR ensures that the EPDM phase retains
some level of carbon black reinforcement. It should be noted that the use of oil
extended (OE) EPDM was seen as beneficial because it reduces the viscosity of
high molecular weight polymers to a level more closely matching that of NR
and BR. This is considered important [11] for achieving an optimum polymer
phase morphology. Also, OE EPDM grades are manufactured using a highly
compatible (paraffinic) oil, so there is an increased probability that the oil will
remain within the EPDM phase during mixing. The effect of an increased total
oil level on the final cured compound hardness is somewhat countered by
EPDM having a significantly higher cured gumstock hardness than either NR or
BR, so extra oil is needed to retain the desired compound hardness in
compounds containing EPDM.
10 TIRE SCIENCE AND TECHNOLOGY

FIG. 3 — Tear analyzer equipment.

Two mixing schemes for masterbatch mixing of the EPDM phase were
evaluated. The first method, herein referred to as ‘‘sequential mixing,’’ starts by
mixing a proportion of the filler and any additional oil to the EPDM. A
second stage of mixing introduces NR/BR, the remaining filler and oil, and
the cure activator system to the EPDM masterbatch. A final third stage of
mixing adds the vulcanization system. The second mixing method,
described as ‘‘parallel’’ or sometimes ‘‘Y-mixing,’’ combines a premixed
EPDM masterbatch similar to that used for sequential mixing with an NR/
BR masterbatch containing a proportion of the filler and oil. The EPDM
and NR/BR masterbatches are blended together, and the cure activator
system is added. A final mixing stage adds the vulcanization system. A
diagram showing the different mixing schemes can be found in Fig. 5. Table
2 describes the ingredient addition sequence at each stage of the mixing
process.

FIG. 4 — Lanxess method ‘‘T ’’ peel adhesion test piece.

HOUGH ET AL. ON COMPOUNDING AND MIXING 11
METHODOLOGY FOR EPDM PERFORMANCE

FIG. 5 — Masterbatch mixing methods.

Transmission electron microscope (TEM) images of cut face samples

stained with osmium tetroxide (Fig. 6) show clear differences between the three
mixing methods. The image taken from the test piece produced by standard
mixing shows the EPDM phase as white areas within the continuous NR/BR
phase, containing little or no carbon black. By contrast, the TEM images for
both the sequential and parallel mixing methods show that the EPDM phase has
retained a noticeable level of carbon black after blending with NR and BR. This
improvement in filler distribution translates to better physical properties (Table
3), particularly resulting in an improved tear strength and an extended De
Mattia flex fatigue life. In the case of tensile and elongation properties, an
improvement is seen for sequential mixing, possibly due to the EPDM phase

TABLE 2 — Compounds used in masterbatch mixing evaluation.

Standard EPDM Sequential Sequential Parallel Parallel

Ingredients mixing MB stage 2 stage 3 stage 2 stage 3
NR SVR CV 50 38.50 38.50 55.00
BR 31.50 31.50 45.00
Keltant 4869C 36.00 120.00
Keltant 5470C 12.00 40.00
N-660 GPF black 30.00 66.67 10.00 14.23
N-347 HAF black 20.00 66.67
Naphtha oil
(Sunthene 4240) 7.00 23.33
Zinc oxide 3.00 3.00 3.00
Stearic acid 2.00 6.67
TBBS 1.00 1.00 1.00
Sulfur (S-80) 2.00 2.00 2.00
EPDM MB 97.00 97.00
Sequential stage 2 177.00
Parallel stage 2 80.00
Total 183.00 323.34 177.00 183.00 114.23 183.00
12 TIRE SCIENCE AND TECHNOLOGY

FIG. 6 — Effect of mixing on phase morphology and filler distribution.

forming smaller dispersed particles. It is interesting to note a reduction in elastic

modulus at 100 and 300% extension for both masterbatch mixing methods,
which is a likely indication of less reinforcement in the continuous NR/BR
phase. Further studies could be undertaken to determine whether mixing to

TABLE 3 — Effect of mixing on properties.

Standard Sequential Parallel

Property mixing mixing mixing
ML(1 þ 4) @ 100 8C, ME 48.5 46.5 45.7
MDR @ 150 8C
Min torque (ML), dNm 0.18 0.15 0.16
Max torque (MH), dNm 1.30 1.15 1.17
MH–ML (delta S), dNm 1.12 1.00 1.01
Hardness, ShA 58.8 55.6 55.6
Tensile strength, MPa 15.8 17.9 15.4
Modulus @ 100%, MPa 2.2 1.6 1.6
Modulus @ 300%, MPa 8.1 6.7 6.6
Elongation at break, % 524 619 535
Nicked crescent tear, kN/m 12 16 18
Rebound resilience, % 56 57 56
De Mattia flex fatigue (to stage 6), kcycles 1250 1625 2000
HOUGH ET AL. ON COMPOUNDING AND MIXING 13
METHODOLOGY FOR EPDM PERFORMANCE

either temperature or power would result in different EPDM phase

morphologies.

Masterbatch Mixing of Filler and Cure System

Having confirmed the benefit of masterbatch mixing for improved carbon
black distribution between the polymer phases, a follow-up evaluation was
carried out to also add a proportion of the cure system to the EPDM
masterbatch. For this trial, sequential mixing was used because it was felt to
offer the best balance of polymer phase morphology, carbon black distribution,
and physical properties. For the purpose of comparison, an NR/BR based
control compound was also tested as being representative of a typical
commercial sidewall compound. In order to give the best possible low
temperature flexibility in the EPDM phase, Keltant 4869C was blended with
Keltant 9950C, which is an amorphous grade having a high molecular weight
and high level of ethylidene norbornene (ENB). Details of the formulations used
in this study are given in Table 4.
The Mooney viscosity, Mooney scorch, and MDR data are given in Table 5.
The Mooney viscosity measurements were found to be very similar for the NR/
BR control and the EPDM/NR/BR compounds. This indicates that the increased
oil level in the EPDM/NR/BR compound compensated well for the high
molecular weight of the EPDM used in this study. MDR analysis highlights
quite a significant difference in curing behavior between the two compounds,
with the EPDM/NR/BR compound having a slower rate of cure and a lower
final cross-link density. Both of these effects could be caused by migration of
the cure system to the NR/BR phase and the inherently slow curing activity of
EPDM. However, if the migration mechanism was dominant, this would imply a
low state of cure in the EPDM phase and, consequently, poor interfacial
adhesion between the polymer phases. Were this the case, it would be expected
that the cured compound would have appreciably lower physical properties than
the NR/BR control compound. Nevertheless, as shown in Table 6, this was not
the case, confirming that the EPDM phase received a reasonable level of cure
and achieved an adequate interfacial adhesion with the NR/BR phase. While
showing lower tensile modulus figures, reflecting the lower MDR delta S, the
EPDM/NR/BR compound displayed tensile properties approaching those of the
NR/BR control compound. Both compounds had similar hardness results,
confirming that the oil level used in the EPDM/NR/BR compound was correct,
and identical rebound resilience measurements indicated that the EPDM phase
had received a good level of cure. Tear strength and abrasion resistance of the
compound containing EPDM were somewhat inferior to the control compound,
maybe suggesting that the interfacial adhesion between the polymer phases still
needs some further improvement, but possibly also reflecting the lack of strain
induced crystallization in the EPDM phase. An inferior compression set,
particularly at 25 8C, but also to a much lesser extent at 23 8C, is likely to be
14 TIRE SCIENCE AND TECHNOLOGY

TABLE 4 — Masterbatch mixing with filler and cure system—formulation details.

NR/BR Sequential Final blend

Ingredients control EPDM MB mixing NR/BR/EPDM
EPDM MB 63.00
Keltant 9950C 50.00 15.00
Keltant 4869C 100.00 30.00
NR (RSSa masticated) 55.00 38.50 38.50
BUNAt ND 22 EZ 45.00 31.50 31.50
N 347 HAF 20.00 20.00 14.00 20.00
N 660 GPF 30.00 30.00 21.00 30.00
Sunthene 4240 7.00 5.00 5.00
Zinc oxide 3.00 3.00 2.10 3.00
Stearic acid 1.50 1.50 1.05 1.50
TMQ 2.00 1.40 2.00
6PPD 3.00
Microcrystalline wax 1.50 1.00 1.00
Rhenogrant TBBS-80 1.25 1.25 0.875 1.25
Rhenogrant S-80 2.00 2.00 1.40 2.00
Total 169.25 209.75 180.825 180.75
a
RSS, ribbed smoked sheets.

caused by crystallinity in the EPDM phase due to Keltant 4869C having a high
ethylene content. If the result was due to a poor state of cure in the EPDM
phase, one might expect that the compression set at 120 8C would also yield a
poor result, but this was not observed.
An advantage in the use of EPDM is seen in the improved heat aged results,
particularly at higher temperature conditions, where tensile strength, elongation
at break, and tear strength all exceed the results obtained from the control
compound. It is known that the fully saturated polymer backbone of EPDM
results in an excellent heat aging performance; however, the mechanism of
improved heat aging when dispersed in a polydiene, which is more susceptible

TABLE 5 — Masterbatch mixing with filler and cure system—compound properties.

Parameters NR/BR Control NR/BR/EPDM

ML (1 þ 4) @ 100 8C
ML 1 þ 4, ME 62.37 60.94
Mooney stress relaxation, log ME/log s 0.482 0.499
MDR @ 160 8C
Min torque (ML), dNm 2.42 2.1
Max torque (MH), dNm 15.37 12.52
Final torque, dNm 13.54 11.88
Delta S (MH–ML), dNm 12.95 10.42
Scorch time TS2, s 160.8 234
Time 90% cure t90, s 338.7 490.08
Tan delta of end value 0.05 0.05
HOUGH ET AL. ON COMPOUNDING AND MIXING 15
METHODOLOGY FOR EPDM PERFORMANCE

TABLE 6 — Masterbatch mixing with filler and cure system—cured properties.

NR/BR Control NR/BR/EPDM

Aged Aged Aged Aged
48 h, 168 h, 48 h, 168 h,
Original 120 8C 70 8C Original 120 8C 70 8C
Tensile modulus 100%, MPa 2.1 3.6 2.7 1.8 2.9 2.2
Tensile modulus 300%, MPa 9.9 12.6 7.6 9.1
Tensile strength, MPa 23.4 7.3 22.8 19.9 8.6 19
Tensile change, % 68.8 2.6 56.8 4.5
Elongation at break, % 584 165 490 606 231 532
Elongation change, % 71.7 16.1 61.9 12.2
Tear strength, N/mm 91.1 33.4 83.5 74 39.9 81.2
Tear change, % 63.3 8.3 46.1 þ9.7
Hardness, ShA 55.5 57 57.4 54.6 55.2 55.4
Compression set
24 h @ 25 8C, % 29.09 48.47
72 h @ 23 8C, % 8.24 11.83
24 h @ 120 8C, % 58.23 59.63
Abrasion resistance, mm3 56 91
Rebound resilience, % 62.5 62.5

to main chain scission, is less well known. It is likely that a reduction of the
percentage of polydiene in a compound by the addition of more heat stable
EPDM will lead to an improvement in heat aging performance. One could
further speculate that free radicals formed by chain scission of the polydiene
backbone could recombine with unused ENB unsaturation on the EPDM
molecule to form new cross-links, thereby contributing to a reduction in the loss
of heat aged properties. This would become a more dominant reaction as the
temperature of heat aging increases.
To confirm that the presence of EPDM would not cause a significant loss of
cured adhesion were it used in a sidewall compound bonded to a tire carcass, a
T-peel adhesion test was carried out (Fig. 4), whereby the EPDM/NR/BR
compound was cured against the NR/BR control compound. For comparison, a
further test was performed on a test piece prepared by curing the control
compound to itself. A separation force of 134 N was achieved for the test piece
based on the EPDM/NR/BR cured to the control compounds, compared with a
result of 178 N for the test piece produced using only the control compound.
This is not, however, an indication of poor adhesion because the failure did not
occur at the interface of the two compounds. Instead the failure mode was a tear
into the EPDM/NR/BR compound, reflecting its lower tear strength.
Static ozone resistance testing was conducted on test pieces held under a
20% strain for a duration of 100 hours. The ozone concentration of 50 parts per
hundred million was maintained with a flow rate of .500 mm/s in ambient
conditions of 40 8C and a humidity of 55%. Neither the NR/BR control
16 TIRE SCIENCE AND TECHNOLOGY

compound nor the EPDM/NR/BR test compound showed any surface cracks on
completion of the test, confirming that under the test conditions used, blending
of EPDM provides ozone resistance equivalent to the use of 6PPD.

Optimization of EPDM Phase

In order to further optimize compound properties, consideration was given to
the characteristics of the EPDM used, particularly with respect to the combined
influence of molecular weight, molecular weight distribution, and diene level.
Only commercially available Keltant grades were used in this study; however, the
authors will withhold specific details from this report until full consideration can
be given to possible new intellectual property. Premixing of the carbon black and
cure system using the sequential mixing process was selected as representing best
practice. Two further additions to the study included a comparison of N-tert-butyl-
benzothiazyl sulfenamide (TBBS) versus N-cyclohexyl benzothiazole sulfenamide
(CBS) to assess whether polarity differences between these accelerators influences
cured properties, and pretreatment of the EPDM phase by mixing it to a state of
prescorch prior to blending with the NR and BR to anchor the accelerator to the
EPDM molecule, thereby limiting its tendency for migration. The NR/BR control
compound described in Table 4 was remixed and again used for comparison in this
study. Details of the EPDM masterbatch (MB) compounds are given in Table 7. To
achieve a state of prescorch in MB3, first MB1 was mixed to a temperature of 140
8C and the mixing conditions recorded. The Mooney scorch time (MS t3) was then
established at 140 8C. MB3 was then mixed using identical mixing conditions to
MB1, but it was allowed to remain in the mixer at 140 8C for an extra time
equivalent to 98% of the measured MS t3 time of MB1 before being transferred to
a two-roll mill for rapid cooling. For the purpose of accurate comparison, the
mixing procedure for MB2 followed that of MB1. Uncured compound properties
are given in Table 8. All compounds containing EPDM showed slower curing
behavior and a lower final cross-link density compared with the NR/BR control
compound, which, as previously mentioned, reflects the lower curing activity of
EPDM. Replacement of TBBS with CBS gave only a marginal reduction in
Mooney scorch time, while a larger reduction was achieved by taking MB3 to a
prescorched state for Compound 3. It is interesting to note that the apparent final
cross-link density (delta S) of Compound 3 is lower than Compound 1, which
might indicate that less of the cure system has migrated from the EPDM phase,
and therefore the final cross-link density of the continuous NR/BR phase is lower.
Table 9 gives physical properties before and after heat aging. All three test
compounds showed tensile strength properties that were comparable with the
NR/BR control compound with higher elongation at break. Tear strength
showed some improvement over the previous study, with marginal gains being
achieved by the use of CBS and by taking the EPDM masterbatch to a state of
prescorch. Differences in abrasion resistance between the NR/BR control
compound and those containing EPDM remained similar to the previous study.
HOUGH ET AL. ON COMPOUNDING AND MIXING 17
METHODOLOGY FOR EPDM PERFORMANCE

TABLE 7 — EPDM optimization—formulation details.

EPDM EPDM EPDM Sequential Final blends NR/BR/EPDM

Ingredients MB1 MB2 MB3a mixing Compound 1/3 Compound 2
EPDM MB1 and
MB3 65.925
EPDM MB2 65.925
Keltant EPDM
(OE) 160.00 160.00 160.00 48.00 48.00
NR (RSSb
masticated) 38.50 38.50 38.50 38.50
BUNAt ND 22
EZ 31.50 31.50 31.50 31.50
N 347 HAF 20.00 20.00 20.00 14.00 14.00 20.00 20.00
N 660 GPF 30.00 30.00 30.00 21.00 21.00 30.00 30.00
Sunthene 4240 2.00 2.00 5.00 5.00
Zinc oxide 3.00 3.00 3.00 2.10 2.10 3.00 3.00
Stearic acid 1.50 1.50 1.50 1.05 1.05 1.50 1.50
TMQ 2.00 2.00 2.00 1.40 1.40 2.00 2.00
Microcrystalline
wax 1.50 1.50 1.00 1.00
Rhenogrant
TBBS-80 1.25 1.25 0.875 0.875 1.25
Rhenogrant
CBS-80 1.25 1.25
Rhenogrant S-80 2.00 2.00 2.00 1.40 1.40 2.00 2.00
Total 219.75 219.75 219.75 181.25 181.25 183.75 183.75
a
Mixed as for MB1 mixing time þ 98% MS t3 @ 140 8C.
b
RSS, ribbed smoked sheets.

The most significant improvements can be seen after heat aging, where the
retention of properties was much improved with the presence of EPDM. Of
particular note is that the tear strength of compounds containing EPDM was
better after both conditions of heat aging than for the aged NR/BR control
compound. It can also be seen that the abrasion resistance of the aged NR/BR
control compound is virtually identical to that of the aged compounds
containing EPDM. This is an important observation, since tires will very
quickly become subjected to conditions that cause heat aging during their
service life. The results indicate that the properties of sidewalls containing
EPDM will be retained better during the service life of the tire than a
conventional tire sidewall based only on a PPD protected NR/BR compound.
Ozone testing was again carried out using the same apparatus conditions as
with the previous study, except that the strain was increased to 25% and the
duration of the test was extended to 168 hours. Once again, no cracks were seen
in either the NR/BR control compound or any of the three test compounds
containing EPDM.
18 TIRE SCIENCE AND TECHNOLOGY

TABLE 8 — EPDM optimization—compound properties.

NR/BR
Control Compound 1 Compound 2 Compound 3
ML (1 þ 4) @ 100 8C
ML 1 þ 4, ME 62.37 63.49 63.72 60.57
Mooney stress relaxation,
log ME/log s 0.464 0.477 0.48 0.481
Mooney scorch @ 125 8C
MS-t3, s 1231 2006 1962 1628
MS-t5, s 1302 2175 2092 1781
MDR @ 180 8C
Min torque (ML), dNm 2.26 1.97 1.96 1.91
Max torque (MH), dNm 14.32 11.44 11.63 10.77
Final torque, dNm 10.46 9.35 9.05 8.86
Delta S (MH–ML), dNm 12.06 9.47 9.67 8.86
Scorch time TS2, s 56.4 82.8 77.4 73.2
Time 90% cure t90, s 120.5 165.2 143.2 155
Tan delta of end value 0.09 0.09 0.09 0.09

Tear analyzer evaluations were carried out on each of the compounds to

compare dynamic properties both before and after heat aging for 168 hours at
100 8C. Stress–strain behavior reflected the tensile modulus results already
shown in Table 9 in that the compounds containing EPDM were very similar to
each other but had a somewhat lower stress for a given strain than the NR/BR
control compound. It was observed, however, that the increase in modulus on
heat aging for the NR/BR control compound was 17% at a selected strain of
15%, while for the compounds containing EPDM the increase was only 12%,
which might translate to reduced sidewall stiffening during the service life of a
tire. Encouragingly, it was not possible to differentiate the compounds
containing EPDM versus the NR/BR control compound for crack growth rate
and the number of cycles to failure, both before and after heat aging, despite the
lower initial tear strength result presented in Table 9. Graphs showing the
fraction of dissipated energy density before and after heat aging are shown in
Fig. 7. Significantly lower values were obtained for Cpd3, produced using the
prescorched EPDM masterbatch, than for the NR/BR control compound or the
other two compounds containing EPDM protection. This surprising result
suggests that the energy loss through flexing of a sidewall could be reduced,
possibly leading to tires with reduced rolling resistance.

Conclusion

The principle of blending with EPDM for ozone resistance of polydiene

elastomers, and in particular blends of NR and BR for tire sidewalls, is well
known, and its effectiveness is proved. Ozone protection by this method has
HOUGH ET AL. ON COMPOUNDING AND MIXING 19
METHODOLOGY FOR EPDM PERFORMANCE

TABLE 9 — EPDM optimization—cured properties.

Property NR/BR Control Compound 1 Compound 2 Compound 3

Tensile modulus 100%, MPa 1.8 1.7 1.7 1.6
Tensile modulus 300%, MPa 9.1 7.1 7.1 6.8
Elongation at break, MPa 514 632 659 651
Tensile strength, MPa 19.9 20.4 21.1 21.1
Hardness, ShA 54.9 52.5 53.2 51.7
Nicked crescent tear, N/mm 111 82.3 86 87.7
Compression set
24 h @ 25 8C, % 25.9 45.9 46.7 47
24 h @ 120 8C, % 55 55.2 55.7 58.1
72 h @ 23 8C, % 11.9 14.9 15.9 16.3
Rebound resilience @ 70 8C, % 63.5 63.5 62.5 63
Rebound resilience @ 23 8C, % 60.6 61.7 61.3 61.6
Abrasion resistance, mm3 53 79 87 82
Heat aging 168 h @ 100 8C
Tensile modulus 100%, MPa 4.2 3.1 2.9 3.2
Tensile modulus 300%, MPa — — — —
Elongation at break, MPa 166 280 259 270
Elongation change, % 67.7 55.7 60.7 58.5
Tensile strength, MPa 8.6 12 10.5 11.8
Tensile change, % 56.8 41.2 50.2 44.1
Hardness, ShA 61.7 58 58.2 57.1
Hardness change, ShA þ6.9 þ5.5 þ5 5.4
Nicked crescent tear, N/mm 34.6 46.9 41.5 38.1
Tear change, % 68.8 43 51.7 56.6
Abrasion resistance, mm3 140 136 136 135
Heat aging 48 h @ 120 8C
Tensile modulus 100%, MPa 4 3 2.9 2.7
Tensile modulus 300%, MPa — — — —
Elongation at break, MPa 149 219 227 249
Elongation change, % 71 65.3 65.5 61.7
Tensile strength, MPa 6.8 8.3 8.4 9.6
Tensile change, % 65.8 59.3 60.2 54.5
Hardness, ShA 55.1 53.2 54 52.7
Hardness change, ShA þ0.2 þ0.7 þ0.8 þ1
Nicked crescent tear, N/mm 27.7 38.8 35 35.8
Tear change, % 75 52.9 59.3 59.2

advantages in terms of the appearance of the tire throughout its service life, as
well as overcoming health and environmental concerns associated with the use
of PPD protective systems, but implementation has proved difficult. Differences
in polarity and solubility as well as dissimilar levels of curing activity have
resulted in blends having poor physical and dynamic properties compared with
normal tire sidewall compounds. Studies have identified several ways of
improving the distribution of fillers and of limiting migration of cure systems
into the more polar NR/BR phase, but seldom have these methods of best
20 TIRE SCIENCE AND TECHNOLOGY

FIG. 7 — Tear analyzer data—fraction of dissipated energy.

practice been combined for optimum effect. The work reported in this paper
shows that through the correct selection of EPDM combined with masterbatch
mixing of the filler and cure system, and by reducing the migration of the cure
system by forming polymer bound accelerator intermediates in the EPDM
masterbatch, it is possible to closely match the properties of a sidewall type
compound, but with improved heat aging performance and dynamic properties.
 HOUGH ET AL. ON COMPOUNDING AND MIXING 21
METHODOLOGY FOR EPDM PERFORMANCE

Further fine tuning of the methodologies presented should help to dispel

concerns about adopting the use of EPDM for ozone protection of tire sidewalls.

Acknowledgments
The authors wish to acknowledge the support of colleagues at ARLANXEO
Performance Elastomers, particularly Martin van Duin and Gosé van Zandvoort.
Thanks also go to the staff of the LANXESS Polymer Testing Laboratory,
Leverkusen.

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[3] OSPAR Commission, ‘‘Publication Number 271/2006: Background document on 4-
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[10] van de Ven, P. M. and Noordermeer, W. M., ‘‘Design of EPDM-Rubber for Blends with NR/BR
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[11] van Duin, M., Krans, J. C. J., and Smedinga, J., ‘‘Covulcanization and Ozone Resistance of
NR/EPDM Blends,’’ Kautschuk Gummi Kunstoffe, Vol. 46, 1993, pp. 445–451.
[12] Ghosh, A. K. and Basu, D. K., ‘‘Natural Rubber—Ethylene-Propylene-Diene Rubber
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[13] Sahakaro, K., Pongpaiboon, C., and Nakason, C., ‘‘Improved Mechanical Properties of NR/
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