Blending of NR BR EPDM by SIDEWALL

Blending of NR/BR/EPDM by Reactive Processing for
Tire Sidewall Applications. I. Preparation, Cure

Characteristics and Mechanical Properties
Kannika Sahakaro,1,2* Nityananda Naskar,1,2y Rabin N. Datta,1,2 Jacques W. M. Noordermeer1,2

1
Dutch Polymer Institute (DPI), 5600 AX Eindhoven, the Netherlands
2
Department of Rubber Technology, Faculty of Science and Technology, University of Twente,
7500 AE Enschede, the Netherlands
Received 12 August 2005; accepted 17 May 2006

DOI 10.1002/app.25088
Published online in Wiley InterScience (www.interscience.wiley.com).
ABSTRACT: EPDM incorporated into blends of natural perties: tensile strength and elongation at break, as com-
rubber/butadiene rubber (NR/BR) improves ozone resist- pared to those prepared by straight mixing, in both gum
ance. In this work, the inferior mechanical properties of and carbon black-filled blends. The increase of tensile
NR/BR/EPDM blends generally obtained by conventional properties in gum and filled reactive blend vulcanizates
straight mixing are overcome by utilizing a reactive pro- does suggest that the reactive processing technique leads
cessing technique. The entire amount of curatives, based to more homogeneous blends due to, either a better cross-
on a commonly employed accelerator N-cyclohexyl-2-ben- link distribution, or more homogeneous filler distribution,
zothiazole sulfenamide (CBS) and sulfur, is first added into or both. Ó 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:
the EPDM phase. After a thermal pretreatment step tuned 2538–2546, 2007
to the scorch time of the EPDM phase, the modified EPDM
is mixed with premasticated NR/BR. The reactive blend Key words: blends; reactive processing; NR/BR/EPDM;
vulcanizates show a significant improvement in tensile pro- tire sidewall
INTRODUCTION the ozone and thermo-oxidative resistances of tire side-

wall compounds.
A tire sidewall compound is conventionally formulated
Ethylene–propylene–diene rubber (EPDM) is a
using natural rubber (NR) and butadiene rubber (BR)
highly saturated elastomer, which is widely used in
with an amine type antidegradant, N-(1,3-dimethylbu-
applications that require good ozone resistance. For
tyl)-N0 -phenyl-p-phenylenediamine (6PPD) as the main
reason of its saturated backbone and only a low
antiozonant.1 Since a tire sidewall in dynamic service
diene-content in the EPDM, blending of EPDM with
condition can easily be attacked by ozone, superior
highly unsaturated elastomers such as NR and BR
ozone resistance and flex-fatigue are the prime proper-
generally results in cure rate mismatch and heteroge-
ties required to provide a long service life. The use of
neous filler distribution in each of the rubber phases.
conventional antiozonants leads to an undesirable sur-
The difference in molar concentrations of double
face discoloration as a result of additive migration.1,2 In
bonds in each of the elastomers results in differences
addition, the amount of active antiozonant is depleted
in polarity, number of allylic sites for sulfur vulcani-
in time after reaction with ozone and by migration to
zation, and reactivity of the crosslink sites.3 Cura-
and washing off the surface. The increasing demand
tives, which are considered as polar molecules, gen-
for life-extension of tires, to reduce cost, and the
erally diffuse more into the higher unsaturated rub-
amounts of used tires, leads to a need of improving
bers, i.e., diene phases, resulting in differences in
concentration of reactants and hence uneven cross-
*Present address: Department of Rubber Technology and link distribution.2,4 Carbon black also prefers to
Polymer Science, Prince of Songkla University, Pattani migrate into the higher unsaturated polymers, caus-
Campus, Pattani 94000, Thailand.
y
Present address: Polymer Science Unit, Indian Association ing a heterogeneous filler distribution in the blend.5–10
for the Cultivation of Science, Jadavpur, Calcutta 700 032, India. However, despite the blend incompatibility of EPDM
Correspondence to: J. W. M. Noordermeer (J.W.M.Noor and diene rubbers, blending of EPDM with highly
dermeer@utwente.nl). unsaturated elastomers still attracts lots of interest,
Contract grant sponsor: Dutch Polymer Institute (DPI); as such blends may provide a broader range of
contract grant number: DPI project no. 356.
applications. EPDM is considered an ozone-resistant
Journal of Applied Polymer Science, Vol. 103, 2538–2546 (2007) polymer. The EPDM phase dispersed in blends with
V
C 2006 Wiley Periodicals, Inc. highly unsaturated elastomers provides an internal
BLENDING OF NR/BR/EPDM BY REACTIVE PROCESSING. I 2539
antiozonant,11 which will not leach out via migration N-cyclohexyl-2-benzothiazolesulfenamide (CBS) or
like conventional antiozonants do. Several approaches Santocure1 (Flexsys B.V.). High abrasion furnace
have been proposed to overcome the cure rate mis- black (HAF-N330, Cabot Corp.) and naphthenic oil
match and achieve covulcanization,12–24 e.g., by using Sunthene 4240 (Sun Petroleum Products Co.) were
bis(diisopropyl)thiophosphoryl disulfide (DIPDIS) as used to prepare the masterbatches in case of filled
a multifunctional additive, maleic anhydride grafted blends. All elastomers, curatives, and other additives
EPDM as compatibilizer, trans-polyoctylene rubber were used as received.
(TOR) or liquid BR as compatibilizing agents, a two-
stage vulcanization technique or by EPDM-modifica- Preparation of blend compounds
tion through a grafting reaction of accelerators onto by reactive mixing
EPDM. The latter approach is similar to the work re-
ported in this article, but the procedures adopted are The two types of blend compounds described in this
different. work, are designated according to the procedures
Hashimoto et al.17 prepared a modified EPDM in adopted for their preparation: straight mix and reac-
solution to achieve bound 2-mercaptobenzothiazole tive mix. With each of the blend types, gum and car-
EPDM. Baranwal and Son19 modified EPDM by bon black-filled compounds were prepared. The
reacting EPDM with accelerators such as 4,40 -dithio- overall recipes for both gum and filled blends are
bismorpholine (DTBM) and 2-mercaptobenzothiazole given in Table I.
(MBT) in solution in the presence of a photosensi-
tizer and UV light. Hopper20–23 modified EPDM by Gum reactive mix
the addition of certain N-chlorothiosulfonamides to
The entire amounts of curatives and other ingredients
the olefinic sites of EPDM in solution and the melt.
were first incorporated into the EPDM only, using a
Cook24 modified EPDM by mixing sulfur donors like
Brabender Plasticorder 350S mixer having a mixing
dithiodicaprolactam (DTDC) and dithiodimorpholine
chamber volume of 370 cm3. The mixer was operated
(DTDM) with EPDM in an internal mixer at elevated
with a rotor speed of 100 rpm, fill factor of 0.7, and
temperature, resulting in EPDM with bound sulfur
an initial temperature of 508C. The EPDM was first
donor moieties. This was subsequently crossblended
masticated for 1 min, and then ZnO, stearic acid, and
with NR and finally mixed with curatives. Various
TMQ were added. After 2 min of mixing, CBS and
aspects of elastomer blends, including blend charac-
sulfur were added and the mixing was continued for
terization, have been reviewed by Hess et al.25 and
another 2 min. The final compound temperature
Mangaraj.26
before dumping from the mixer was in the range of
In the present work, the first part of a series, it is
115–1208C. Immediately after dumping, the compound
shown how a reactive processing technique, in which
was sheeted on a two-roll mill to a thickness of about
a common N-cyclohexyl-2-benzothiazole sulfenamide
2 mm. The resulting EPDM compound was tested for
(CBS) is grafted onto EPDM prior to blending with
its cure characteristics using a Rubber Process Analyzer
NR/BR, can be utilized to overcome the difficulties
(RPA 2000, Alpha Technologies) at 1408C, 0.833 Hz,
associated with cure incompatibility of NR/BR/
and 0.2 degree strain according to ISO 6502. Scorch
EPDM blends. The efficiency of the reactive process-
time (ts2), i.e., the time to incipient cure, was deter-
ing technique is assessed by the improvement of the
mined and used as a reference point to assign various
mechanical properties of the blend vulcanizates.
pretreatment times of the EPDM, as shown in Figure 1.
EXPERIMENTAL TABLE I
Formulation of NR/BR/EPDM Compounds
Materials
Gum blend Filled blend
The elastomers selected for the blend were natural Ingredient content (phr) content (phr)
rubber (SIR20, Standard Indonesian Rubber), butadi- NR 35 35
ene rubber (Kosyn KBR01, Korea Kumho Petrochem- BR 35 35
ical Co.), and EPDM rubber containing ethylidene EPDM 30 30
norbonene (ENB) as third monomer (Keltan 578z, Zinc oxide 4 4
Stearic acid 2 2
DSM Elastomers B.V., the Netherlands). Keltan 578z
TMQ 1 1
contains 4.5 wt % of ENB and 67 wt % of ethylene. CBS 1.98 (7.5 mmol) 1.98 (7.5 mmol)
The other compound ingredients used were extra Sulfur 2.5 2.5
pure grade zinc oxide (Merck, Germany), finely di- HAF N330 – 50
vided sulfur (Merck), 95% pure stearic acid (Aldrich, Naphthenic oil – 10
Total formulation
Germany), poly (2,2,4-trimethyl-1,2-dihydroquino-
weight 111.48 171.48
line) or TMQ (Flexsys B.V., the Netherlands), and
Journal of Applied Polymer Science DOI 10.1002/app

2540 SAHAKARO ET AL.
Preparation of blend compounds

by straight mixing
Gum straight mix
The ratio of compound ingredients in the straight-
mixed compound was the same as that of reactive-
mixed given in Table I. The blend compound was
prepared in the Brabender Plasticorder 350S oper-
ated under the same conditions. NR was first masti-
cated for 1 min, and then BR and EPDM were added
and mixed for another 1 min. ZnO, stearic acid, and
TMQ were subsequently added and the mixing was
continued for another 2 min. Finally, CBS and sulfur
Figure 1 RPA cure curve of the EPDM compound at were added into the compound and further mixed
1408C with indications of different pretreatment times. ts2 1 for 2 min to complete the mixing. The final com-
denotes pretreatment time of scorch time less 1 min; etc. pound temperature before dumping from the mixer
was in the range of 115–1208C. The dumped com-
The EPDM compound was then pretreated in a compound was immediately sheeted on a two-roll mill.
pression molding machine (Wickert WLP1600 labora- The resulting compound was tested for its cure char-
tory press) at 1408C and 100 bar to a predetermined acteristics using the RPA 2000 at 1408C according to
time taken from the RPA cure curve. The resulting ISO 6502.
pretreated EPDM sheet was immediately removed
from the mold and left to cool down to room temper-
ature in open atmosphere. The pretreated EPDM was Filled straight mix
later cross-blended with premasticated NR/BR on a
Schwabenthan two-roll mill to a final NR/BR/EPDM A straight mix filled compound was obtained by
ratio in the blend equal to 35 : 35 : 30. mixing the MB1 masterbatch of Table II with the
other ingredients according to the recipe given in
Table I, on the two-roll mill.
Filled reactive mix
All carbon black-filled blends were prepared accord-
ing to the overall recipe given in Table I. Three dif- Vulcanization
ferent masterbatches of rubbers, carbon black, and The optimum cure time (tc,90) of the fully com-
naphthenic oil were prepared in a Shaw K1 inter- pounded blends was determined as the time needed
meshing internal mixer, having a mixing chamber to reach 90% of the maximum torque in the RPA
volume of 4000 cm3, according to the recipes given 2000 at 1408C, 0.833 Hz, and 0.2 degree strain. The
in Table II. The mixer was operated with an initial blends were then vulcanized during the optimum
mixing temperature of 508C, a rotor speed of 100 rpm, cure time tc,90 in a Wickert WLP1600 laboratory com-
and a fill factor of 0.54. For MB1 and MB2, NR was pression press at 1408C and 100 bar.
first masticated for 1 min, and then BR/EPDM or BR
was added and mixed for another 1 min, prior to
the addition of HAF black and oil. The mixing was Tensile tests
continued for another 3–4 min until a stable ram
position. The masterbatches were dumped and im- Type 2 dumb-bell test pieces were die-cut from the
mediately sheeted on a two-roll mill. compression molded sheet and tensile tests were car-
The reactive mix filled compounds were prepared ried out according to ISO 37, with a Zwick tensile
by initially adding the entire amounts of all curing tester Model Z 1.0/TH1S at a constant crosshead
ingredients and additives into the EPDM master- speed of 500 mm/min.
batch MB3 on the two-roll mill. The cure characteris-
tics of the EPDM masterbatch were measured by TABLE II
Formulation of Carbon Black Masterbatches
using the RPA 2000 at 1408C and the pretreatment
times were determined as explained before. The Ingredient MB1 MB2 MB3
EPDM compounds were subsequently pretreated in NR 35 50 –
the compression molding to the predetermined BR 35 50 –
times, and finally blended on the two-roll mill with EPDM 30 – 100
HAF N330 50 50 50
MB2 NR/BR masterbatches for the required overall
Naphthenic oil 10 10 10
composition as given in Table I.

RESULTS
Cure characteristics of the blends
Figure 2 shows a cure curve of a gum reactive mix
prepared by using ts2 2 pretreated EPDM in com-
parison with that of a straight mix, and Figure 3
shows a cure curve of a HAF filled reactive mix pre-
pared by using ts2 þ 1 pretreated MB3 EPDM in
comparison with that of a straight mix. By applying
the reactive processing method, both scorch time
and cure time of the blend are significantly reduced.
Considering the maximum torque levels of the gum
blends, both show more or less equivalent values. Figure 3 RPA cure curves of the reactive mixed 50 phr
However, in the case of filled blends, the reactive HAF-filled NR/BR/EPDM blend, prepared with ts2 þ 1
mix shows a lower maximum torque than the pretreated EPDM, and of a straight mixed filled blend at
straight mix. 1408C.
The cure curves of reactive mixed gum NR/BR/
EPDM blends prepared by using EPDM with differ- than scorch time. The tensile strength shows the
ent pretreatment times are shown in Figure 4. The most pronounced dependence on the EPDM pre-
blends with EPDM of different pretreatment times treatment time. By increasing the pretreatment time,
show a shift of scorch time, cure time, and maxi- the tensile strength of the blend initially increases,
mum torque. A shorter EPDM pretreatment time but dramatically drops as the pretreatment time ap-
gives a longer scorch time and cure time but a some- proaches the EPDM scorch time. By pretreatment of
what lower maximum torque. Plateaus or flat cure the EPDM compound beyond its scorch time, the
curves are observed for the blends. The RPA 2000 blend remains visually heterogeneous during the
rheometer data: minimum torque (FL), maximum blending with NR/BR on the two-roll mill, indicat-
torque (Fmax), torque difference (Fmax FL), scorch ing that the EPDM has lost its ability to be mixed.
time (ts2), and cure time (tc,90) for all blends are In Figure 6, the tensile moduli at 100% and 300%
given in Table III. strain, tensile strength, and elongation at break of
the HAF-filled reactive blends are shown as a func-
tion of EPDM pretreatment times. The EPDM pre-
Tensile properties of the blend vulcanizates
treatment times show no significant effect on the ten-
Figure 5 shows the tensile moduli at 100% and sile moduli. However, the tensile strength and elon-
300%, tensile strength, and elongation at break of gation at break are again influenced by the EPDM
the gum reactive blends, prepared using different pretreatment times. The highest tensile strength and
EPDM pretreatment times relative to scorch time, ts2. elongation at break are observed for an EPDM pre-
The tensile moduli and tensile strength reach their treatment time of scorch plus 1 min (ts2 þ 1). In con-
maximum values at a pretreatment time of scorch trast to the gum blends, in spite of pretreatment of
less 1.5 min (ts2 1.5). The elongation at break remains
more or less the same for pretreatment times shorter
Figure 4 RPA cure curves of the reactive mixed gum

Figure 2 RPA cure curves of the reactive mixed gum NR/BR/EPDM blends prepared with EPDM with different
NR/BR/EPDM blend, prepared with ts2 2 pretreated pretreatment times at 1408C. ts2 1 denotes pretreatment
EPDM, and of a straight mixed gum blend at 1408C. time of scorch time less 1 min; etc.

TABLE III
Cure Characteristics of the NR/BR/EPDM Blends
RPA data at 1408C
Type of blend EPDM pretreatment time (min) FL (dN m) Fmax (dN m) Fmax FL (dN m) ts2 (min) tc,90 (min)
Gum straight 0 0.34 4.15 3.81 24.98 40.95
Gum reactive 7.52 (ts2 4) 0.23 3.97 3.74 1.79 7.53
8.52 (ts2 3) 0.23 4.12 3.89 1.51 6.37
9.52 (ts2 2) 0.28 4.26 3.98 0.93 5.21
10.52 (ts2 1) 0.33 4.30 3.97 0.89 5.25
11.52 (ts2) 0.46 4.37 3.91 0.73 5.35
Filled straight 0 0.78 10.06 9.28 3.03 18.82
Filled reactive 3.15 (ts2 2) 0.63 9.03 8.40 1.25 11.16
5.15 (ts2) 0.69 8.94 8.25 1.01 8.61
6.15 (ts2 þ 1) 0.67 8.48 7.81 0.93 7.39
7.15 (ts2 þ 2) 0.61 8.83 8.22 0.57 7.01
the filled EPDM compound beyond scorch time to tively. The energy required to break each sample can
ts2 þ 1 and ts2 þ 2, the blend remained visually ho- be obtained by calculating the area under those
mogeneous during the blending with NR/BR on the curves. The energy to break for the gum reactive
two-roll mill. A visually heterogeneous blend was mix is 2.6 times higher than that of the gum straight
only observed when the ts2 þ 3 pretreatment time mix, and the energy to break for the filled reactive
was used. mix is 2.0 times higher than that of the filled straight
On comparing the tensile stress–strain behaviors mix.
of both gum and filled reactive blends, prepared In Figure 9, the stress–strain curves of the op-
with optimum EPDM pretreatment times, i.e., ts2 1.5 timum gum and filled reactive mixed blends are
for gum and ts2 þ 1 for filled, with those of straight compared. Both gum and filled blends yield similar
mixed blends, the improvement in tensile properties elongation at break. The tensile moduli and tensile
due to the reactive processing technique is clearly strength of the filled blends are increased as a result
visible. Figures 7 and 8 show representative stress– of carbon black reinforcement.
strain curves, a comparison between the straight mix The tensile properties of the straight mixes in com-
and reactive mix, of gum and filled blends respec- parison with those of the reactive mixes are sum-
Figure 5 Moduli at 100% and 300% strain, tensile strength, and elongation at break of gum reactive NR/BR/EPDM
blends, prepared using different EPDM pretreatment times relative to scorch time, ts2.

Figure 6 Moduli at 100% and 300% strain, tensile strength, and elongation at break of 50 phr-HAF filled reactive NR/
BR/EPDM blends, prepared using different EPDM pretreatment times relative to scorch time ts2.
marized in Figure 10. Here, the reactive mixed celerator CBS and sulfur into the EPDM phase and
blends with the highest tensile properties are dem- subsequent thermal pretreatment, and next blending
onstrated. The gum blend was prepared by using an with the premasticated NR/BR, a significant increase
EPDM pretreatment time equal to ts2 1.5, and the in tensile strength and elongation at break is ob-
filled blend was obtained by using the ts2 þ 1 EPDM tained. The moduli at 100% and 300% strain do not
pretreatment time. change very much. The significant improvement in
tensile strength and elongation at break for the reac-
tive blends, does suggest that the ternary blends pre-
DISCUSSION
pared through reactive mixing possess a better cross-
The results in Figures 7–10 have demonstrated that, link distribution and/or carbon black distribution
for NR/BR/EPDM blends, by first premixing the ac- between the three rubber components, as compared
Figure 7 Stress–strain curves of gum NR/BR/EPDM Figure 8 Stress–strain curves of filled NR/BR/EPDM
blends: straight mix versus reactive mix with EPDM pre- blends: straight mix versus reactive mix with EPDM pre-
treatment time ts2 1.5 at 1408C. treatment time ts2 þ 1 at 1408C.

strength shows the most pronounced dependence on

the EPDM pretreatment time. The tensile moduli,
tensile strength, and elongation at break of the gum
reactive blends show their maximum values at a pre-
treatment time of scorch time minus 1.5 min (ts2 1.5),
whereas those of the filled blends show the maxi-
mum properties at a pretreatment time of scorch
time plus 1 min (ts2 þ 1). The high viscosity of the
filled blends affects the torque reading at the begin-
ning of the RPA measurement, and hence the scorch
times obtained by the RPA are slightly shorter for
the filled blends relative to the gum compounds at
the same stage of chemical cure. By increasing the
pretreatment time, the tensile strength of the blend
Figure 9 Stress–strain curves of the reactive mixed NR/
BR/EPDM blends: gum versus filled. initially increases; however, the tensile strength dra-
matically drops after the pretreatment surpasses the
scorch time, especially in the case of the gum blend.
By pretreating the EPDM compounds for too long,
to those of the blends prepared by conventional the EPDM is no longer processable, and the blends
straight mixing. The accelerator used in this study: become visually heterogeneous during the blending
CBS, is the most commonly used accelerator in the with NR/BR on the two-roll mill. The results indi-
rubber industry, and the experimental principles cate that a suitable pretreatment time needs to be
used for the pretreatment of the EPDM are very sim- met to optimize the tensile properties of the blends.
ple and easier to implement on an industrial scale, Comparing the cure characteristics of the NR/BR/
compared to the EPDM modification techniques in EPDM blends obtained by means of the reactive and
solution as mentioned in the introduction. straight mixing (Figs. 2 and 3), there is only a small
The pretreatment time of the EPDM for reactive difference in the maximum torque levels for both
mixing with NR/BR shows an influence on the ten- gum blends, but in the case of filled blends, the
sile properties of the blends, as shown in Figures 5 filled straight mix shows a higher maximum torque.
and 6. The effect is more pronounced in the gum This can be attributed to a poorer carbon black dis-
blend compared to the filled blend, and the tensile tribution among the rubber phases for the straight
Figure 10 Tensile properties of gum and filled NR/BR/EPDM blends; straight mixes versus reactive mixes. [Color figure
can be viewed in the online issue, which is available at www.interscience.wiley.com.]

mix, as will be characterized in detail in the next ar-

ticle of this series.
The EPDM pretreatment step for the reactive mix-
ing results in a remarkable decrease of both the
scorch time and cure time of the blend compounds
to values common for simple NR/BR systems. It is a
strong indication that the EPDM phase has been acti-
vated by the pretreatment step to vulcanize at simi-
lar speed as NR and BR, in spite of its much lower
unsaturation levels. Following the studies mentioned
in the introduction, it is obvious to assume a grafting
reaction of the CBS onto the EPDM molecular chain.
At the early stage of vulcanization, the generally
accepted mechanism starts with a reaction of acceler-
ator CBS with the activator ZnO to give an active
accelerator complex, which subsequently reacts
with molecular sulfur to give an active sulfurating
agent.27,28 This sulfurating species then reacts with
the allylic hydrogens of the ENB third monomer of
the EPDM chains, resulting in an EPDM intermedi-
Figure 12 Cocrosslinking between pretreated EPDM and
ate or crosslink precursor, as shown in Figure 11. diene rubbers (NR/BR).
We have characterized this intermediate, as will be
reported in the next part of this series. Since the pre-
treatment step was stopped more or less at the the reactive mixing technique, the co-crosslinking
beginning of cure, further reactions of the EPDM- between EPDM and diene phases, as schematically
bound intermediates with other EPDM chains re- displayed in Figure 12, is also improved. Since a
mained minimal. The pretreated EPDM remained light crosslinking may also take place after the pre-
processable in the step of crossblending with NR/BR treatment step, the migration of carbon black in
on the two-roll mill. the filled blend is also reduced, and hence results in
After the pretreatment step, the EPDM with pend- a more homogeneous carbon black distribution be-
ant CBS fragments results in a restriction of the cura- tween the three rubber phases.
tive migration from the EPDM phase towards the
higher unsaturated NR/BR phases and consequently
in an improved crosslink distribution. By applying
CONCLUSIONS
The tensile properties of NR/BR/EPDM rubber blends
are significantly increased by using a reactive pro-
cessing technique: the entire amounts of curatives
and compounding ingredients are first incorporated
in the EPDM-phase; the latter is then subjected to a
suitable preheating till close to scorch; and finally
the pretreated EPDM is blended with premasticated
NR/BR. The curatives consisted of the common
accelerator CBS and elemental sulfur. The scorch
and cure times of the final blends prepared with the
reactive mixing are significantly reduced to values
common for NR and BR compounds, relative to those
blends prepared by conventional mixing sharing
more typical EPDM-values. The tensile properties of
the reactive blends are dependent on the EPDM pre-
treatment times. Under optimum conditions, the ten-
sile strength and elongation at break are significantly
higher for both gum and filled blend vulcanizates.
The authors thank Dr. Auke G. Talma for fruitful dis-

Figure 11 EPDM-bound intermediate for the reactive blends. cussions.

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Blending of NR/BR/EPDM by Reactive Processing
for Tire Sidewall Applications. II. Characterization
Kannika Sahakaro,1,2* Auke G. Talma,1,2 Rabin N. Datta,1,2 Jacques W. M. Noordermeer1,2

1
Dutch Polymer Institute (DPI), 5600 AX Eindhoven, The Netherlands
2
Faculty of Science and Technology, Department of Rubber Technology, University of Twente,
7500AE Enschede, The Netherlands
Received 12 August 2005; accepted 21 July 2006

DOI 10.1002/app.25113
ABSTRACT: Cure incompatibility in NR/BR/EPDM blends ments, attached to the EPDM. NR/BR/EPDM (35/35/30)
is a crucial problem, affecting blend properties. In a previ- ternary blends are prepared by reactive mixing of the pre-
ous study, it was demonstrated that the mechanical proper- treated EPDM with CBS fragments attached with premasti-
ties of such blends can be significantly improved by utiliz- cated NR/BR on a two-roll mill. Their blend morphological
ing a reactive processing technique, in which a pretreated features are studied using the atomic force microscopy
EPDM is first prepared by incorporating all compounding (AFM) and transmission electron microscopy (TEM) micro-
ingredients in the EPDM and subsequent preheating, prior scopic techniques, in comparison with those of blends pre-
to crossblending with premasticated NR/BR. In the present pared by a conventional straight mixing method. Both the
article, the pretreated EPDM-moieties are prepared using tapping mode AFM phase images and TEM micrographs
two different accelerators, N-cyclohexyl-2-benzothiazole sul- clearly show that reactive mixing leads to more homogene-
fenamide (CBS) and 6-nitro MBTS. The latter was synthe- ous blends. Ó 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:
sized and applied for the purpose of IR characterization. 2547–2554, 2007
The infrared (IR) spectra of the pretreated, extracted EPDM
demonstrate absorption peaks associated with the IR Key words: blends; reactive processing; morphology; tire
absorption of the functional groups in the accelerator frag- sidewall; infrared spectroscopy
INTRODUCTION for an increased reactivity of the EPDM toward sulfur

1 curing, at a speed comparable to that of NR and BR.
In the first part of this series it has been shown that
Furthermore, the grafting of the MBT would raise the
significant improvement in tensile strength and elonga-
polarity of the EPDM, leading to a more homogeneous
tion at break of terpolymer NR/BR/EPDM vulcanized
distribution of carbon black over the various phases;
blends can be achieved by reactive processing of the
contrary to straight blends of the three polymers,
EPDM-phase prior to mixing with the NR/BR. The re-
where carbon black tends to preferentially partition to-
active processing essentially consists of mixing all com-
ward the NR and BR phases.
pounding ingredients and curatives into the EPDM-
In this second part of the series, the first objective
component first, then heat-treating the EPDM preblend
is to characterize the pretreated EPDM by means
for a duration tuned to the scorch time, subsequently
of infrared (IR) spectroscopy to prove the grafting
mixing this pretreated EPDM into the NR/BR phase,
mechanism involved, as suggested in the previous
and finally curing the resulting blend. As curatives, the
study; and the second is to study the morphological
most common accelerator N-cyclohexyl-2-benzothia-
features of the NR/BR/EPDM blend vulcanizates by
zole sulfenamide (CBS) and elemental sulfur were
using atomic force microscopy (AFM) and transmis-
used. The concept of grafting the mercaptobenzothia-
sion electron microscopy (TEM) techniques. Both are
zole (MBT) moiety of the CBS onto the EPDM molecu-
to create a better understanding of the significant
lar chain was postulated. This grafting would account
improvement in tensile properties of the blends pre-
pared by the reactive mixing when compared with
*Present address: Department of Rubber Technology and those of conventional straight mixes.
Polymer Science, Prince of Songkla University, Pattani
Campus, Pattani 94000, Thailand.
Correspondence to: J. W. M. Noordermeer (j.w.m.
noordermeer@utwente.nl). EXPERIMENTAL
Contract grant sponsor: Dutch Polymer Institute (DPI);
contract grant number: 356. Materials
Journal of Applied Polymer Science, Vol. 103, 2547–2554 (2007) The blends consist of the same ingredients as men-
V
C 2006 Wiley Periodicals, Inc. tioned in part I. 6-Nitro-MBTS was prepared using
rotor speed of 100 rpm, fill factor of 0.7, and an

initial temperature of 508C. The EPDM was first
masticated for 1 min, and then ZnO, stearic acid,
and TMQ were added. After 2 min of mixing, CBS
or 6-nitro-MBTS and sulfur were added and the mix-
ing was continued for another 2 min. The final com-
pound temperature before dumping from the mixer
was in the range of 115–1208C. Immediately after
dumping, the compound was sheeted on a two-roll
mill to a thickness of about 2 mm. The resulting
EPDM compound was tested for its cure characteris-
tics using a Rubber Process Analyzer (RPA 2000,
Alpha Technologies) at 1408C, 0.833 Hz, and 0.28
strain according to ISO 6502. Scorch time (ts2), i.e.,
Figure 1 Preparation of 6-nitro MBTS by a direct nitration
method. time to incipient cure was determined and used as a
reference point to assign a pretreatment time of the
EPDM, as detailed in the previous part.1 A pretreat-
2,20 -dithiobis (benzothiazole) (MBTS, 99%, Aldrich), ment time of scorch time minus 2 min (ts2 2) was
65% nitric acid (Merck), and 96% sulfuric acid (Fluka). used for the EPDM compound containing CBS, and a
Staining agent for the TEM experiment was a 2% pretreatment time of scorch time minus 1 min (ts2 1)
osmic acid solution in water (Merck). was applied for the one with nitro-MBTS, as indicated
in Figure 2. The EPDM pretreatment was carried out
Preparation of 6-nitro-MBTS in a compression molding machine (Wickert WLP1600
laboratory press) at 1408C and 100 bar using a tensile
2,20 -Dithiobis (6-nitro-benzothiazole) (6-nitro-MBTS) sheet mold with a thickness of 2 mm.
was prepared by a direct nitration method,2 as
shown in Figure 1, to use this as accelerator instead
of the CBS in the compound formulation. Aromatic IR-characterization of the pretreated EPDM
nitro-compounds have strong characteristic peaks in 1 cm 8 cm-pretreated EPDM samples were sub-
the IR absorption, and hence 6-nitro-MBTS was cho- merged in regularly refreshed acetone for at least 48 h
sen for characterization purposes. 2,20 -Dithiobis (ben- to extract any unreacted accelerator species. The sam-
zothiazole) (MBTS) was first slowly dissolved in con- ples were then dried in a vacuum oven at room tem-
centrated sulfuric acid at room temperature, result- perature for 24 h. The IR spectra of dried samples
ing in a clear dark-brown solution. The MBTS were acquired by using the attenuated total reflec-
solution in acid was then cooled in ice to a tempera- tance infrared technique (ATR/IR) with a spectrome-
ture of 0–58C. Subsequently, a mixture of nitric acid ter FTS-60 (BIO-RAD Laboratories B.V., The Nether-
and sulfuric acid was slowly added. The reaction lands). The IR spectra were recorded with 512 scans at
mixture was left stirring at ambient temperature for a resolution of 8 cm1 in the range of 4000–600 cm1.
60 min. The solid product was recovered in ice-
water, filtered, neutralized by washing with water,
and finally dried in a vacuum oven at 508C. The Preparation of blend compounds
dried product was characterized by its melting tem- The two types of blend compounds referred to in
perature, FTIR, and 1H NMR spectra. this work are designated according to the proce-
dures adopted for their preparation: straight mix
Grafting of CBS and 6-nitro-MBTS onto EPDM
TABLE I
The entire amounts of curatives and other ingre- EPDM Compounds for the Pretreatment
dients, to eventually end up in the blends, were first Weight (g)
incorporated into the EPDM only using the Bra- Ingredient CBS 6-Nitro-MBTS
bender Plasticorder 350S mixer having a mixing
EPDM 30 30
chamber volume of 370 cm3. The amounts of all
Zinc oxide 4 4
compounding ingredients in the EPDM are given in Stearic acid 2 2
Table I. The amounts in Table I (particularly the TMQ 1 1
30 phr EPDM) are to be read as the total NR/BR/ CBS 1.98 (7.5 mmol) –
EPDM (35/35/30) blend compound formulation, 6-Nitro-MBTS – 1.58 (3.75 mmol)
Sulphur 2.5 2.5
minus the NR and BR, as specified in Table I of
Total weight 41.48 41.08
part I of this series.1 The mixer was operated with a

BLENDING OF NR/BR/EPDM BY REACTIVE PROCESSING. II 2549
RESULTS
6-Nitro-MBTS
Figure 3 shows the IR spectrum of 6-nitro-MBTS in
comparison with that of MBTS. The 6-nitro-MBTS
clearly shows two strong IR absorption bands at
1524 and 1346 cm1 attributed to the characteristic
absorption peaks of aromatic nitro- (N¼ ¼O) com-
pounds,3,4 which normally appear at wavenumbers
1530 6 20 cm1 and 1350 6 30 cm1.
The melting point of 6-nitro-MBTS measured by
using a heating rate of 28C/min from ambient tem-
perature to 3008C (Stuart Scientific melting point ap-
Figure 2 RPA cure curves of the EPDM compounds con- paratus SMP3, England) was in the range of 200–
taining CBS and 6-nitro-MBTS at 1408C with the indication 2058C, whereas that of original MBTS was in the
of the times being used later for the pretreatment. [Color
figure can be viewed in the online issue, which is available range of 178–1828C. From the 1H NMR spectra
at www.interscience.wiley.com.] acquired using deuterated chloroform as a solvent,
four different protons in MBTS were observed at 7.4,
and reactive mix. For each of the two blend types, 7.5, 7.8, and 8.0 ppm, whereas three different pro-
gum and carbon black-filled compounds were pre- tons in 6-nitro-MBTS resonate at 8.1, 8.4, and
pared. The overall recipes for both gum and filled 8.7 ppm as a result of the nitro electron withdrawing
blends are given in Table II. group, as shown in Figure 4.
The preparation of the various mixes such as gum
reactive mix, filled reactive mix, gum straight mix,
IR spectra of accelerator-grafted EPDM
and filled straight mix was described in detail in
part I of this series. ATR Fourier-IR spectroscopy was used in this study,
since the pretreated EPDM was only partially solu-
Vulcanization ble in common solvents. Even though the pretreat-
ment step only aimed to attach accelerator fragments
The optimum cure time (tc,90) of the fully com-
to the EPDM, a limited amount of crosslinking in
pounded blends was determined as the time needed
this reactive intermediate was apparently inevitable.
to reach 90% of the maximum torque in the RPA
However, the crosslinking in the pretreated EPDM
2000 at 1408C, 0.833 Hz, and 0.28 strain according to
was still minimal, since the material remained proc-
ISO 6502. The blends were then vulcanized in a
essible when being mixed with NR/BR.
Wickert WLP1600 laboratory compression press at
Figures 5 and 6 show the ATR-IR spectra of sol-
1408C and 100 bar.
vent extracted, pretreated EPDM prepared with CBS
and 6-nitro-MBTS, in comparison with the IR spec-
Atomic force microscopy trum of pure EPDM. The important functional
groups and their assignments are listed in Table III.
Vulcanized samples were prepared for AFM meas-
For pretreated EPDM with CBS, the characteristic
urements by cryo-microtoming the surfaces of the
signal of C¼ ¼N is observed at 1544 cm1. For pre-
samples with a diamond knife at –1508C using a
Leica ultra microtome. The AFM images were ac-
quired using a NanoScope III multimode atomic TABLE II
force microscope (Digital Instruments, Santa Barbara, Formulation of NR/BR/EPDM Compounds
CA in the Tapping Mode with phase imaging, at Gum blend Filled blend
ambient temperature. Ingredient content (phr) content (phr)
NR 35 35
BR 35 35
Transmission electron microscopy EPDM 30 30
Zinc oxide 4 4
70 nm thin sections of the blend vulcanizates were cry-
Stearic acid 2 2
ogenically cut with a diamond knife using a Leica ultra TMQ 1 1
microtome at 1508C. The sections were deposited on CBS 1.98 (7.5 mmol) 1.98 (7.5 mmol)
a carbon support film on copper grid (200 mesh) and Sulphur 2.5 2.5
then vapor stained using 2% osmium tetroxide for HAF N330 – 50
Naphthenic oil – 10
15 min. TEM measurements were performed with a
Total formulation weight 111.48 171.48
Philips CM 30 transmission electron microscope.

AFM images of the blend vulcanizates

The significant improvement of the tensile properties
of the blends prepared using the reactive processing
technique, when compared with those of blends pre-
pared with straight mixing, is certainly also partly
related to their blend morphology. In the present
work, both AFM and TEM were used to characterize
the morphology.
AFM works by bringing a sharp tip, located at the
end of a microfabricated cantilever, into close prox-
imity with the sample and then moving this fine tip
over the sample to map the contours of the surface.
The tip–sample interaction causes a change in the
Figure 3 FTIR spectra of 6-nitro-MBTS in comparison with amplitude, the phase, and the resonance frequency
that of original MBTS.
of the vibrating cantilever, and hence the spatial var-
iations of these changes can be presented in height
treated EPDM with 6-nitro-MBTS, two strong aro- or interaction (amplitude, phase, or frequency shift).5–10
matic nitro N¼¼O absorption peaks are clearly visible The height image represents surface topography,
at 1540 and 1401 cm1. and amplitude or phase images represent micro-
As these samples were solvent extracted prior to morphological features.
the ATR-measurement, the clear presence of earlier In this work, the blend samples were examined
absorption peaks indicates a substantial amount of using tapping mode AFM. In the tapping mode, the
MBT-groups, remnants of CBS, and 6-nitro-MBT AFM probe is driven to oscillation at its resonance fre-
groups chemically linked to the EPDM molecular quency by a piezoceramic element near the cantilever
chains. base, and damping of the cantilever’s amplitude due
1
Figure 4 H NMR spectrum of 6-nitro-MBTS in comparison with that of original MBTS.

TABLE III
Infrared Absorption Peaks and Their Assignments
Infrared absorption
peak (cm1) Functional group
2925, 2843 CH stretching
1544
C¼¼N stretching
1540, 1401
N¼¼O aromatic nitro
1462, 1378 CH bending (scissoring)
720 CH out-of plane bending
710–570 CS stretching, sulfides (weak)
less contrast or less distinct phases, indicating a bet-

ter homogeneity of the cure state distribution. Lower
Figure 5 ATR-IR spectra of pretreated EPDM in compari- cured EPDM domains do still exist, but in a lower
son with that of pure EPDM. [Color figure can be viewed proportion when compared with those observed in
in the online issue, which is available at www.interscience. the straight mixed blend.
wiley.com.] Figure 8 represents the tapping mode phase images
of 50 phr HAF-filled NR/BR/EPDM blends obtained
to tip–sample force interaction is the mechanism used by conventional straight mixing (left) and by reactive
for surface profiling.10 Figure 7 shows the phase mixing (right). Carbon black particles and filled
images of gum straight and reactive mixed blends, polymers show a lighter phase, whereas unfilled
and Figure 8 shows the phase images of the filled areas appear dark. By comparing these two images,
blends. The phase contrast is caused by differences in the AFM image of reactive mix on the right even
local elastic moduli or local hardness in the blend. more clearly illustrates a more homogeneous distri-
Hence, differences in local crosslink density and/or bution of either carbon black or EPDM phase, or
local filler concentration in the ternary blends result in both, in the blend. The darker areas that can be
different tip–sample interactions and subsequently, attributed to the EPDM phase possessing a lower
image contrasts. In general, in the phase image carbon black affinity when compared with the NR
obtained by tapping mode AFM, the higher modulus and BR phases are clearly smaller in the reactive
or harder polymer appears light and the lower modu- mixed blend.
lus or softer polymer appears dark.
The phase images of the gum NR/BR/EPDM (35/
35/30) blends prepared by both straight and reactive TEM images of the blend vulcanizates
mixing in Figure 7 clearly show at least two different TEM images of the gum blends are shown in Figure
phases, attributed to a dark EPDM phase and a light 9, and those of HAF-filled blends are shown in Fig-
diene (NR/BR) phase. The dark or softer EPDM ures 10 and 11. In the TEM,11 the electrons pass
phase is more distinguishable in the straight mixed through the sample section to a phosphorous screen.
blend. Considering the phase image of the blends Electrons that pass through less dense areas and
prepared by the reactive mixing, the image shows areas where the atomic numbers of the particles are
low are scattered to a smaller extent and so hit the
screen in greater number, creating more light. This is
Figure 6 ATR-IR spectra of pretreated EPDM in comp- Figure 7 Tapping mode AFM phase images of gum NR/
arison with that of pure EPDM in the range of 2000– BR/EPDM blends: straight mix (left) and reactive mix
1200 cm1. [Color figure can be viewed in the online issue, (right). [Color figure can be viewed in the online issue,
which is available at www.interscience.wiley.com.] which is available at www.interscience.wiley.com.]

Figure 8 Tapping mode AFM phase images of 50 phr

HAF-filled NR/BR/EPDM blends: straight mix (left) and re-
active mix (right). [Color figure can be viewed in the online
issue, which is available at www.interscience.wiley.com.] Figure 10 TEM images of 50 phr HAF-filled NR/BR/
EPDM blends: straight mix (left) and reactive mix (right)
at a magnification of 10,500.
in contrast with electrons that pass through more
dense areas and areas where the atomic numbers of boundaries in the images of the reactive mix are less
the particles are high. Therefore, the diene phases sharp, indicating a better carbon black distribution.
NR and BR, which are more stained by osmium te-
troxide than EPDM, become dense areas and appear
dark in the images. The EPDM phase contains a very
small amount of double bonds in the molecule, and DISCUSSION
is by far less stained by osmium tetroxide. The
Pretreated EPDM
EPDM phase therefore appears light in the TEM
images. The pretreatment of EPDM by heating the com-
The TEM images of the gum blends in Figure 9 pound containing sulfur, CBS or 6-nitro-MBTS, and
are complicated by the presence of the three types of ZnO initiates a normal sulfur vulcanization reaction.
rubbers in the blends. The lightest areas are the The generally accepted mechanism for sulfur vulcan-
EPDM phase; however, the darker areas are a mix- ization in the presence of activator ZnO starts with
ture of NR and BR, which cannot be clearly dis- the generation of active accelerator complexes be-
cerned. The EPDM particles are different in sizes tween accelerator and activator, which later interact
and dispersed in the NR/BR phases. with sulfur to form an active sulfurating agent.
Figures 10 and 11 are the TEM images of the These active sulfurating agents then react with allylic
HAF-filled blends, obtained by reactive mixing, hydrogen sites on the rubber molecules, resulting in
when compared with those obtained by straight mix- a rubber bound intermediate.12–15 Postulated EPDM-
ing. The reactive mix clearly shows a finer disper- bound intermediates generated in the presence of CBS
sion of carbon black among the phases. The zone and 6-nitro-MBTS are shown in Figures 12 and 13.
Figure 9 TEM images of gum NR/BR/EPDM blends: Figure 11 TEM images of 50 phr HAF-filled NR/BR/
straight mix (left) and reactive mix (right) at a magnifica- EPDM blends: straight mix (left) and reactive mix (right)
tion of 10,500. at a magnification of 21,000.

Since allylic hydrogen sites are not located in the

EPDM main chain, the CBS or 6-nitro-MBTS frag-
ments must attach to the EPDM molecules at the
positions provided on the third monomer ethylidene
norbonene. As a result of the limited pretreatment
time used, the further crosslinking reaction is quen-
ched, and the pretreated EPDM remains processable Figure 13 Postulated formation of EPDM-bound interme-
diate by pretreatment of EPDM compound containing 6-
indeed. The accelerator fragments are initially bound
nitro-MBTS.
to the EPDM chains, and hence the migration of the
curatives toward the NR/BR phase is restricted. A
better curative distribution in the reactive blend con- ing a better homogeneity of the cure state distribu-
sequently results in a more homogeneous crosslink tion. The pretreated EPDM does restrict curative dif-
distribution, which reflects in a remarkable improve- fusion toward the NR/BR because a large part is al-
ment in tensile properties, as shown in our previous ready chemically fixed to the EPDM, so the curative
study. concentration is better distributed between each
The ATR spectra of the pretreated EPDM in Fig- phase. In the straight mixed vulcanizate, the dis-
ures 5 and 6, prepared by using both the CBS and 6- persed undercured EPDM phase acts as a flaw or
nitro-MBTS accelerators, clearly show the additional weak point in the blend, hence resulting in inferior
peaks associated with the vibrations of the functional tensile properties. In the reactive mixed vulcanizate,
groups in the accelerator fragments attached to the lower cured EPDM domains do still exist, but smaller
EPDM. The CBS grafted EPDM has a distinct peak and in a much lower proportion when compared
at the wavenumber of 1544 cm1 attributed to the with those observed in the straight mixed blend.
C¼¼N stretch in thiazoles. The 6-nitro-MBTS grafted In the AFM images of the filled blends in Figure 8,
EPDM shows two distinct peaks assigned to the IR a more homogeneous distribution is most clearly
absorption of the aromatic nitro groups at 1524 and observed. This can be the result of both a better
1346 cm1. Other functional groups on the accelera- crosslink distribution and/or a finer filler dispersion.
tor fragments, i.e., CS and ortho-disubstituted ben- The EPDM pretreatment step apparently makes it
zene, are not distinguished in the spectra. The IR more difficult for carbon black to migrate from the
absorption band of the CS stretching vibration is EPDM phase toward the NR/BR phases. Normally,
normally in the range of 750–570 cm1, but the the NR/BR phases have a higher affinity for carbon
assignment of this band is difficult in IR spectra, black than EPDM. The grafted accelerator moieties
since the band is of variable intensity.4 The ortho-dis- raise the polarity of the EPDM slightly, enhancing its
ubstituted benzene has various absorption bands, affinity for carbon black. Second, pretreated EPDM
but the intensities of most of the peaks are weak. A may already consist of a lightly crosslink network,
strong aromatic ring absorption band at 760–705 which also hampers migration of carbon black out of
cm1 is in the same range as that of the CH out- the EPDM phase into the NR/BR phases.
of-plane bending in EPDM, and hence cannot be dis- The TEM images observed for the filled blends are
tinguished. There is a clear evidence provided by in a good agreement with the AFM images. The re-
the ATR spectra to conclude that CBS-fragments active mixing leads to more homogeneous blends,
and/or 6-nitro-MBTS are indeed chemically grafted and hence improves the blend properties.
to the EPDM.
Blend morphology CONCLUSIONS
The AFM images of the gum blends in Figure 7 Accelerator-grafted EPDM was prepared under a
show that the dark EPDM phase is less distinct from normal rubber processing condition prior to blend-
the main phase (NR/BR) in the reactive mix, indicating with premasticated NR/BR. The entire amount
of curatives and compounding ingredients was first
incorporated in the EPDM phase, then pretreated at
elevated temperature using a predetermined time
selected based on its scorch time. Extracted, pre-
treated EPDMs prepared using CBS and 6-nitro-
MBTS as the accelerators and characterized by
means of IR spectroscopy clearly show absorption
peaks assigned to the functional groups of grafted
Figure 12 Postulated formation of EPDM-bound interme- accelerator fragments. Both AFM and TEM images
diate by pretreatment of EPDM compound containing CBS. of reactive vulcanizates of gum and filled NR/BR/

EPDM (35/35/30) ternary blends prepared by reac- 5. Niedermeier, W.; Stierstorfer, J.; Kreitmeier, S.; Metz, O.;
tive mixing illustrate a better homogeneity of the Goritz, D. Rubber Chem Technol 1994, 67, 148.
6. Magonov, S. N.; Hwangbo, M. H. Surface Analysis with STM
blends, in comparison with those of straight mixed and AFM; VCH: Weinheim, 1996.
vulcanizates. 7. Galuska, A. A.; Poulter, R. R.; McElrath, K. O. Surf Interface
Anal 1997, 25, 418.
Clemens Padberg and Mark Smithers are acknowledged 8. Haeringen, D. T.-V.; Schönherr, H.; Vancso, G. J.; van der
Does, L.; Noordermeer, J. W. M.; Janssen, P. J. P. Rubber Chem
for help with the AFM and TEM experiments, respectively.
Technol 1999, 72, 862.
9. Jeon, I. H.; Kim, H.; Kim, S. G. Rubber Chem Technol 2003, 76, 1.
References 10. Yerina, N.; Magonov, S. Rubber Chem Technol 2003, 76, 846.
11. Sawyer, L. C.; Grubb, D. T. Polymer Microscopy; Chapman
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J Appl Polym Sci 2007, 103, 2538. 12. Kapur, R. S.; Koenig, J. L.; Shelton, J. R. Rubber Chem Technol
2. Talma, A. G. Akzo Nobel, Memorandum RPP9940022; Akzo 1974, 47, 911.
Nobel: Deventer, The Netherlands, 1999. 13. Morrison, N. J.; Porter, M. Rubber Chem Technol 1984, 57, 63.
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quencies; Wiley: New York, 1994. manian, V.; Walker, K. A. Rubber Chem Technol 2003, 76, 529.
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Blending of NR/BR/EPDM by Reactive Processing
for Tire Sidewall Applications. III. Assessment of the
Blend Ozone- and Fatigue-Resistance in Comparison
with a Conventional NR/BR Compound
Kannika Sahakaro,1,2* Rabin N. Datta,1,2 Johan Baaij,3 Jacques W. M. Noordermeer1,2

1
Dutch Polymer Institute, 5600AX Eindhoven, The Netherlands
2
Department of Rubber Technology, Faculty of Science and Technology, University of Twente, 7500AE Enschede,
The Netherlands
3
Elastomer Research Testing, 7420 AC Deventer, The Netherlands
Received 12 August 2005; accepted 17 May 2006

DOI 10.1002/app.25101
ABSTRACT: The NR/BR blend compound formulations parison with those of equivalent conventional NR/BR com-
for tire sidewall applications contain a set of stabilizers added pounds. The reactive NR/BR/EPDM blend vulcanizates
to prevent degradation mainly due to oxygen, ozone, and show excellent tensile strength, elongation at break, tear
heat. 6PPD is the most effective and widely used antiozonant strength, fatigue-to-failure, and ozone resistance in both static
in tire compounds, but is a highly staining material causing a and dynamic conditions. The properties are equivalent or
surface discoloration of the tire sidewall. Incorporation of 30 even superior to those of the conventional NR/BR tire side-
phr EPDM into blends of NR/BR improves the ozone resist- wall compounds. The simple straight mixed NR/BR/EPDM
ance to the required level, without the need of 6PPD. The first blend vulcanizates distinctively possess inferior mechanical
two parts of this series have described a reactive processing properties compared to those of the reactive mix. Ó 2006
technique applied to enhance the covulcanization and blend Wiley Periodicals, Inc. J Appl Polym Sci 103: 2555–2563, 2007
homogeneity, together with their characterization. In the pres-
ent article, the properties of the NR/BR/EPDM blends pre- Key words: blends; reactive processing; tire sidewall;
pared by both reactive and straight mixing are tested in com- fatigue resistance; ozone resistance
INTRODUCTION sequently cross-blended into the NR/BR phase. The

1,2 grafting of the MBT raises the polarity of the EPDM
In the first two parts of this series it has been
and hence increases the reactivity of EPDM towards
shown that by utilizing a reactive processing of the
sulfur curing and leads to a more homogeneous dis-
EPDM phase, in which the mercaptobenzothiazole
tribution of carbon black over the various phases.
(MBT) moiety of the common accelerator N-cyclo-
The EPDM rubber possesses excellent resistance to
hexyl-2-benzothiazole sulfenamide (CBS) is grafted
ozone, heat, ageing, and weathering due to its highly
onto the EPDM molecular chain prior to mixing into
saturated chemical structure, containing only non-
premasticated NR/BR, significant improvement in
conjugated carbon–carbon double bonds pendant to
tensile strength, elongation at break and blend homo-
the backbone chain. It has long been recognized that
geneity of the terpolymer NR/BR/EPDM vulcanized
incorporation of 20–40 phr EPDM into conventional
blends can be achieved. All curatives and reinforcing
tire sidewall compounds of NR and BR blends is suf-
fillers are first incorporated into the EPDM phase,
ficient to compensate for a loss of ozone resistance
then the EPDM compound is thermally pretreated
due to exclusion of the effective but highly staining
for a duration related to the scorch time, and sub-
and discoloring antiozonant, i.e., N-(1,3-dimethylbu-
tyl)-N0 -phenyl-p-phenylenediamine (6PPD).3–7 The
*Present address: Department of Rubber Technology and
Polymer Science, Prince of Songkla University, Pattani presence of a dispersion of ozone resistant particles,
Campus, Pattani 94000, Thailand. i.e., EPDM phase, in blends of diene rubbers impedes
Correspondence to: J. W. M. Noordermeer (j.w.m. the rate at which the microvoids, caused by ozone
noordermeer@utwente.nl). attacked on the exposed surface, coalesce into mac-
Contract grant sponsor: Dutch Polymer Institute (DPI); roscopic cracks.8 Waddell4 gave an extensive review
contract grant number: DPI project no. 356.
describing the surface discoloration problem and
Journal of Applied Polymer Science, Vol. 103, 2555–2563 (2007) various approaches to formulate a black tire sidewall
V
C 2006 Wiley Periodicals, Inc. with a use of ozone-resistant polymers, including
TABLE I
Compound Formulations
Compound formulation (F1–F8)
Gum HAF filled
Component F1 F2 (straight) F3 (reactive) F4 F5 F6 (straight) F7 (reactive) F8 (reactive)
NR 50 35 35 50 50 35 35 35
BR 50 35 35 50 50 35 35 35
EPDM 0 30 30 0 0 30 30 30
ZnO 4 4 4 4 4 4 4 4
Stearic acid 2 2 2 2 2 2 2 2
CBS 1.98 1.98 1.98 1.98 1.98 1.98 1.98 1.98
Sulfur 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5
6PPD 2.5 0 0 2.5 0 0 0 0
TMQ 1 1 1 1 1 1 1 0
Wax 1.5 1.5 1.5 1.5 1.5 1.5 1.5 0
HAF N330 0 0 0 50 50 50 50 50
Sunthene 4240 0 0 0 10 10 10 10 10
Total weight 115.48 112.98 112.98 175.48 172.98 172.98 172.98 170.48
EPDM, halobutyl rubbers, and brominated isobuty- Preparation of blend compounds

lene-co-para-methylstyrene. The incorporation of EPDM
There are eight different compounds denoted from
into NR compounds improves the ozone resistance,
F1 to F8, as the overall recipes shown in Table I.
but the blends exhibit a higher tangent delta and a
Compounds F1–F3 are gum and F4–F8 are carbon
higher fraction of dissipated energy.9 Under normal
black-HAF filled. For both gum and filled com-
running conditions, the tire sidewalls are subjected
pounds, conventional NR/BR blends and NR/BR/
to extensive flexing and continuous distortion under
EPDM blends obtained by both straight and reactive
load at a temperature higher than ambient, due to
mixing were prepared.
heat build up. In addition, the sidewalls are suscep-
The preparation of gum NR/BR (F1), gum straight
tible to ozone attack leading to degradation. The tire
mix NR/BR/EPDM (F2), and gum EPDM compound
sidewall must have good resistance to fracture over
for reactive mixing (F3) were prepared using a
a range of conditions covering rapid as well as slow
Brabender Plasticorder 350S mixer having a mixing
crack growth.10 The effect of inclusion of EPDM into
chamber volume of 370 cm3. The mixer was operated
the tire sidewall compounds on flex-fatigue perform-
with a rotor speed of 100 rpm, fill factor of 0.7, and an
ance, ozone resistance, as well as other mechanical
initial temperature of 508C. All HAF-filled compounds
properties is therefore very important especially
(F4–F8) were prepared by using the correspond-
from an application perspective.
ing masterbatches of rubber/HAF/oil, pre-prepared
In the final part of the series, the properties of
according to the formulations given in Table II of
NR/BR/EPDM blends, prepared by both reactive and
part I of this series. The masterbatches were mixed
straight mixing techniques, are assessed in compari-
with curatives and other ingredients using a Sch-
son with those of conventional NR/BR compounds.
wabenthan two-roll mill under a controlled tempera-
In addition to the carbon black filled-compounds for
ture of 508C.
tire application, gum vulcanizates are also investi-
The mixing procedures for both reactive and straight
gated to evaluate the properties of the reactive mixed
mixed NR/BR/EPDM blends of both gum and filled
NR/BR/EPDM blends in comparison with those of
conventional straight mixes.
EXPERIMENTAL TABLE II
Dynamic Ozone Test Conditions
Materials Test
The blends consist of the same ingredients as men- Condition 1st 2nd 3rd 4th
tioned in part I. Additional ingredients in the com- Ozone conc. (pphm) 50 6 5 50 6 5 100 6 5 100 6 5
pound formulations for this study are N-(1,3-dimethyl- Elongation (%) 10 20 20 30
butyl)-N0 -phenyl-p-phenylenediamine (Santoflex 6PPD, Temperature (8C) 40 6 2 40 6 2 40 6 2 40 6 2
Flexsys B. V., the Netherlands) and microcrystalline Relative humidity (%) 50 6 5 50 6 5 50 6 5 50 6 5
Frequency (Hz) 0.5 0.5 0.5 0.5
wax (Sunolite 240, Flexsys B. V., the Netherlands). All
Time (h) 72 48 24 72
ingredients were used as received.

BLENDING OF NR/BR/EPDM BY REACTIVE PROCESSING. III 2557
Tensile and tear test

Type 2 dumb-bell test specimens were die-cut from
the compression molded sheets and tensile tests
were carried out according to ISO 37, with a Zwick
tensile tester Model Z 1.0/TH1S at a constant cross-
head speed of 500 mm/min.
Trouser test specimens of 100 7.5 mm2 with a
cut of depth 40 mm were die-cut and the test was
performed according to ISO 34 Method A with the
Zwick tensile tester at a constant crosshead speed of
100 mm/min.
Figure 1 EPDM cure curves of gum and 50 phr HAF Fatigue-to-failure test
filled EPDM compounds at 1408C for pretreatment step,
indicating the pretreatment times used. Fatigue-to-failure test was carried out using a Mon-
santo fatigue-to-failure tester as described in ASTM
D 4482-99 at an extension ratio, i.e., the extended
compounds are described in detail in part I of this length of a specimen to the unextended length, of
series. There are two more additional additives added 2.0. A dumbbell test specimen undergoes a tensile-
to the recipes, compared to those recipes given in strain cycle and the number of cycles required to
part I, i.e., 6PPD and microcrystalline wax. For the cause failure, as indicated by complete rupture of the
Brabender mixing of the gum compounds, 6PPD and test specimen, is recorded. In this test, 12 test speci-
wax were added into the compounds together with mens of each sample were tested and the median
ZnO, stearic acid, and TMQ. For the two-roll mill mix- value of the number of cycles required to cause fail-
ing of the filled compounds, stearic acid, ZnO, CBS, ure was recorded.
TMQ, 6PPD, wax, and sulfur were sequentially
added. Static and dynamic ozone test
For reactive mixing, the EPDM compounds with
the entire amounts of curatives and other ingredients Ozone resistance of the blend vulcanizates in both
were first pretreated to a predetermined pretreat- static and dynamic conditions was tested according
ment time related to the scorch time of the EPDM to ISO 1431-1 using an Argentox ozone test cabinet
phase, as described in detail in part I of this series. (Argentox Ozone Technology, Germany).
Based on this previous study, a pretreatment time of For the static ozone test, the test specimens of
scorch time minus 2 min (ts22), and a pretreatment 20 mm in width and 2 mm of thickness, as shown in
time of scorch time plus 1 min (ts2þ1) were selected Figure 2, were clamped, elongated to 20% and tested
for gum and filled blends respectively, as shown in under the following conditions: ozone concentration
Figure 1. The thermal pretreatment of EPDM was car- 50 6 5 pphm; temperature 408C 6 28C; relative
ried out at 1408C in a compression molding machine humidity 50% 6 5% for 168 h.
(Wickert WLP1600 laboratory press) using a tensile For the dynamic ozone test, specimens and test
sheet mold with a thickness of 2 mm. configuration are shown in Figure 2.
The pretreated EPDM compounds of both gum Test specimens are normally clamped at the re-
and filled were finally cross-blended with NR/BR on quired elongation. However, in this case, the speci-
a two-roll mill.
Vulcanization
The optimum cure time (tc,90) of the fully com-
pounded blends was determined as the time needed
to reach 90% of the maximum torque in the RPA
2000 at 1508C, 0.833 Hz, and 0.28 strain according to
ISO 6502. The blends were vulcanized in a compres-
sion press (Fontijne, Holland) at 1508C.
The resulting blend vulcanizates were left condi- Figure 2 Test specimens and test configuration in dynamic
tioning at room temperature for at least 16 h prior to ozone cabinet. [Color figure can be viewed in the online
being tested. issue, which is available at www.interscience.wiley.com.]

mens with modified ends were not tightened

between grips, but hanged and elongated using a
specially built sample holder (ERT B.V., the Nether-
lands) to prevent an excessive stress concentration
and hence breakage at the grips during the ozone
test. The test specimens were attached to the sample
holder consisting of a stationary part (top) at a fixed
position and a moving part (bottom) which is driven
to travel to a specific elongation.
Under unspecified conditions, the test is normally
carried out at an ozone concentration of 50 6 5 pphm.
In this test, after the first test at 50 6 5 pphm ozone
concentration, 10% elongation for 72 h, only com-
Figure 4 RPA cure curves of the 50 phr-HAF filled blend
pound F5 without antidegradants showed cracks on compounds at 1508C. [Color figure can be viewed in the on-
the surface. Further tests on the same test specimens line issue, which is available at www.interscience.wiley.com.]
were then carried out consecutively to differentiate
between each compound. The tests conditions are the maximum torque levels of the gum blends, the
shown in Table II. NR/BR blend shows the highest maximum torque,
whereas both of the NR/BR/EPDM blends show
more or less equivalent values. On the other hand,
RESULTS
the NR/BR cure curve shows a higher degree of re-
Cure characteristics of the blends version compared to the NR/BR/EPDM blends.
In the case of filled blends, the maximum torque
Figure 3 shows a cure curve of the gum NR/BR
of the reactive NR/BR/EPDM blend is lower than
blend F1 in comparison with those of the gum NR/
those of straight mixed NR/BR/EPDM blend and
BR/EPDM straight mixed F2 and reactive mixed F3
NR/BR blends, respectively. The straight mixed
blends. Figure 4 shows the cure curves of the 50 phr
NR/BR/EPDM blend shows only a slightly longer
HAF-filled NR/BR blends F4 and F5, in comparison
cure time compared to the NR/BR blend, but the re-
with the 50 phr HAF-filled NR/BR/EPDM straight
active NR/BR/EPDM blends clearly show shorter
mix F6 and reactive mixes F7 and F8. The RPA cure
scorch and cure times. The NR/BR/EPDM filled
characteristics data is also summarized in Table III.
blends again show better torque retention, i.e., less
The gum blend compounds show significant dif-
reversion, compared to the NR/BR filled blends.
ferences in both scorch and cure times, whereas the
differences in the filled blend compounds containing
HAF carbon black are less pronounced. The simple Tensile and tear properties
addition of highly saturated EPDM into NR/BR Figures 5–7 show the tensile moduli at 100 and
gum compound increases both scorch time and cure 300%, tensile strength and elongation at break of the
time. However, by applying the reactive processing blend vulcanizates, respectively. The gum NR/BR/
method, a significant reduction in both scorch time EPDM blends exhibit higher moduli, at both 100 and
and cure time of the blend is observed, as a result of 300% strain, than the gum NR/BR blend. The higher
the EPDM thermal-pretreatment step. Considering moduli are clearly caused by the presence of the
EPDM phase in the blend. For the filled blends, a
more or less similar modulus at 100% strain is ob-
served for all cases, but the reactive NR/BR/EPDM
filled blends F7 and F8 show a clearly lower modu-
lus at 300% strain compared to the NR/BR and
straight mixed NR/BR/EPDM blends. The highest
modulus at 300% strain observed for the NR/BR
blend containing no 6PPD, TMQ and wax.
The tensile strength of both gum and filled NR/
BR/EPDM blends prepared by the reactive process-
ing method are comparable to those of NR/BR
blends, but significantly higher than the NR/BR/
EPDM blends prepared by straight mixing. Both the
Figure 3 RPA cure curves of the gum blend compounds gum and filled reactive NR/BR/EPDM blends show
at 1508C. [Color figure can be viewed in the online issue, a slightly higher elongation at break compared to
which is available at www.interscience.wiley.com.] the NR/BR blends, but again significantly higher

TABLE III
Cure Characteristics of the Compounds at 1508C
Compound formulation (F1–F8)
Gum HAF filled
RPA data F1 F2 (straight) F3 (reactive) F4 F5 F6 (straight) F7 (reactive) F8 (reactive)
Min. torque, FL (dN m) 0.26 0.28 0.24 0.61 0.68 0.66 0.58 0.61
Max. torque, Fmax (dN m) 4.23 3.95 3.93 9.21 9.78 9.08 8.28 8.65
FmaxFL (dN m) 3.97 3.66 3.69 8.60 9.10 8.42 7.70 8.04
ts2 (min) 8.45 12.00 1.17 3.85 4.21 2.63 0.73 0.87
tc,90 (min) 14.78 22.06 4.01 8.25 9.09 10.21 4.37 4.67
than the straight NR/BR/EPDM blends. The results standard, this fatigue test implies a rupture failure
are in agreement with those reported in part I of this mechanism that stems from the growth of flaws in
series. the specimen, and fatigue data give primarily an
Figure 8 shows the trouser tear strength of the blend estimation of the crack initiation behavior of a rubber
vulcanizates. Considering the mean tear strength of vulcanizate.
the gum NR/BR and of the reactive NR/BR/EPDM Considering the fatigue-to-failure of the gum blends
blends, both of them show equivalent values, but shown in Figure 9, the NR/BR blend shows a supe-
higher than the straight mixed NR/BR/EPDM blend. rior fatigue life compared to the gum NR/BR/EPDM
In case of the filled blends, the reactive NR/BR/ blends. However, between the gum NR/BR/EPDM
EPDM blend F7 containing TMQ and wax shows the blends, the reactive mix gives a significant improve-
highest value, and the NR/BR/EPDM blends show ment in fatigue life compared to the straight mix. In
a higher tear strength than the NR/BR blends F4 case of the filled blends, by applying the reactive
and F5. On comparing the tear strength of the NR/ processing method, a number of cycles to failure of
BR blends, F4 versus F5, the exclusion of 6PPD the reactive NR/BR/EPDM blend vulcanizate is
apparently has a negative effect on the tear strength observed which is approximately two-fold higher
of the blend vulcanizate. On comparing the NR/BR/ than that of the blend prepared by simple straight
EPDM blends with equivalent ingredient composi- mixing. In addition, the fatigue-to-failure (Kc) of the
tions, F6 versus F7, the tear strength of the reactive filled reactive NR/BR/EPDM blend shows even
NR/BR/EPDM blend is clearly better than that of significantly higher values than the filled NR/BR
the straight mix. The exclusion of antidegradants in blends.
F8 also results in a reduction of tear strength of the
blend vulcanizate.
Static and dynamic ozone resistance
All specimens are free of cracks after the static ozone
Flex-fatigue
test for 168 h at an ozone concentration of 50 pphm,
The cyclical flexing of the test specimens initiates temperature of 408C, and 20% elongation.
cracks and finally leads to complete rupture of the A subsequent series of dynamic ozone tests, car-
test specimens. According to the ASTM D 4482 test ried out consecutively on the same test specimens
Figure 5 Moduli at 100 and 300% strain of the blend

vulcanizates. Figure 6 Tensile strength of the blend vulcanizates.

Figure 7 Elongation at break of the blend vulcanizates. Figure 9 Fatigue-to-failure of the blend vulcanizates at an
extension ratio of 2.
under the heavier test conditions described in Table II, testing conditions of the 4th test, i.e., 100 pphm ozone
illustrates the resistance to ozone cracking of the concentration and 30% elongation. All the gum blend
NR/BR/EPDM blends in comparison with the con- vulcanizates in Figure 12 show small cracks on the
ventional NR/BR blends with 6PPD as antiozonant. elongated area. However, the test specimens of the
After the 1st and 2nd test, there are no cracks ob- gum NR/BR/EPDM blends rupture completely soon
served on the surface of any test specimens, except after cracks appear, indicating a low cut growth re-
on those of compound F5: NR/BR with no 6PPD. sistance of the NR/BR/EPDM blends compared to
The exclusion of 6PPD from the NR/BR blend clearly the NR/BR blends.
gives no protection of the rubber against ozone attack, Cracks can also be observed on the surface of the
and cracks in a direction perpendicular to the elon- filled blend vulcanizates. Figure 13 shows many
gation are clearly observed, as shown in Figure 10. small cracks on the edge but only a few on the sur-
Figure 10 also clearly shows surface discoloration face of the F4 NR/BR blend with 6PPD. The test
and staining, caused by the use of 6PPD in the F1 specimens of F6, F7, and F8 show a lower number of
and F4 compounds. cracks and better surface appearance. However,
After the 3rd test at 20% elongation and 100 pphm these specimens ruptured soon after the develop-
ozone concentration for 24 h, very small cracks can ment of the cracks, again due to lower cut growth
be seen on the surface of compound F4 through a resistance.
2 magnifying glass, as shown in Figure 11. The F5
vulcanizates are badly damaged. On the other hand,
there are still no cracks visible with 2 magnification DISCUSSION
for the blend vulcanizates of compounds F1, F2, F3,
F6, F7, and F8. Figure 11 also shows a badly stained As has been demonstrated in parts I and II of this
F1 gum NR/BR vulcanizate due to 6PPD, in compar- series, the reactive processing technique significantly
ison with the light colored F2 gum NR/BR/EPDM improves tensile properties and blend morphology
blend vulcanizate. of NR/BR/EPDM blends. This study covers such
Figures 12 and 13 show photographs of the blend blend properties as relevant for tire sidewall applica-
vulcanizates exposed to ozone under the most severe tion, e.g., flex-fatigue and ozone resistance, in direct
comparison with conventional NR/BR sidewall com-
pounds. The cure characteristics of the blends shown
in Table III and Figures 3, 4, reveal a shorter scorch
time and cure time of the reactive NR/BR/EPDM
blends compared to NR/BR and straight mixed NR/
BR/EPDM blends, respectively. This is the result of
the preactivated EPDM as, described in detail in
part II. Irrespective of the somewhat higher maxi-
mum torques of the NR/BR compounds compared
to those of the reactive NR/BR/EPDM blends, both
gum and filled reactive ternary blend vulcanizates of
NR/BR/EPDM yield more or less equivalent tensile
properties: tensile moduli, tensile strength, and elon-
gation at break. The inclusion of 30 phr of EPDM
Figure 8 Trouser tear strength of the blend vulcanizates. into the NR/BR blend by means of the reactive pro-

Figure 10 Photographs of blend vulcanizates of compound F1, F4, and F5 after 2nd test. [Color figure can be viewed in
the online issue, which is available at www.interscience.wiley.com.]
cessing technique, clearly retains the properties of firming the improvement of crosslink and/or filler
the simple NR/BR blend, as a result of a good cross- distribution among the various rubber phases in the
link distribution between the various rubber phases ternary blend. The primary controlling parameters
and/or a better homogeneous carbon black distribu- affecting the fatigue life are inhomogeneities or flaws
tion in the blends. Simple straight mixed NR/BR/ present in each sample, caused by the blending, mix-
EPDM again results in the poorest tensile properties, ing, curing, and sample cutting.11 The reactive NR/
reproducible with the results reported in part I. BR/EPDM blends show a much better blend homo-
The tear strengths of the gum NR/BR and reactive geneity compared to that of equivalent straight mix,
NR/BR/EPDM blend vulcanizates are equivalent, and hence possess significantly longer fatigue life.
but clearly better than the straight mixed gum NR/ The static ozone test produced no visible cracks in
BR/EPDM. On the other hand, the filled NR/BR/ either compound. The presence of microcrystalline
EPDM blends show higher tear strengths compared wax in the compounds is apparently sufficient to
to the equivalent filled NR/BR blends, and the high- protect the rubber under static conditions due to the
est value is observed for the reactive NR/BR/EPDM formation of a surface film of bloomed wax.3,12
containing TMQ and wax: compound F7. The higher However, under dynamic conditions, the inelastic
tear strength of such reactive NR/BR/EPDM blend wax film breaks and allows ozone to attack. As tire
vulcanizates again must be the result of a better sidewalls are subjected to both static and dynamic
homogeneity of either crosslink distribution or ozone exposures, therefore, an antiozonant for dy-
carbon black distribution or both. The dispersion of namic service condition, e.g., 6PPD, is required.
EPDM particles inside the NR/BR matrix could also From the dynamic ozone test results it is seen, that
impede the tear propagation and hence increases the addition of 30 phr of EPDM into the conven-
tearing energy or tear strength. tional NR/BR blends gives the blends the same good
The superior fatigue-to-failure of the gum NR/BR resistance to ozone cracking in both static and dy-
blends, shown in Figure 9, over the gum NR/BR/ namic conditions as 2.5 phr of 6PPD.
EPDM blends, and also the better fatigue property of The dynamic ozone test results for both gum and
the filled reactive NR/BR/EPDM blends compared filled blends suggest that the 6PPD can be totally
to the NR/BR and the straight mixed NR/BR/EPDM omitted from the compound formulation when re-
blends, are partially due to their lower modulus, as placed by EPDM. The ternary blends show excellent
shown in Figure 5. Considering the NR/BR/EPDM physical appearance because of absence of the stain-
blends only, the reactive mixes do have distinctively ing antiozonant. Considering the ozone resistance of
better fatigue-to-failure than the straight mixes, con- the NR/BR/EPDM blends, the blend vulcanizates
Figure 11 Photographs of blend vulcanizates of compound F1,F2, F4, and F5 after 3rd test. [Color figure can be viewed
in the online issue, which is available at www.interscience.wiley.com.]

Figure 12 Photographs of gum blend vulcanizates during the 4th test, observed after 24, 48, and 72 h ozone exposure.
[Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]
Figure 13 Photographs of 50 phr HAF-filled blend vulcanizates during the 4th test, observed after 24, 48, and 72 h
exposure. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

obtained by both straight mix and reactive mix show dynamic conditions of the NR/BR/EPDM blend
a similar quality, suggesting that the resistance to vulcanizates with 30 phr of EPDM is excellent and
ozone cracking is only due to the presence of a suffi- 6PPD can totally be omitted from the tire sidewall
cient amount of highly saturated EPDM, irrespective compound. The overall properties of the reactive
of crosslink and/or filler distribution and blend mixed NR/BR/EPDM blends are clearly better than
morphology. The ozone resistance of the F8 NR/BR/ those of the straight mixed NR/BR/EPDM blends,
EPDM blends indicates that both 6PPD and micro- obviously due to the improvement of crosslink and/
crystalline wax can be omitted from the formulation. or carbon black distribution in the blends as seen in
This preliminary laboratory study on the perform- part II, and the reproducibility of the reactive pro-
ance of NR/BR/EPDM blends prepared by using cessing technique.
the reactive processing technique, gives a promising
perspective for application in tire sidewalls. The re-
active processing technique is simple to implement References
and the properties of the ternary blend without 1. Sahakaro, K.; Naskar, N.; Datta, R. N.; Noordermeer, J. W. M.
staining antiozonants are equivalent to those of a J Appl Polym Sci 2007, 103, 2538.
conventional NR/BR tire sidewall compound. 2. Sahakaro, K.; Talma, A. G.; Datta, R. N.; Noordermeer, J. W. M.
J Appl Polym Sci 2007, 103, 2547.
3. Layer, R. W.; Lattimer, R. P. Rubber Chem Technol 1990, 63,
CONCLUSIONS 426.
4. Waddell, W. H. Rubber Chem Technol 1998, 71, 590.
The physical properties of NR/BR/EPDM blend 5. Sandstrom, P. H.; Lal, J. (to Goodyear Tire & Rubber, Co.).
vulcanizates prepared by using the reactive process- U.S. Pat. 4,003,420 (1977).
6. Sandstrom, P. H.; Lal, J. (to Goodyear Tire & Rubber, Co.).
ing technique under optimum conditions, are equiv-
U.S. Pat. 4,004,627 (1977).
alent or even superior to conventional NR/BR tire 7. Van de Ven, P. M.; Noordermeer, J. W. M. Rubber World
sidewall compounds. The tensile strength and elon- 2000, 222, 55.
gation at break of the reactive filled NR/BR/EPDM 8. Doyle, M. J. Presented at the International Tire Exhibition
blends and the NR/BR filled blends are more or less Conference, Akron, Ohio, September 10–12, 1996.
9. Sumner, A. J. M.; Kelbch, S. A. Rubber World 1995, 213, 38.
equivalent. The reactive filled NR/BR/EPDM blends
10. Kim, H. J.; Hamed, G. R. Rubber Chem Technol 2000, 73, 743.
show superior tear strength and fatigue-to-failure to 11. Young, D. G.; Kresge, E. N.; Wallace, A. J. Rubber Chem
those of the equivalent filled NR/BR blend com- Technol 1982, 55, 428.
pound. The ozone resistance under both static and 12. Veith, A. G. Rubber Chem Technol 1972, 45, 293.

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Blending of NR/BR/EPDM by Reactive Processing for

Tire Sidewall Applications. I. Preparation, Cure

Kannika Sahakaro,1,2* Nityananda Naskar,1,2y Rabin N. Datta,1,2 Jacques W. M. Noordermeer1,2

Received 12 August 2005; accepted 17 May 2006

INTRODUCTION the ozone and thermo-oxidative resistances of tire side-

Journal of Applied Polymer Science DOI 10.1002/app

Preparation of blend compounds

Journal of Applied Polymer Science DOI 10.1002/app

Figure 4 RPA cure curves of the reactive mixed gum

Journal of Applied Polymer Science DOI 10.1002/app

Journal of Applied Polymer Science DOI 10.1002/app

Journal of Applied Polymer Science DOI 10.1002/app

strength shows the most pronounced dependence on

Journal of Applied Polymer Science DOI 10.1002/app

mix, as will be characterized in detail in the next ar-

The authors thank Dr. Auke G. Talma for fruitful dis-

Journal of Applied Polymer Science DOI 10.1002/app

Journal of Applied Polymer Science DOI 10.1002/app

Kannika Sahakaro,1,2* Auke G. Talma,1,2 Rabin N. Datta,1,2 Jacques W. M. Noordermeer1,2

Received 12 August 2005; accepted 21 July 2006

INTRODUCTION for an increased reactivity of the EPDM toward sulfur

rotor speed of 100 rpm, ﬁll factor of 0.7, and an

Journal of Applied Polymer Science DOI 10.1002/app

Journal of Applied Polymer Science DOI 10.1002/app

AFM images of the blend vulcanizates

Journal of Applied Polymer Science DOI 10.1002/app

less contrast or less distinct phases, indicating a bet-

Journal of Applied Polymer Science DOI 10.1002/app

Figure 8 Tapping mode AFM phase images of 50 phr

Journal of Applied Polymer Science DOI 10.1002/app

Since allylic hydrogen sites are not located in the

Blend morphology CONCLUSIONS

Journal of Applied Polymer Science DOI 10.1002/app

Journal of Applied Polymer Science DOI 10.1002/app

Kannika Sahakaro,1,2* Rabin N. Datta,1,2 Johan Baaij,3 Jacques W. M. Noordermeer1,2

Received 12 August 2005; accepted 17 May 2006

INTRODUCTION sequently cross-blended into the NR/BR phase. The

EPDM, halobutyl rubbers, and brominated isobuty- Preparation of blend compounds

Journal of Applied Polymer Science DOI 10.1002/app

Tensile and tear test

Journal of Applied Polymer Science DOI 10.1002/app

mens with modiﬁed ends were not tightened

Journal of Applied Polymer Science DOI 10.1002/app

Figure 5 Moduli at 100 and 300% strain of the blend

Journal of Applied Polymer Science DOI 10.1002/app

Journal of Applied Polymer Science DOI 10.1002/app

Journal of Applied Polymer Science DOI 10.1002/app

Journal of Applied Polymer Science DOI 10.1002/app

Journal of Applied Polymer Science DOI 10.1002/app

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