J Polym Res (2016) 23:228
DOI 10.1007/s10965-016-1123-1
ORIGINAL PAPER
Physico-mechanical properties and automotive fuel resistance
of EPDM/ENR blends containing hybrid fillers
Sarawut Prasertsri 1 & Kanokwan Kurakanok 1 & Nattapon Sukkapan 1
Received: 17 October 2015 / Accepted: 12 October 2016
# Springer Science+Business Media Dordrecht 2016
Abstract This research aimed to investigate the effect of
blend ratios on cure characteristics, mechanical and dynamic
properties, morphology and automotive fuel resistance of
ethylene-propylene diene rubber (EPDM) and epoxidized nat-
ural rubber (ENR) blends containing carbon black and calcium
carbonate hybrid filler. The composition of EPDM/ENR
blends varied were 100/0, 70/30, 50/50, 30/70 and
0/100 %wt/wt. All ingredients used for preparing each blended
compound, except for the curatives, were mixed in a kneader.
Thereafter, the compound was further mixed with curatives on
a two-roll mill and then were vulcanized together with shaped
by compression molding before determining cure characteris-
tics, mechanical properties, morphology and weight swelling
ratio in three automotive fuels; gasohol-91, diesel and engine
oils. The results indicated that Mooney viscosity and cure time
of EPDM/ENR blends tended to decrease with increasing
ENR content, while cure rate index and crosslink density in-
creased. Tensile strength of all EPDM/ENR blends is lower than
that of the individual EPDM and ENR. This is attributed to the
incompatibility between nonpolar and polar nature of EPDM and
ENR, respectively, supporting by the glass transition temperature
form dynamic mechanical thermal analysis (DMTA) and scan-
ning electron micrographs (SEM). Owing to the differences in
polarity of automotive fuels and rubbers, weight swelling of
EPDM/ENR vulcanizates decreased in diesel and engine oils,
but increased in gasohol-91 with increasing in ENR content.
* Sarawut Prasertsri
sarawut.p@ubu.ac.th; sarawut.pra@gmail.com
1
Laboratory of Advanced Polymer and Rubber Materials (APRM),
Rubber Science and Technology Program, Department of Chemistry,
Faculty of Science, Ubon Ratchathani University, Ubon
Ratchathani, Thailand
Keywords Rubber blends . Cure characteristics . Mechanical
property . Automotive fuel resistance
Introduction
Elastomer blends are widely used in rubber industries for a
variety of purposes, such as enhancement of mechanical, dy-
namic, thermal ageing properties as well as improvement of
processing characteristics and reduction in product cost [1–4].
The properties of rubber blends are generally controlled by
many factors such as blend ratios, phase morphology, blend-
ing conditions and distribution of compounding ingredients
[5]. Although the properties of polymer blends obviously de-
pend on the properties of each component, it is the fact that
these complex systems exhibit a behavior which does not
simply follow the sum of the properties of each component.
The most important factor governing the ultimate properties
such as strength or toughness along with the blend composi-
tion is intermolecular bonding force between phases. Sae-Oui
et al. [6] revealed that improvement in oil, thermal and ozone
resistance of silica-filled natural rubber (NR)/chloroprene rub-
ber (CR) blends can be obtained by increasing CR content.
However, tensile strength of the blends does not follow the
mixture rule, i.e., the tensile strength slightly reduces with
increasing NR content up to 50/50 CR/NR ratio and further
increase in NR content results in a sharp drop of tensile
strength due to incompatibility between NR and CR.
Blending of EPDM with NR imparts the blend with good heat
and ozone resistance as well as chemical resistance. Botos
showed that 25/75 and 50/50 NR/EPDM blends possess the
best resistance against thermal ageing and UV irradiation, re-
spectively [7]. George and co-workers studied the gas perme-
ability of NR/styrene-butadiene rubber (SBR) blends [8] and
NR/carboxylated styrene-butadiene rubber (XSBR) blends
228 Page 2 of 7
[9]. They found a reduction in the nitrogen and oxygen per-
meability of the blends with increasing the synthetic rubber
content.
Ethylene-propylene diene monomer (EPDM) is valuable
synthetic rubber for its excellent thermal aging and ozone
resistance due to a highly unsaturated backbone. Nevertheless,
it exhibits unsatisfactory compatibility with most oils, gasoline,
kerosene, aromatic and aliphatic hydrocarbons due to
nonpolarity. This is the drawback of EPDM for utilizing in
automotive applications especially for contact automotive fuel.
Therefore, blending of EPDM with other polymers is a very
useful technique for the preparation and development of mate-
rials with properties superior to those of individual constituents.
Al-Gahtani [10] found that the presence of EPDM in the
EPDM/acrylonitrile butadiene rubber (NBR) blends to accom-
pany by an enhancement in technological properties, which
depends on the composition of EPDM and the increased con-
tent of crosslink density. In addition, the degree of reinforce-
ment in NBR/EPDM blends usually increases with carbon
black (FEF) loading. According to Botros and Tawfic [11] re-
ported that the 25/75 EPDM/NBR blend possessed the highest
aged mechanical properties together with good thermal stability
and the fatigue resistance of the vulcanizates is also greatly
improved superior to those of individual constituents. El-
Sabbagh and co-workers [12] found that the addition of NBR
to EPDM improved the motor oil swelling resistance of EPDM,
however blending of EPDM and NBR generally exhibited a
non-synergistic effect with respect to the physical properties.
Blends based on non-polar EPDM and polar ENR have dem-
onstrated great potential applications in many fields. Poh and
Teh have reported on the adhesion properties of EPDM/ENR
blends based pressure-sensitive adhesive [13]. With varying
EPDM/ENR blend ratios, the shear strength increased with in-
creasing percentage of ENR in the blends and peel strength of
adhesives increased steadily up to 60 % ENR before decreasing
with further increase in ENR owing to the incompatibility.
AfifiAhmed and Sayed [14] were investigated the ultrasonic
and mechanical properties of unfilled EPDM/ENR blend sys-
tem with ENR content of 0, 25, 50, 75 and 100 wt%. They
found that the blend exhibits good mechanical properties in
the range of 0–25 wt% ENR. Recently, we have studied the
changes in properties of hybrid-filled 70/30 EPDM/ENR in
which the calcium carbonate (CaCO3) was partially replaced
by crumb rubber [15]. The CaCO3/crumb rubber ratios were
varied from 0/60 to 60/0 by weight, while the total loading of
fillers was kept constant at 60 parts per hundred parts of rubber
(phr). The suitable crumb rubber loadings in 70/30 EPDM/ENR
blends having hybrid fillers are in the range of 10–30 phr to
realize the deterioration of their mechanical properties and to
reduce production costs. Although the blend of EPDM/ENR is
not at all new, the relationship between oil resistance property
and blend ratios in EPDM/ENR system has not been reported
nor widely known in comparison with EPDM/NBR system.
J Polym Res (2016) 23:228
Seeking to identify new options for automotive applications,
this research work focused on the elucidation of fuel resistance
in EPDM/ENR containing high loading of carbon black/CaCO3
hybrid fillers. In order to explore the effect of blend ratios on
automotive fuel resistance, the various chemical natures of fuels
used for weight swelling measurement were gashol-91, diesel
and engine oil (heavy duty diesel type). Cure characteristics,
mechanical and dynamic properties, morphology of various
EPDM/ENR blends were also investigated.
Experimental
Materials
Ethylene-propylene diene rubber (EPDM; Vistalon™ 3666)
having ethylidene norbornene (ENB) of 4.5 %wt was supplied
by ExxonMobil Chemical (Thailand) Ltd., Thailand.
Epoxidized natural rubber (ENR, Epoxyprene-50) having ep-
oxidation level of 50 %mole was provided from Muang Mai
Guthrie Public Co., Ltd., Thailand. Other chemicals were pro-
cured from indigenous sources and were used as such. Stearic
acid and zinc oxide (ZnO) were obtained from Chemmin Co.
Ltd. Carbon black (N330) and calcium carbonate (Precipitated
CaCO3) were supplied by Thai Carbon Product Co. Ltd., and
P.S. Science Chemical Ltd., respectively. N-(1,3-dimethylbutyl)-
N′-phenyl-p-phenylene diamine (6-PPD) was brought from
Imperial Industrial Chemicals (Thailand) Co.,Ltd. Sulfur was
supplied by The Siam Chemical Public Ltd. and accelerators
which were 2,2′-dithiobis (benzothiazole) (MBTS) zinc
diethyldithiocarbamate (ZDEC) and tetramethylthiuram disulfide
(TMTD) were purchased from Chemmin Co. Ltd. Three auto-
motive fuels were gashol-91, diesel and engine oil which were
supplied from a petroleum station of PTT Public Co., Ltd. The
gasohol-91 is the 10 % ethanol mixed with 90 % gasoline in
octane 91.
Mixing and vulcanization procedure
Five rubber compounds of different EPDM/ENR compo-
sitions containing carbon black/calcium carbonate hybrid
filler were prepared. The blend ratios of EPDM/ENR were
100/0, 70/30, 50/50, 30/70 and 0/100 %wt/wt. The other
rubber chemical used contain (in parts per hundred parts
of rubber; phr): stearic acid, 2.0; ZnO, 6.0; carbon black,
40; calcium carbonate, 60; paraffinic oil, 5; 6-PPD, 2.0;
TMTD, 0.8; ZDBC, 2.5; MBTS, 1.5; sulfur 2.0. All ingre-
dients, except the curatives were mixed with a kneader at a
set temperature of 50 °C with a fill factor of 0.75. The
EPDM and ENR were firstly blended before adding steric
acid, ZnO, fillers and processing oil, 6-PPD, respectively.
The total mixing time in the kneader was 13 min.
Thereafter, the blended masterbatches having different
J Polym Res (2016) 23:228
EPDM/ENR ratios were mixed with curatives on a two-
roll mill for 5 min. Then, the cure characteristics in term of
scorch time (ts2), cure time (tc100), cure rate index (CRI)
and torque difference (MH-ML) were measured using os-
cillating disc rheometer (ODR) at 160 °C in accordance
with ASTM D 2084. The vulcanized specimens were pre-
pared by using hydraulic hot press according to their re-
spective cure time from ODR results.
Testing
The dynamic mechanical properties were determined
using a dynamic mechanical thermal analyzer; DMTA
(Gabo, Explexor TM 25 N). The specimens were evaluat-
ed in tension mode at a constant frequency of 10 Hz and a
dynamic strain of 0.1 %. The temperature was raised from
−80 to 80 °C with a heating rate of 2 °C/min under liquid
nitrogen flow. Storage modulus (E′) and loss tangent (tan
δ) of each sample were recorded as a function of temper-
ature. For the scanning electron microscopy (SEM) mea-
surement, the rupture specimens after tensile testing were
coated with gold and then the morphological images was
performed at an accelerating voltage of 20 kV. The Shore
A durometer was used for the hardness test according to
ASTM D2240. Tensile properties were determined on a
Universal extensometer with 1000 N of load cell and the
testing speed of 500 mm/min. For the fuel resistance anal-
ysis, the vulcanized samples with initial weight of about
0.5 g were immersed in 70 ml of the selected automotive
fuel at room temperature for 7 days. The percentage of
swelling was calculated from Eq. (1).
Swelling ð%Þ ¼ ½ðWs −Wu Þ=Wu   100 ð1Þ
Where Wu and Ws represent the weight of unswollen and
swollen rubber, respectively.
Fig. 1 Mooney viscosity of EPDM/ENR compounds at different blend
ratios
Page 3 of 7 228
Fig. 2 Cure characteristics EPDM/ENR compounds at different blend
ratios
Results and discussion
The dependence of Mooney viscosity on EPDM/ENR blend
ratio is presented in Fig. 1. As can be seen, the viscosity of the
blends sharply decreases when ENR content is increased up to
50 %wt and then it is nearly constant. This is attributed to the
dilution effect from the substitution of the high viscosity of
EPDM portion by the low viscosity ENR portion. Moreover,
the higher break down of 50 % mole of polyisoprene in ENR
chains during mixing process could be expressed and lead to a
decrease in molecular weight compared to the saturated
EPDM chains [7]. Figure 2 displays the cure characteristics
of EPDM/ENR blends including scorch time, cure time and
cure rate index (CRI). It is found that scorch time does not
significantly change by increasing ENR content, while cure
time of the blends progressively decreases. The shorter cure
time and higher CRI occurred in ENR rich blend are arisen
from two main factors; (i) EPDM has fewer double bonds
leading to slower cure than ENR and (ii) ENR contains epoxy
rings in the molecule which could result in acid-catalyzed
epoxy ring opening reaction by sulfoxide and sulfenic acid
Fig. 3 Torque difference of EPDM/ENR compounds at different blend
ratios
228 Page 4 of 7
Fig. 4 Dynamic mechanical
properties of EPDM/ENR
vulcanizates at different blend
ratios. a Storage modulus and (b)
tanδ
via oxidative sulfur crosslinking reaction [16]. It is reported
earlier that the torque difference is directly propotiontional to
the crosslink density [6]. As can be seen in Fig. 3, the increas-
ing of torque difference value of EPDM/ENR blends is the
effect on increasing of crosslink density which results form
more content of ENR which can catalyst the crosslink reac-
tion. This means that the higher degree of crosslinking is
found in ENR-rich blends.
The dynamic mechanical analysis was used to examine the
compatibility of rubber blends and also measured the glass
transition temperature (Tg) of rubber. The effect of blend ratios
on the storage modulus (E′) and tan δ of the samples are
illustrated in Fig. 4. All curves in Fig. 4(a) shows three re-
gions: (i) a glassy high modulus region where the segment
mobility is restricted, (ii) a transition region where a drastic
drop in the E′ value with increasing temperature and (iii) a
rubbery region where a drastic decay in the modulus with
temperature [17]. EPDM shows a high modulus below its Tg
Fig. 5 SEM micrographs of tensile fractured surface of EPDM/ENR samples at different blend ratios; (a) 100/0, (b) 70/30, (c) 50/50, (d) 30/70 and (e)
0/100 %wt/wt
J Polym Res (2016) 23:228
followed by a substantial reduce in its magnitude around
−42 °C, whereas ENR shows the change in E′ around 0 °C.
It can be seen that the E′ values of the blends are intermediate
between those of pure components depending on blend ratios.
The temperature dependence of tan δ for EPDM, ENR and
their blends is depicted in Fig. 4(b). From the tan δ curves,
EPDM and ENR vulcanizates, respectively, show tan δmax at
about −42.5 and 0.2 °C corresponding to their glass transition
temperature (Tg). In addition, ENR shows maximum value of
tan δmax indicating its excellent damping behavior. For all
blend samples, there are two distinct tanδ peak of each phase
indicating the incompatible blends. As can be seen, the coin-
cident with the obvious increase in the ΔTg of the individual
rubber is believed to be caused by low cure compatibility and
the immiscibility between EPDM and ENR phases in the
blends. However, it is noteworthy that tan δmax of EPDM
phase is found to drastically decrease with increasing the con-
centration of ENR. This is because the additional ENR phase
J Polym Res (2016) 23:228
Fig. 6 Hardness of EPDM/ENR vulcanizates at different blend ratios
Fig. 7 Tensile strength of EPDM/ENR vulcanizates at different blend
ratios
is in glassy state at −42.5 °C which is Tg of EPDM, hence the
rigid epoxide of ENR cloud restrict the segmental mobility of
EPDM chains.
Figure 5 show the SEM micrographs of the tensile frac-
tured surface of EPDM/ENR samples with different blend
ratios. As can be seen in Fig. 5(a) and (d), the fresh EPDM
and ENR samples display the more homogenous surface mor-
phology compared to their blends. This indicates that these
Fig. 8 Percentage of swelling in (a) gasohol-91, (b) diesel and (c) engine oil of EPDM/ENR at different blend ratios
Page 5 of 7 228
rubbers had low miscibility with each other. Especially, at
the blends containing 30 and 50 %wt of ENR, the dispersed
particles are large with irregular shapes, moreover some voids
are presented. It might be due to a lack of interfacial interac-
tion between the filler-rubber and rubber-rubber. This result
can be supported by the Tg shift from dynamic mechanical
properties. However, more homogeneous phase dispersion
appears when ENR component in the blend is in excess (see
Fig. 5(c)).
The mechanical properties, in term of hardness and tensile
strength of EPDM/ENR blends are shown in Figs. 6 and 7,
respectively. For the effect of blend ratios, the hardness in-
creases with increasing ENR content. Since ENR contains
oxirane groups on its structure, higher stiffness would be more
pronounced in ENR-rich blends. Also, an increase in crosslink
density of the blends with increasing ENR content causes an
increase of hardness. However, it could be notice that the
strength of the blends in this study was not depended on de-
gree of crosslinking. As can be seen in Fig. 7, the tensile
strength of EPDM vulcanizate is found to be 8.21 MPa, while
ENR vulcanizate is 10.41 MPa. After blending, a negative
deviation from rule of mixtures in terms of strength is achieved
which is an indication of immiscible of EPDM/ENR blends as
discussed previously. Hence, the strength of the blends might
be enhanced by incorporating the third component to act a
compatibilizer such as maleic anhydride grafted polybutadiene
(PB-g-MAH) between EPDM and ENR in the further study.
The swelling behavior of EPDM, ENR and 50/50
EPDM/ENR blends in selected automotive fuels as a function
of immersion time are compared in Fig. 8. It is found that, the
percentage of swelling tends to increase with increasing im-
mersion time and the rate of swelling depends on the nature of
each automotive fuel. In term of effect of automotive fuel
types, the percentages and rate of swelling in gasohol-91 are
much higher than those in diesel and engine oils, respectively.
This is because engine oil is larger molecular size and higher
viscosity than those of diesel and gasohol-91, respectively.
This result implies that the molecular size and viscosity of fuel
228 Page 6 of 7
Fig. 9 Percentage of swelling in selected automotive fuels of
EPDM/ENR samples at different blend ratios
will reflect to the penetration ability into the blends [18]. After
interval of immersion time, it is interesting to note that the
percentage of swelling of EPDM in diesel and engine fuels
is greater than that of ENR. The effect of blend ratio on swell-
ing degree is displayed in Fig. 9. Normally, the higher degree
of crosslink density in rubber vulcanizates, a result in lower
degree of oil penetration into rubber phases occurred. In this
interesting in this blends that, for all selected automotive fuels,
the swelling of EPDM/ENR blends in diesel and engine fuels
are found to decrease with increasing ENR content, while
those in gasohol-91 increased. The swelling behaviors in die-
sel and engine fuels of EPDM/ENR blends are clearly in good
agreement with degree of crosslinking which confirm by
ODR results, as previously shown in Fig. 3. On the other
hand, the greater swelling degree in gasohol-91 of ENR-rich
blends was observed, even though having better crosslink
density. This is because of gasohol-91 containing 10 % etha-
nol blend with conventional gasoline. Therefore, these small
polar components in gasohol-91 were penetrated in ENR eas-
ily than diesel and engine fuels which composed of entire
hydrocarbons [19]. Owing to the differences in polarity of
automotive fuels and rubbers, here we show, for the first time,
that weight swelling of EPDM/ENR vulcanizates decreased in
diesel and engine oils, but increased in gasohol-91 with in-
creasing in ENR content.
Conclusion
Taken as a whole, the cure characteristics, automotive fuel
resistance and mechanical and dynamic properties of
EPDM/ENR blends containing hybrid fillers are depended
on their blend composition and degree of compatibility. The
results reveal that increasing ENR content in the blends gives
the reduction in Mooney viscosity and cure time. However,
the cure rate, degree of crosslinking and hardness are found to
J Polym Res (2016) 23:228
increase with increasing ENR content. Unfortunately, tensile
strength of the blends does not follow the mixture rule such
that the tensile strength slightly reduces with increasing ENR
content up to 50/50 EPDM/ENR ratio and further increase in
ENR content results in an increase of tensile strength. The
reduction in strength of the blends is believed to be caused
by low cure compatibility and the immiscibility between
EPDM and ENR phases in the blends which is coincident with
the obvious increase in the ΔTg of the individual rubber. The
resistances to diesel and engine oils are found to increase with
increasing ENR content in the blends, while the resistance to
gasohol-91 shows the opposite trend, revealing the relation-
ship between fuel resistance and blend ratios of EPDM/ENR
based on their chemical nature. This finding is expected to
have a benefit in terms of versatile selection of the different
polarity of fuels matching with various blend ratios of
EPDM/ENR. The obtaining materials is feasible with interest-
ing fuel resistance properties for some rubber parts in automo-
tive applications.
Acknowledgments The financial support from the Thailand Research
Fund (Grant No. RDG5650068) is gratefully acknowledged. The author
would like to acknowledge the facility support from the Faculty of
Science, Ubon Ratchathani University.
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