Research Article

Received: 5 June 2008, Revised: 6 August 2008, Accepted: 13 August 2008, Published online in Wiley InterScience: 17 November 2008

(www.interscience.wiley.com) DOI: 10.1002/pat.1293

Reinforcement of compatibilized NR/NBR

blends by fly ash particles and
precipitated silica
C. Kantala a, E. Wimolmala a, C. Sirisinha b and N. Sombatsompopa *
Effects of precipitated silica (PSi) and silica from fly ash (FA) particles (FASi) on the cure and mechanical properties
before and after thermal and oil aging of natural rubber (NR) and acrylonitrile–butadiene rubber (NBR) blends with
and without chloroprene rubber (CR) or epoxidized NR (ENR) as a compatibilizer have been reported in this paper. The
experimental results suggested that the scorch and cure times decreased with the addition of silica and the compound
viscosity increased on increasing the silica content. The mechanical properties for PSi filled NR/NBR vulcanizates were
greater than those for FASi filled NR/NBR vulcanizates in all cases. The PSi could be used for reinforcing the NR/NBR
vulcanizates while the silica from FA was regarded as a semi-reinforcing and/or extending filler. The incorporation of
CR or ENR enhanced the mechanical properties of the NR/NBR vulcanizates, the ENR being more effective and
compatible with the blend. The mechanical properties of the NR/NBR vulcanizates were improved by post-curing
effect from thermal aging but deteriorated by the oil aging. Copyright ß 2008 John Wiley & Sons, Ltd.

Keywords: silica; nitrile rubber; mechanical properties; reinforcement; natural rubber

INTRODUCTION
Acrylonitrile–butadiene rubber (NBR) is a copolymer of acryloni-
trile and butadiene which has a very good resistance to
hydrocarbon oil. Polarity of NBR can be adjusted, depending
on acrylonitrile content, to suit the applications of final rubber
products; the greater the acrylonitrile content the higher the oil
resistance. Due to molecular restriction, the glass transition
temperature (Tg) of NBR shifts a the higher temperature when the
acrylonitrile content is increased. Due to the absence of
strain-induced crystallization, unfilled NBR vulcanisate suffers
from its low mechanical properties. In contrast, natural rubber
(NR) is a non-polar rubber which has very good mechanical
properties as a result of formation of strain-induced crystal-
lization at high deformation strains. Compared to NBR, NR is less
expensive and, therefore, a blending of NR with NBR is usually
carried out for cost reduction of the final products requiring
inherent NBR properties. It has been reported[1–3] that one of the
important factors controlling oil resistance in unfilled blends of
polar rubber with NR is phase morphology, i.e., the smaller the NR
dispersed phase size the higher the resistance to hydrocarbon oil
of blends. Incorporation of suitable additives could improve the
phase compatibility of polar/non-polar rubber blends to some
extent via an alteration in interfacial properties and/or bulk shear
viscosity.[2,4–6] Previous work on NR/NBR blends[2] suggested that
reduction in the phase morphology of NR/NBR blends enhanced
the phase compatibility and this could be achieved by the use of
compatibilizers. Examples of compatibilizers used in NR/NBR blends
include maleated ethylene propylene diene rubber (EPDM-g-MA),
maleated ethylene octene copolymer (EOR-g-MA)[2], and poly-
chloroprene rubber (CR).[4]
Silica filler is one of the widely known reinforcing fillers for
rubber products and usually applicable to light-colored rubber
448
products. The silica filler possesses a small primary particle size
which gives rise to noticeably high reinforcing efficiency as
compared to other non-black fillers. Since precipitated silica (PSi)
contains a large amount of silanol groups (Si–OH) on its surfaces,
it can be considered as a highly polar and reactive filler.[7] Many
published works have studied the silica–rubber interaction and
its influences on properties of rubbers via primary chemical
bonds with functionalized polymers, such as chlorosulfonated
polyethylene (CSM),[8] epoxidized NR (ENR),[9] carboxylated nitrile
rubber (XNBR),[10] chloroprene rubber (CR)[11,12], and chlorinated
polyethylene (CPE).[5,13] Apart from the PSi, the silica from natural
resources, namely, rice husk ash, and fly ash (FA) received from
thermal power plant stations has recently gained interest.[14–23] It
has been reported[14–16,21–24] that a natural silica provides good
mechanical properties, particularly, dynamic mechanical proper-
ties and compression set if suitably treated with silane coupling
agents. Thongsang and Sombatsompop[15] suggested that FA
contained approximately 40–45 wt% of silica with similar
silanol groups on its surfaces. When added to NR[14–15] or
* Correspondence to: N. Sombatsompop, Polymer Processing and Flow (P-PROF)
Group, School of Energy, Environment and Materials, King Mongkut’s Univer-
sity of Technology Thonburi (KMUTT), Bangmod, Thungkru, Bangkok 10140,
Thailand.
E-mail: narongrit.som@kmutt.ac.th
a C. Kantala, E. Wimolmala, N. Sombatsompop
Polymer Processing and Flow (P-PROF) Group, School of Energy, Environment
and Materials, King Mongkut’s University of Technology Thonburi (KMUTT),
Bangmod, Thungkru, Bangkok 10140, Thailand
b C. Sirisinha
Rubber Research Unit (RTU), Faculty of Science, Mahidol University, Salaya
Campus, Salaya, Nakornprathom 10400, Thailand

Polym. Adv. Technol. 2009, 20 448–458 Copyright ß 2008 John Wiley & Sons, Ltd.
REINFORCEMENT OF NR/NBR BLEND BY SILICA
NR/styrene–butadiene rubber blends (NR/SBR blends),[16] the FA
provided higher and smaller magnitude of vulcanisate elasticity
and reinforcing effect, respectively, than the PSi at given filler
loading.
This paper was part of ongoing investigations into the use of
PSi and silica from fly ash (FA) particles (FASi) as reinforcing fillers
in rubber materials, the NR/NBR vulcanizate blend with and
without the addition of either CR or ENR compatibilizer being of
interest in this present work. The cure characteristics, mechanical
and morphological properties of the blend vulcanizates were
then monitored before and after thermal and hydraulic oil aging.
EXPERIMENTAL
Raw materials
NR (NR, STR20), supplied by Huay Chuan Co., Ltd (Bangkok,
Thailand), and acrylonitrile butadiene rubber (NBR) used in this
work, supplied by Zeon Advanced Polymix Co., Ltd. (Bangkok,
Thailand) under the trade name N32, with bound acrylonitrile
content 33.5%, were used in this work in the form of rubber blend
at a fixed NR/NBR blend ratio of 20:80. Two compatibilizers were
used in this work: CR, having Mooney viscosity of 44.5,was
supplied by Zeon Advanced Polymix Co., Ltd. (Bangkok, Thailand)
and Epoxidized NR (ENR-50) having Mooney viscosity of 80, was
supplied by Muang Mai Gutty Co., Ltd (Bangkok, Thailand).
Silicafrom FASi or commercially PSi was used as fillers in the NR/
NBR blend. The FASi were supplied by Mae Moh Power Station of
KNR Group Co., Ltd. (Lampang, Thailand). The characteristics
(dimensions, average particle size, shape and surface area,
density, and pH) of the FASi can be found in a previous work.[14]
Our previous results[14] suggested that the major component of
FA was SiO2 (
46%) and both FA and commercial silica had the
same functional groups (e.g. silanol and siloxane groups at wave
numbers of around 3400 and 1100 cm1, respectively). In this
work, the FASi were used in the as-received form (no extraction of
the silica being carried out), and the required silica (FASi) content
in the FASi added to the rubber compounds had to be calculated
based on the fact that there was 46 percent by weight (wt%) silica
in FASi since part of this study was concerned with the effect
of silica content on the properties of NR/NBR vulcanizate.
Bis-(3-triethoxysilylpropyl) tetrasulfane (Si69), [(C2H5O)3–Si–(CH2)3–
S4–(CH2)3–Si–(C2H5O)3], was used as a chemical coupling agent,
supplied by JJ-Degussa (Bangkok, Thailand) Co., Ltd. The Si69
content used in this work was fixed at 4.0 wt% of silica. The
Table 1. Vulcanizing recipes for silica filled NR/NBR vulcanizates
Ingredients
1. NBR (ACN33.4%)
2. NR (STR20)
3. CR or ENR-50
4. Zinc oxide (ZnO)
5. Stearic acid
6. TMTD (tetramethylthiuram disulfide)
7. MBTS (2,20 -dithiobis (benzothiazole))
8. PSi or FASi
9. Si69
10. Sulfur (325 mesh)
Polym. Adv. Technol. 2009, 20 448–458 Copyright ß 2008 John Wiley & Sons, Ltd.
detailed procedures for surface treatment by Si69 can be found in
our previous studies.[15]
Sample preparation of NR/NBR blend
The formulations of the NR/NBR blend compounds with either FA
or commercial silicas, in parts per hundred rubber (phr), are listed
in Table 1. The compounding process was commenced by
masticating the NR and NBR at the required blend ratio on a
laboratory two-roll mill (Yong Fong Machinery Co., Ltd.,
Samutsakon, Thailand) for 5 min. The masticated NR/NBR was
then compounded with prepared chemicals and fillers as listed in
Table 1 on the two-roll mill for a further 30 min, the compound
being then kept at 258C with 50% humidity prior to further use.
The resultant NR/NBR compound was then compression-molded
to a 90% cure using a hydraulic press (LAB TECH Co., Ltd., Bangkok
Thailand) at 170 kg/cm2, using 1608C cure temperature, in order
to obtain vulcanized rubber. The cure time used for any individual
compound was pre-determined by an Oscillating Die Rheometer
(Model ODR GT 7070-S2, GOTECH Testing Machine, Inc., Taiwan).
Characterizations
Cure and viscosity characteristics
Scorch time and cure time values of the NR/NBR blend
compounds were assessed by an Oscillating Die Rheometer
(Model ODR GT 7070-S2, GOTECH Testing Machine, Inc., Taiwan)
using a test temperature of 1608C. Complex viscosity of the NR/
NBR compounds under oscillatory shear flow was measured
using the Rubber Process Analyzer (RPA2000, Alpha Technologies,
USA) with the frequency sweep test. The test temperature used
was 1008C.
Mechanical properties
Tensile properties of NR/NBR composites were monitored in
terms of tensile modulus, tensile strength, and elongation at
break, according to ASTM D412 (2006) using dumbbell-shaped
samples, the tests being carried out using the universal testing
machine Model Autograph AG-I, Shimadzu (Tokyo, Japan). The
tensile test speed used was 500 mm/min. Tear strength was
determined according to ASTM D624 (2007) using angle
specimens (die C) and a Shimadzu tear strength testing machine.
Both tensile and tear properties used a testing speed of 500 mm/
min. A hardness durometer (Shore A) Model 475, PTC instruments
Function Content (phr)
Matrix 80
Matrix 20
Compatibilizer 5
Activator 2.5
Activator 0.75
Accelerator 1.25
Accelerator 0.35
Reinforcing filler Varied 0, 15, 30, 45
Coupling agent 4 wt% Of silica
Crosslinker 1
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 C. KANTALA ET AL.

(MA, USA), was used for hardness tests, the test conditions being
in accordance with ASTM D 2240 (2003).
Thermal and oil aging
The silica filled NR/NBR compounds were conditioned at 708C for
168 hr in an oven according to ASTM D573-04 (2004) and the
property changes before and after the thermal aging were then
assessed. The hydraulic oil aging effect was studied through
ASTM D471 (2006). The silica filled NR/NBR was immersed in
hydraulic oil (ISO46M PENNZOIL) at 1258C for 70 hr.
SEM studies
Failure and compatibilization mechanisms of NR/NBR blends
were investigated using a JEOL (JSM-6400) SEM machine at 15 kV
accelerating voltage with Back scattering electron (BSE). The
fractured surfaces of the blend were prepared by immersion in
liquid nitrogen, the test samples being surface-coated with
osmium tetroxide. The experimental procedure can be obtained
elsewhere.[25]
contents of silica fillers (PSi and FASi) and compatibilized by either
CR or ENR. Considering the PSi filled NR/NBR compounds, it was
found that increasing silica content resulted in decrease in scorch
and cure times for both non-compatibilized and compatibilized
NR/NBR compounds. The decrease in scorch time involved an
increased viscosity of the rubber blend compound with presence
of silica filler, which would then result in a change in the thermal
history of the blend compound leading to lower activation
energy for curative dissociation. The addition of CR or ENR
compatibilizer had no effect on the scorch and cure times.
Comparing the cure properties of the rubber filled with PSi and
FASi, it was found that the effects of silica and compatibilizer
loadings on the changing trends of the scorch and cure times and
the torque difference for the FASi filled NR/NBR compounds were
very similar to those for the PSi filled NR/NBR compounds.
However, the cure time for given silica content and compatibilizer
for the FASi filled NR/NBR compounds was lower. This may be due
to the presence of metal oxides in the FASi acting as the cure
activators during the vulcanization reaction, and thus activating
the vulcanization process of the filled NR/NBR compounds.

RESULTS AND DISCUSSION Rheological behavior

Cure and rheological characteristics of NR/NBR compounds
Cure characteristics
Table 2 shows the cure characteristics (scorch and cure times and
torque difference) for NR/NBR compounds filled with different
Figure 1 shows the relationship between complex viscosity and
frequency for NR/NBR blends compatibilized by either CR (Fig. 1a)
or ENR (Fig. 1b) at 5 phr for various PSi loadings. It can be seen
that as the PSi content was increased the complex viscosity
increased due to the rigidity of the silica for both compatibilization

Table 2. Cure characteristics for NR/NBR vulcanizates with and without CR or ENR compatibilizer for different loadings of silica fillers

Cure characteristics

Filler Silica Scorch time 90% Cure time Torque difference

system Compatibilizer content (phr) (min:sec) (min:sec) (dN-m)

PSi No compatibilizer 0 3:02 6:08 38.5

15 2:24 4:56 52.4
30 1:56 4:30 64.6
45 1:43 4:35 82.2
CR at 5 phr 0 3:07 6:38 39.2
15 2:23 5:22 53.3
30 2:14 5:07 67.4
45 1:45 4:41 80.4
ENR at 5 phr 0 2:48 6:03 39.6
15 2:35 5:26 52.5
30 2:10 4:48 64.4
45 1:50 4:15 74.1
FASi No compatibilizer 0 3:02 6:08 38.5
15 2:53 4:36 44.1
30 2:36 4:12 47.5
45 2:09 3:48 51.7
CR at 5 phr 0 3:07 6:38 39.2
15 2:37 4:39 52.5
30 2:18 4:19 60.9
45 2:03 3:50 69.2
ENR at 5 phr 0 2:48 6:03 39.6
15 2:33 4:39 49.3
30 2:13 4:00 59.8
45 1:54 3:19 69.3
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REINFORCEMENT OF NR/NBR BLEND BY SILICA

Figure 1. Complex viscosity as a function of test frequency for NR/NBR blend compatibilized by either CR (Fig. 1a) or ENR (Fig. 1b) for various PSi
contents.

systems, and a high filler–filler interaction of the PSi particles. The
addition of CR compatibilizer had no effect on the viscosity
whereas that of ENR compatibilizer enhanced the viscosity of the
blend. This suggests that the ENR performed better compatibility
than the CR, which gave better molecular interaction between
the NR and NBR molecules. This claim was also supported by
Mariamma et al.[26] Another reason for the increase in blend
viscosity due to the addition of ENR was the high viscosity of the
ENR itself as compared with the viscosities of NR and NBR phases.
The complex viscosity was observed to decrease with increasing
test frequency in a psuedoplastic character. Figure 2 shows the
effect of silica from FASi on the complex viscosity change of the
FASi filled NR/NBR blend compatibilized with either CR or ENR at
5 phr. The changes in the complex viscosity by the addition of
silica and compatibilizer for the FASi filled NR/NBR compounds
were again similar to those for the PSi filled NR/NBR, although the
magnitude of the viscosity changes for FASi filled NR/NBR
compound was less. This may result from the fact that FASi had
lower filler–filler interaction via hydrogen bond as a result of
lower numbers of hydroxyl groups on its surfaces.[24]
Mechanical and morphological properties of NR/NBR
vulcanizates and aging effect
Figure 3 shows the tensile modulus at 100% elongation for NR/
NBR vulcanizates with and without CR or ENR compatibilizer for
different Si69-treated PSi contents before and after thermal and
hydraulic oil aging. It was observed that increasing PSi loading

Figure 2. Complex viscosity as a function of test frequency for NR/NBR blend compatibilized by either CR (Fig. 1a) or ENR (Fig. 1b) for various FASi
contents.
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 C. KANTALA ET AL.

Figure 3. Effect of Si69-treated PSi loading on tensile modulus at 100% elongation for the NR/NBR vulcanizates with and without CR or ENR
compatibilizer before and after thermal and hydraulic oil aging.

resulted in a progressive improvement of the tensile modulus of
the NR/NBR vulcanizates as expected, which could be attributed
to the dilution effect in association with the cure promotion
phenomenon as illustrated from the results of torque difference
given in Table 2. The tensile modulus of the blend was higher
after the heat aging, this being expected because of thermal
post-curing effect resulting in the increase in crosslink density.[16]
Immersion of the treated PSi filled NR/NBR vulcanizates in
hydraulic oil at 1258C for 70 hr did not affect the tensile modulus
significantly, probably due to the counter-balancing effects of
post-curing and plasticizing effects. Considering the effect of
compatibilizer type, it was found that the addition of ENR gave
slightly higher tensile modulus than that of CR, confirming that
ENR was more effective for compatibilizing the NR and NBR as
already mentioned. The changing trend of the tensile modulus as
a function of silica content and thermal and oil aging for the FASi
filled NR/NBR (Fig. 4) was similar to that for the PSi filled NR/NBR,
but the sensitivity of the modulus change to the silica loading in
the FASi filled NR/NBR was lower.
Figure 5 shows the tensile strength of the NR/NBR vulcanizates
with and without CR or ENR compatibilizer for different
Si69-treated PSi contents before and after thermal and hydraulic
oil aging. Similar to tensile modulus results, the tensile strength of
the NR/NBR vulcanizates increased with increasing PSi content.
Apart from the silica reinforcing effect, it could be explained by
the phase morphology of the blend as given in Fig. 6. It can be
seen that the NR phase (bright) became smaller within the NBR
phase (dark) when the PSi was loaded. The reduction of the
rubber phase size was probably caused by the increase in the
blend viscosity (as shown in Fig. 1) by the addition of silica. If this
was the case, the shearing stress during the compounding would
be higher and reduced the phase size which led to higher surface
area for both higher NR–NBR and silica–rubber interactions.
The molecular interactions between the NR/NBR blend and

Figure 4. Effect of Si69-treated FASi loading on tensile modulus at 100% elongation for the NR/NBR vulcanizates with and without CR or ENR
compatibilizer before and after thermal and hydraulic oil aging.
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REINFORCEMENT OF NR/NBR BLEND BY SILICA

Figure 5. Tensile strength for NR/NBR vulcanizates with and without CR or ENR compatibilizer for different Si69-treated PSi contents before and after
thermal and hydraulic oil aging.

Si69-treated PSi and the compatibilizer (CR or ENR) are illustrated
in Fig. 7. It can be seen that both compatibilizers exhibited
polar–polar interaction and physical entanglement with NBR
and NR phases whereas the silica formed ether linkages of Si69
and –OH groups on PSi, and –C–S– linkages by the reactive sites
on the NBR molecules with Si69.[16] Figure 4 also illustrates the
effects of thermal and hydraulic oil aging on the tensile strength
of the NR/NBR blend. A slight increase in the tensile strength after
thermal aging (708C) was caused by the post-curing effect while a
considerable drop in the tensile strength after hydraulic oil aging
(1258C) resulted from thermal degradation of non-oil resistant NR
phase along with the plasticizing effect, which decreased the
magnitude of molecular entanglement. Figure 8 indicate that the
tensile strength decreased by the presence of silica from FASi,
and the tensile strength remained unchanged as the FASi content
was increased up to 45 phr. The differences in reinforcement
levels between the PSi and FASi fillers were associated with a
number of reasons including (a) a number of hydroxyl groups, (b)
particle size, and (c) dispersion level. Work by Thongsang et al.[27]
suggested that the number of hydroxyl groups for reacting with
the rubber via Si69 in the PSi was greater than that in the FASi,
and the particle size of PSi was much smaller than that of FASi.
That is why the PSi filler would give greater reinforcement in the
rubber matrix. The dispersion level of the FASi particles in NR/NBR

Figure 6. SEM micrographs of the fractured surfaces of NR/NBR vulcanizates with and without CR or ENR compatibilizer for Si69-treated PSi 45 phr
(3000): (a) no-compatibilizer; (b) CR 5 phr; (c) ENR 5 phr; (d) PSi 45 phr; (e) CR 5-PSi 45 phr; (f ) ENR 5-PSi 45 phr.
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 C. KANTALA ET AL.

Figure 7. A chemical reaction of Si69-treated silica and compatibilizer in NR/NBR blend. (a) ER and (b) ENR compatibilizer.

matrix could be considered using the SEM micrographs of
fractured surfaces of FASi filled NR/NBR vulcanizates as given in
Fig. 9, which reveals that the large FASi particles yielded a poor
dispersion within the NR/NBR matrix. The poor dispersion was
probably caused by the breakage of large FASi aggregates into
small primary particles whose surface were not chemically
treated by Si69 and this increased filler–filler interaction among
FASi primary particles.[27]
Figure 10 shows the ultimate elongation of the NR/NBR
vulcanizates with and without CR or ENR compatibilizer for
different Si69-treated PSi contents before and after thermal and
hydraulic oil aging. The elongation at break increased with
454
loading 15 phr PSi, but started to decrease at higher PSi loading.
The increase in the elongation at break was due to silica
reinforcement as discussed in Fig. 7, whereas the decrease in
the elongation may be associated with an incomplete surface
treatment of the PSi by Si69 during the experiment.[28] Since the
surface treatment of PSi by Si69 was carried out by spraying
the Si69 onto the silica powder only the silica on the surface had
compete surface treatment. The silica particles at the bottom of
the high-speed mixer may not be in contact with the Si69. The
reduction of elongation after thermal aging was caused by the
post-curing effect while that after hydraulic oil aging resulted
from the thermal degradation of non-oil resistant NR phase. It

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REINFORCEMENT OF NR/NBR BLEND BY SILICA

Figure 8. Tensile strength for NR/NBR vulcanizates with and without CR or ENR compatibilizer for different Si69-treated FASi contents before and after
thermal and hydraulic oil aging.

should be noted that the changes in elongation at break (the
results not shown) for the FASi filled NR/NBR vulcanizates were
similar to those in the tensile strength shown in Fig. 8.
Figure 11 illustrates the tear strength of the NR/NBR
vulcanizates with and without compatibilizer for different PSi
loading before and after 708C thermal and 1258C hydraulic oil
aging. It was observed that the tear strength of NR/NBR
vulcanizates was improved by the addition of silica as expected.
The addition of CR or ENR compatibilizer greatly enhanced the
tear strength, and again this could be reasoned using the SEM
micrographs in Fig. 6. The effect of thermal and hydraulic oil
aging on the tear strength of NR/NBR vulcanizates was similar to
that on the tensile strength. The tear strength of the FASi filled
NR/NBR vulcanizates is given in Fig. 12. It can be seen that
although the changing trend of the tear strength as a function of
FASi loading was similar to that of PSi loading, the tear strength
values by the FASi were much lower than those by the PSi. The
lower magnitude of the reinforcement provided by FASi was
believed to be caused by the larger particle size along with the
poor dispersion of the FASi particles as previously mentioned.
Figures 13 and 14 show the effects of PSi and FASi loadings on
hardness for NR/NBR vulcanizates with and without compati-
bilizer before and after thermal and hydraulic oil aging,
respectively. The hardness of NR/NBR vulcanizates increased

Figure 9. SEM micrographs of the fractured surfaces of NR/NBR vulcanizates with and without CR or ENR compatibilizer for Si69-treated FASi 45 phr
(3000): (a) No-compatibilizer; (b) CR 5 phr; (c) ENR 5 phr; (d) FAS 45 phr; (e) CR 5-FAS: 45 phr; (f ) ENR 5 FAS: 45 phr.
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 C. KANTALA ET AL.

Figure 10. Elongation at break for NR/NBR vulcanizates with and without CR or ENR compatibilizer for different Si69-treated PSi contents before and
after thermal and hydraulic oil aging.

Figure 11. Tear strength for NR/NBR vulcanizates with and without CR or ENR compatibilizer for different Si69-treated PSi contents before and after
thermal and hydraulic oil aging.

Figure 12. Tear strength for NR/NBR vulcanizates with and without CR or ENR compatibilizer for different Si69-treated FASi contents before and after
thermal and hydraulic oil aging.
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REINFORCEMENT OF NR/NBR BLEND BY SILICA

Figure 13. Hardness for NR/NBR vulcanizates with and without CR or ENR compatibilizer for different Si69-treated PSi contents before and after thermal
and hydraulic oil aging.

Figure 14. Hardness for NR/NBR vulcanizates with and without CR or ENR compatibilizer for different Si69-treated FASi contents before and after
thermal and hydraulic oil aging.

with silica content, the results corresponding well to the tensile
modulus results. It was also found that the thermal aging slightly
increased the hardness while the hydraulic oil aging decreased
the hardness of the vulcanizates in both silica filler systems.
CONCLUSIONS
In this work, cure characteristics and mechanical and morpho-
logical properties of silica filled NR/NBR vulcanizates with and
without compatibilization were studied before and after thermal
and oil aging. It was found that the addition of silica into NR/NBR
compounds caused the decrease in scorch and cure times with
higher compound viscosity, the decreasing effect on cure time of
the silica from FASi being more pronounced. The incorporation of
CR or ENR compatibilizer had no effect on the cure characteristics
of the blend vulcanizates. The PSi could be used for reinforcing
the NR/NBR vulcanizates while the silica from FA was regarded as
semi-reinforcing and/or extending filler. Most of the mechanical
properties (modulus, tensile and tear strengths, and hardness) of
the vulcanizates increased with increasing silica content. The
reinforcing effect could be enhanced by the incorporation of ENR
compatibilizer. The overall mechanical properties for the PSi filled
NR/NBR vulcanizates were superior to those for FASi filled NR/NBR
vulcanizates. Thermal aging caused the increases in the overall
mechanical properties of the NR/NBR vulcanizates except for the
elongation at break while the oil aging deteriorated the
vulcanizate properties.
Acknowledgements
The authors thank the Commission on Higher Education (Centre
for Utilizations of Polymers and Natural Resources, CUP-NATURE)
and the Thailand Research Fund together with Compound Pro-
fessional Co., Ltd. (RDG4850076) for financial support throughout
this work.
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REFERENCES
[1] C. Sirisinha, S. Baulek-Limcharoen, J. Thunyarittikorn, J. Appl. Polym.
Sci. 2001, 82, 1232–1237.
[2] C. Sirisinha, S. Limcharoen, J. Thunyarittikorn, J. Appl. Polym. Sci.
2003, 89, 1156–1162.
[3] C. Sirisinha, P. Sae-oui, J. Guaysomboon, J. Appl. Polym. Sci. 2003, 90,
4038–4046.
[4] A. J. Tinker, Blends of Natural Rubber with Specialty Synthetic Rubbers,
in Industrial Composites Based on Natural Rubber. Malaysian Rubber
and Development Board, Kuala Lumpur, 1998, 103–113.
[5] S. Pattanawanidchai, P. Sae-oui, C. Sirisinha, J. Appl. Polym. Sci. 2005,
96, 2218–2224.
[6] J. Clarke, B. Clarke, P. K. Freakley, I. Sutherland, Plast. Rubber Compos.
2001, 30, 39–44.
[7] J. T. Byers, Rubber World 1998, 281, 38–47.
[8] A. Roychoudhury, P. P. De, N. K. Dutta, N. Roychoudhury, B. Haidar, A.
Vidal, Rubber Chem. Technol. 1993, 66, 230–241.
[9] S. Varughese, D. K. Tripathy, J. Appl. Polym. Sci. 1992, 44, 1847–1852.
[10] S. Bandyopadhyay, P. P. De, D. K. Tripathy, S. K. De, Rubber Chem.
Technol. 1996, 69, 637–647.
[11] S. S. Choi, J. Appl. Polym. Sci. 2002, 83, 2609–2616.
[12] P. Sae-oui, C. Sirisinha, U. Thepsuwan, K. Hatthapanit, Eur. Polym. J.
2006, 43, 185–193.
[13] N. Phewthongin, P. Sae-oui, C. Sirisinha, J. Appl. Polym. Sci. 2006, 100,
2565–2571.
458
www.interscience.wiley.com/journal/pat Copyright ß 2008 John Wiley & Sons, Ltd.
C. KANTALA ET AL.
[14] N. Sombatsompop, S. Thongsang, T. Markpin, E. Wimolmala, J. Appl.
Polym. Sci. 2004, 93, 2119–2130.
[15] S. Thongsang, N. Sombatsompop, Polym. Compos. 2006, 27, 30–40.
[16] N. Sombatsompop, E. Wimolmala, T. Markpin, J. Appl. Polym. Sci.
2007, 104, 3396–3405.
[17] Z. A. M. Ishak, A. A. Bakar, Eur. Polym. J. 1995, 31, 259–269.
[18] P. Saeoui, C. Rakdee, P. Thanmathorn, J. Appl. Polym. Sci. 2002, 83,
2485–2493.
[19] H. M. Da Costa, L. L. Y. Visconte, R. C. R. Nunes, C. R. G. Furtado, J. Appl.
Polym. Sci. 2002, 83, 2331–2346.
[20] L. Sereda, M. M. Lozpez-Gonzalez, L. L. Y. Visconte, R. C. R. Nunes,
C. R. G. Furtado, E. Riande, Polymer 2003, 44, 3085–3093.
[21] K. Garde, W. J. McGill, C. D. Woolard, Plast. Rubber Compos. 1999, 28,
1–10.
[22] N. A. N. Alkadasi, D. G. Hundiwale, U. R. Kapadi, J. Appl. Polym. Sci.
2004, 91, 1322–1328.
[23] S. Mishra, S. H. Sonawane, N. Badgujar, K. Gurav, D. Patil, J. Appl.
Polym. Sci. 2005, 96, 6–9.
[24] S. Thongsang, N. Sombatsompop, J. Macromol. Sci. Phys. 2007, B46,
825–840.
[25] C. Sirisinha, P. Saeoui, J. Guaysomboon, Polymer 2004, 45, 4909–4926.
[26] G. K. Mariamma, K. Jacob, K. Varkey, K. T. Thomas, N. M. Mathew,
J. Appl. Polym. Sci. 2002, 85, 292–306.
[27] S. Thongsang, N. Sombatsompop, A. Ansarifar, Polym. Adv. Technol.
2008, 19, 1296–1304.
[28] M. A. Ansarifar, R. Nijhawan, J. Rubber Res. 2000, 3, 169–184.
Polym. Adv. Technol. 2009, 20 448–458