Materials and Design 55 (2014) 664–673

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Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Effect of expanded graphite and modified graphite flakes

on the physical and thermo-mechanical properties of styrene
butadiene rubber/polybutadiene rubber (SBR/BR) blends
Asish Malas, Parthajit Pal, Chapal Kumar Das ⇑
Materials Science Centre, IIT Kharagpur, Kharagpur 721302, West Bengal, India

a r t i c l e i n f o a b s t r a c t

Article history: The aim of the present research work is to develop expanded graphite (EG) and isocyanate modified
Received 13 July 2013 graphite nanoplatelets (i-MG) filled SBR/BR blends, which can substitute natural rubber (NR) in some
Accepted 14 October 2013 application areas. The present study investigated the effect of i-MG on the physical, mechanical and
Available online 24 October 2013
thermo-mechanical properties of polybutadiene rubber (BR), styrene butadiene rubber (SBR) and SBR/
BR blends in the presence of carbon black (CB). Graphite sheets were modified to enhance its dispersion
Keywords: in the rubber matrices, which resulting in an improvement in the overall physical and mechanical
Blends
properties of the rubber vulcanizates. Compounds based on 50:50 of BR and SBR with 3 wt% nanofillers
Composites
Mechanical properties
with CB were fabricated by melt mixing. The morphology of the filled rubber blends was investigated by
Rubber wide angle X-ray diffraction (WAXD) and high resolution transmission electron microscopic (HR-TEM)
Thermal properties analyses. The intercalated and delaminated structures of the nanofiller loaded rubber blends were
observed. Scanning electron microscopic (SEM) analysis of the cryo-fractured surfaces of the rubber com-
pounds showed more rough and tortuous pathway of the fractured surfaces compared to the fractured
surfaces of the only CB loaded rubber composites. Filled rubber compounds exhibit increase in the DS
(torque difference) value, reduced scorch and cure time compared to their respective controls. Dynamic
mechanical thermal analysis (DMTA) of the filled rubber compounds shows an increase in the storage
modulus compared to the controls. Isocyanate modified graphite nanoplatelets (i-MG) containing rubber
compounds in the presence of CB showed an increase in the mechanical, dynamic mechanical, hardness,
abrasion resistance and thermal properties compared to the alone CB filled rubber vulcanizates.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction components but also on their physical structure [2]. Vulcanization

Recently, development of high performance tires having low
rolling resistance, good wear resistance and better wet grip at
the same time, is the ongoing direction of the tire industries. It is
customary to use a mixture of two or more elastomers to achieve
new polymeric composite materials with industrial application
and feasible utilization; since this idea is more susceptible and less
costly than developing a new polymer [1]. The exact reason to
prepare a blend of two elastomers is to associate two or more
desirable features of the individual vulcanized elastomers in a
single material. While these blends are apparently easy to be
obtained; in the case of certain blends, the result is often less sat-
isfactory than expected and can be less compared to the results
provided by the individual elastomers. The physical properties of
the blends depend not only on the properties of the individual
⇑ Corresponding author. Tel.: +91 3222 283978; fax: +91 3222 255303.
E-mail addresses: malasasish@gmail.com (A. Malas), chapal12@yahoo.co.in,
ckd@matsc.iitkgp.ernet.in (C.K. Das).
and compatibility are the two important factors must take into ac-
count when preparing the elastomeric blends [2]. The price of the
natural rubber (NR) has been increased and at the same time
polymeric materials synthesized from a single monomer have
not been able to fullfill the performance needs in many fields [3].
Styrene butadiene rubber (SBR) is a copolymer synthesized from
styrene and butadiene monomer, shows superior wear resistance,
heat aging, water resistance and gas tightness, but its adhesivity,
oil resistance and elasticity are not so good compared to the NR
[4–6].
High cis-polybutadiene rubber (BR) exhibit low glass transition
temperature value (105 °C) compared to the SBR and NR, which
permits it to show superior wear resistance and low rolling resis-
tance. Superior wear resistance and low rolling resistance of BR
contribute to the tires a good longevity and low fuel consumption.
As a result of low transition temperature of BR, the wet grip of the
tire is lowered that is why BR is always used in combination with
SBR or NR in the tire tread compounds [7].

0261-3069/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.matdes.2013.10.038
 A. Malas et al. / Materials and Design 55 (2014) 664–673
Because of its favorable properties, NR is consumed in large
extent in the aerospace, defense industry, heavy duty truck and
medical fields [8–10]. But taking the high cost of NR in concern
compared to synthetic rubbers, the attention is given to the utiliza-
tion of synthetic rubber blends like SBR/BR, SBR/NR blends, etc.,
which can partially replace NR. SBR/BR blends are always utilized
in the passenger car radial (PCR) tire tread compounds. Das et al.
successfully dispersed multiwalled carbon nanotubes (MWCNTs)
in the S-SBR/BR blends without damaging their unique properties
and observed improved mechanical properties compared to the
unfilled rubber [11]. Thermal degradation characteristics of a blend
have been utilized to identify SBR/BR blends from SBR based com-
posites by Amraee et al. [12]. Wu et al. prepared silica modified
SBR/BR blends by melt blending and noticed improved mechanical
properties of the blends [3]. Carbon black (CB), silica and layered
silicates are used as popular reinforcing fillers in both the academic
and industrial sectors for the rubber reinforcement. Thermody-
namics of the nanoscale filler dispersion in the different polymer
matrices can be interpreted by the help of entropic and enthalpic
factors, which confirms the positive or negative dispersion of
pristine or organically modified fillers [13–15]. The adsorption,
physiadsoption and intercalation of a considerable amount of sur-
face area of macromolecules introduce entropy loss. Therefore, the
dispersion of nanofillers requires adequate favorable enthalpic
contributions to overcome the entropy loss. Aiming for the devel-
opment of polymeric nanocomposites, Vaia and co-workers devel-
oped a lattice based model of polymer melt intercalation in
organically modified mica type silicates. They have calculated the
entropic and enthalpic contributions to the free energy of mixing
[13] and used this model to assess the compatibility of polystyrene
with alkylammonium modified silicates [14]. According to this lat-
tice based model, the entropic penalty of polymer confinement
may be compensated by the increased conformational freedom of
the surfactant chain as the layers separate. Balazs and coworkers
used numerical self-consistent field calculations (SCF) to investi-
gate the interactions between two closely spaced surfaces and
the surrounding polymer melt. They developed an analytical SCF
theory to model the interactions among the functionalized chains,
nonfunctionalized polymers, and the clay sheets. They observed
that the results obtained from the numerical and analytical SCF
models show good agreement on the behavior of the system
[15]. Natural graphite (NG) sheets exhibit similar layered structure
like organically modified clay but having very small interlayer
spacing. To increase the dispersion of NG in the different polymer
matrices, it is further modified to expanded graphite (EG), graph-
ene oxide (GO), etc. resulting in an increase in the interlayer spac-
ing of NG.
Now in recent days, expanded graphite (EG), graphene oxide
(GO) and graphene nanosheets (GNS) are partially exfoliated in
the different rubber matrices to increase their mechanical, electri-
cal, thermo-mechanical and physical properties [13–16]. Wang
and co-workers studied the effect of expanded graphite on the
overall properties of acrylonitrile butadiene rubber (NBR) (latex
compounding) and noticed considerable improvement in the
mechanical and dynamic mechanical properties of the rubber com-
posites [16]. Yang and co-workers investigated the effects of EG
and modified EG on the mechanical and functional properties of
NBR (latex compounding). They noticed improvement in the
respective properties of the filled composites [17]. Wang et al. syn-
thesized EG loaded NBR nanocomposites by both melt blending
and latex compounding, and observed better overall properties
for the nanocomposites prepared by latex compounding [18]. Zhan
and co-workers prepared NR/GNS composites by an ultrasonically-
assisted latex mixing technique. They observed superior mechani-
cal, dynamic mechanical properties and cure characteristics for the
GNS loaded rubber composites [19].
665
In the present investigation, EG/CB and modified graphite nano-
platelets (i-MG)/CB filled rubber composites based on BR, SBR and
SBR/BR (1:1) were synthesized by melt blending and characterized
looking for tire tread applications.
2. Experimental details
2.1. Materials
Emulsion styrene butadiene rubber (SBR) (Grade: 1502) con-
taining 23% styrene content and high cis-polybutadiene (BR:
KBR-01, nickel-catalyzed polybutadiene, cis content >94%) were
supplied from Korea Kumho Petrochemicals Co., Ltd.
Graphite Fine Powder (Extra Pure) was obtained from Loba Che-
mie Pvt. Ltd., Mumbai (India). Nitric acid (HNO3), Sulfuric acid
(H2SO4) and acetone were bought from Merck, India. 2,4-Toluene
di-isocyanate (TDI) and N,N-Dimethylformamide (DMF) were pur-
chased from Sigma–Aldrich, India. Carbon black, type: Intermedi-
ate Super Abrasion Furnace (ISAF), Grade: N234 (average particle
size 24–33 nm) was procured from Hi-tech carbon. Other com-
pounding additives like sulfur, zinc oxide, stearic acid and N-cyclo-
hexyl-2-benzothiazyl sulphenamide (CBS) were purchased from
Bayer (M) Sdn Bhd Malaysia.
2.2. Methods
2.2.1. Preparation of EG and isocyanate modified graphite sheets (i-
MG)
In the present work, EG was prepared from natural graphite
(NG) by well-known acid process combining with thermal exfolia-
tion [20]. To incorporate more number of polar groups on the sur-
face of EG, it was then further oxidized by H2SO4/HNO3 (3:1) at
90 °C for 12 h with vigorous stirring. A homogeneous suspension
of oxidized EG (2 g) in 100 mL dehydrated DMF was prepared in
a 100 mL three necked flask equipped with a magnetic stirring
bar under nitrogen atmosphere. TDI (2 g) was then added with
continuous stirring under nitrogen atmosphere at 80 °C for 24 h.
The reaction mixture was next poured into 200 mL of acetone to
coagulate the product. The resultant product (Isocyanate modified
graphite, i-MG) was then filtered and washed completely with
additional acetone. Lastly, the resulting product was dried at
100 °C under vacuum for 48 h [21].
2.2.2. Preparation of the rubber nanocomposites
The EG and i-MG containing SBR/BR composites in the presence
of CB were fabricated by melt blending. EG/CB and i-MG/CB with
other curatives were incorporated into the BR, SBR and SBR/BR
(1:1) blends in separate batches by melt blending in a laboratory
scale open two roll mixing mill (the speed ratio of the rotor was
1:1.4) at room temperature. The amount of nanofillers (wt%) with
respect to rubber was kept constant at 3. The compositions of the
rubber compounds are represented in Table 1. Vulcanization of the
rubber composites was carried out in a compression molding ma-
chine at 160 °C for an optimum cure time of 30 min.
3. Characterization techniques
Curing characteristics of the rubber composites were analyzed
in Monsanto Rheometer R-100 testing instrument at 160 °C with
3° arc for 60 min.
Wide angle X-ray diffraction (WAXD) analysis of EG, i-MG and
hybrid rubber compounds was done in Rigaku Miniflex Diffractom-
eter with Co Ka radiation at a generator voltage of 40 kV. The scan-
ning rate was 3°/min between 10° and 70°, chart speed 10 mm/2h,
current 20 mA and wavelength 0.179 nm at room temperature. The
666 A. Malas et al. / Materials and Design 55 (2014) 664–673

Table 1
Formulations of the rubber composites.

Ingredients Designation
BC SC SBC BEC SEC SBEC Bi–MC Si–MC SBi–MC
Content (wt%)
SBR 100 50 – 100 50 – 100 50
BR 100 – 50 100 – 50 100 – 50
EG – – – 3 3 3 – – –
i-MG – – – – – – 3 3 3
Stearic acid 2 2 2 2 2 2 2 2 2
CBS 1 1 1 1 1 1 1 1 1
Zinc oxide 4 4 4 4 4 4 4 4 4
CB-ISAF (N234) 40 40 40 30 30 30 30 30 30
Sulfur 2 2 2 2 2 2 2 2 2
Processing oil 2 2 2 2 2 2 2 2 2

d-spacings of the EG, oxidized EG and i-MG were calculated from

the Bragg’s equations nk = 2d sin h.
The microstructures of the rubber nanocomposites were
studied by high resolution transmission electron microscope (HR-
TEM, JEOL 2100). For HR-TEM analysis, ultra thin cross sections
of the specimens were cut by using Leica Ultra Cut UCT Ultra
microtome instrument equipped with a diamond knife.
Dynamic mechanical thermal analysis (DMTA) of nanocompos-
ites was carried out by using a TA instrument DMA 2980 model in
tension mode at a constant frequency of 1 Hz, a strain of 0.1%, in
the temperature range of 110 °C to +80 °C and at a heating rate
of 3 °C/min.
Mechanical properties of the SBR/BR based nanocomposites
were done by using a Universal tensile testing machine (Hounsfield
H 10KS) under ambient conditions (at 25 ± 2 °C). Tensile strength
and tear strength were tested according to ASTM: D412-06ae2
and ASTM: D624-00 (2012) standard respectively. For each set, five
samples were tested and the results given were the average values.
The measured length of the sample was 25 mm, and the speed of
jaw separation was 500 mm/min. The hardness of the rubber com-
posites was measured by Shore A hardness tester as per ASTM:
D2240-05(2010) standard. Fig. 1. FT-IR spectra of NG, EG, o-EG and i-MG.
DIN abrasion test of the nanocomposites was performed by the
DIN abrasion tester in order to analyze the average abrasion mass
loss% of the rubber compounds (ASTM: D5963-04 (2010)).
ACO vibration mode of the keto form and OAH deformation
Scanning electron microscopic (SEM) analysis of the cryo-frac-
respectively [22,23]. The pronounced peaks at 2956 cm1,
tured surfaces of the nanocomposites was carried out in Carl ZEISS
2860 cm1 (o-EG) and 1719 cm1 (o-EG) were due to CAH stretch-
EVO 60 scanning electron microscope. The fractured samples were
ing and AC@O group stretching of ACOOH group respectively
gold coated in prior before SEM analysis.
[24,25]. The considerable peaks at 1389 cm1 and 1257 cm1
Energy dispersive X-ray spectroscopic (EDS) analysis of EG, oxi-
(o-EG) might be due to CAO and AOH of ACOOH groups [26].
dized EG and i-MG was done in energy dispersive X-ray (EDX)
The prominent peak at 1058 cm1 was due to CAOAC stretching
spectrometer (INCA) (OXFORD EDS detector) attached to Carl ZEISS
vibration [27]. Physical and chemical interactions between the
SUPRA 40 Field Emission Scanning Electron Microscope.
polymer and nanofillers were enhanced due to the presence of dif-
Thermo gravimetric analysis (TGA) of the nanocomposites was
ferent polar groups on the surface of EG and i-MG. The peak at
carried out in a DuPont TGA-2100 thermal analyzer in the temper-
1541 cm1 of i-MG was raised due to either amides or carbamates
ature range 30–700 °C with a heating rate of 10 °C/min.
esters and resembles to the coupling of the CAN stretching vibra-
FT-IR analysis of EG and i-MG was carried out from 650 cm1 to
tion with the CHN deformation vibration [28]. After the treatment
4000 cm1 range in Thermonicolet/Nexus 870 FT-IR spectrometer.
of o-EG with TDI, the peak at 3410 cm1 disappeared and a weak
peak at around 3300 cm1 corresponding to secondary amino
4. Results and discussion groups was raised indicating the consumption of hydroxyl groups
by isocyanate groups during modification and also the band at
4.1. FT-IR analysis 1719 cm1 disappeared followed by the appearance of new peaks
at 2340 cm1 (C@N@O asymmetric stretching) and 1650 cm1
FT-IR spectra of the EG, o-EG and i-MG synthesized from natural (amide carbonyl stretching mode) [29,30].
graphite (NG) flakes are represented in the Fig. 1. Further oxidation
of EG results in an increase in the number of polar groups such as 4.2. EDS analysis
hydroxyl (AOH), carboxylic acid (ACOOH) and epoxide on the
surface of the EG. The intense peaks at 3410 cm1 (o-EG), For further investigation to confirm the presence of different
1650 cm1 and 1391 cm1 (EG) were due to AOH stretching mode, elements (C, O and N) in the nanofillers, the bulk EDS analysis of
 A. Malas et al. / Materials and Design 55 (2014) 664–673 667

Fig. 2. EDX spectra of (a) EG, (b) o-EG and (c) i-MG.

Fig. 3. WAXD patterns of (a) NG, EG, o-EG and i-MG, (b) EG filled rubber composites and (c) i-MG filled rubber composites.

EG, o-EG and i-MG was carried out and shown in the Fig. 2. It can
be observed from the respective Figure that ‘O’ element was there
for the o-EG, which proves the presence of different ‘O’ containing
groups on the surface of o-EG. The presence of ‘O’ and ‘N’ elements
in the EDX spectra of i-MG indicated the isocyanate modification of
o-EG.
4.3. WAXD analysis
Fig. 3a shows the X-ray diffraction patterns of natural graphite
powder (NG), o-EG and isocyanate modified graphite (i-MG)
sheets. As shown in the Fig. 3a, NG flakes show (0 0 2) and (0 0 4)
diffraction peaks at 2h = 30.94° and 64.56° (Co Ka source),
668 A. Malas et al. / Materials and Design 55 (2014) 664–673
corresponding to the d-spacings of 0.335 nm and 0.168 nm respec-
tively. For o-EG, the (0 0 2) peak was observed at 2h = 29.83°, corre-
sponding to the basal spacing of 0.347 nm and at the same time the
respective peak was broadened with very less intensity compared
to the (0 0 2) peak of NG. The shifting of the (0 0 2) peak towards
lower 2h value indicates separation and partial exfoliation (incom-
plete exfoliation) of graphite sheets. Another two peaks, (1 0 0) and
(1 0 1) were appearing at 2h = 49.48° and 51.33° after thermal
expansion following the oxidation of EG, which correspond to the
2D in-plane symmetry along the graphene sheets [31,32]. For
i-MG, the (0 0 2) peak and the other peak’s positions were almost
same compared to the o-EG. Fig. 3b represents the WAXD patterns
of EG loaded rubber composites and it can be seen that the EG/rub-
ber composites exhibit an intense peak at 2h = 30.94°, correspond-
ing to the d-spacing of 0.335 nm. This peak was exactly same as
that observed for natural graphite flakes, which confirmed that
the graphite sheets were still in order and multilayer, and thus
retained their original basal spacing [33]. Therefore, it also demon-
strated that the processing technique used for the preparation of
rubber composites in this study was unable to exfoliate the EG
platelets in the rubber matrices completely. Fig. 3c displayed the
WAXD patterns of modified graphite nanoplatelets filled rubber
composites. It can be noticed that the intense peak of i-MG was
almost disappeared and broadened for the i-MG loaded rubber
composites, which indicated a uniform dispersion of i-MG in the
rubber matrices. A small halo and other peaks at around 2h = 22°,
37°, 40° and 42.5° were raised due to the amorphous rubbers
and other compounding ingredients respectively.
4.4. SEM analysis
To observe the dispersion, interfacial adhesion and reinforcing
mechanism of EG and i-MG in the different rubber composites,
the cryo-fractured surfaces of the rubber composites were ana-
lyzed by SEM. Fig. 4 represents the SEM images of the rubber com-
posites. It can be seen from the images that EG flakes were
randomly distributed in the different rubber matrix and the lateral
size of the EG was exposed for the loaded rubber composites pre-
pared by melt blending, which indicated moderate interfacial
bonding between EG and the rubber matrices. But for the i-MG
loaded rubber composites, the microstructure of the fractured sur-
faces displayed the close contact and high embedding of i-MG
flakes with rubber matrices, indicating a good interracial interac-
tion between i-MG and the rubber matrices. SEM images of the
EG and i-MG filled rubber compounds showed rough, tortuous
fractured surface and broad tear paths. It can be suggested that
EG and i-MG sheets were dispersed in the rubber matrix in the
presence of CB and changed the crack lines depending on their ori-
entation in the polymer matrices.
4.5. HR-TEM analysis
Fig. 5 shows the HR-TEM images of the EG and i-MG filled rub-
ber composites based on different synthetic rubbers. The dark lines
in the images dictate the presence of EG and i-MG nanosheets with
thickness in the nanometer range. It was seen from the images that
few EG sheets were agglomerated in the different rubber matrices
in the presence of CB, which was due to the utilization of direct
melt blending technique for the fabrication of the rubber compos-
ites and also due to minimum basal spacing of the EG sheets, which
restricts the rubber chains to enter the intergallery spaces. i-MG
flakes exhibit higher d-spacing compared to the EG. Therefore,
polymer chains can easily be intercalated into the gallery space
of i-MG flakes. i-MG/CB loaded rubber composites show intercala-
tion and partial exfoliation of i-MG sheets in the different rubber
matrices.
4.6. DMTA analysis
The effects of EG and isocyanate modified graphite (i-MG) on
the dynamic mechanical properties of BR, SBR and SBR/BR blends
were investigated by dynamic mechanical thermal analysis. The
temperature dependent storage modului (E0 ) and loss tangents
(tan d) of the rubber composites are represented in the Fig. 6a–d.
Both the elastic and viscous behaviors of the composite materials
affect the resulting strain in the samples due to the application
of an oscillating force. The storage modulus can be regarded as
the elastic modulus of the rubber composites and loss tangent is
interconnected to the energy drenched due to energy dissipation
as heat. It can be seen from the Fig. 6a and b that EG and i-MG
loaded SBR/BR composites in the presence of CB showed a drastic
increase in the storage modulus in a wide range of temperature
compared to the BR based nanocomposites. But, in comparison
with SBR based nanocomposites, SBR/BR based composites showed
an increase in the storage modulus only at very low temperature
region and then decrease in the storage modulus from low temper-
ature to a high temperature region, which was due to very low
transition temperature of BR. Homogeneous mixing of SBR with
BR and as well as good dispersion of nanofillers in the rubber blend
increases its stiffness, which resulting in an increase in the storage
modulus of the SBR/BR based nanocomposites. Fig. 6c and d
displayed the temperature dependent tan d curves of the various
rubber composites. Conventionally, the greater tan d value of the
rubber composites in the region of 20 to 10 °C can be accounted
to figure out the superior anti-skid properties of the rubber com-
posites under wet conditions and lower tan d value of the rubber
materials in the range of 50–60 °C indicates the low rolling resis-
tance of the rubber stuffs [34,35]. We can see from the respective
figures that the tan d values of the EG and i-MG filled SBR/BR based
composites in the region of 20 to 10 °C were higher than tan d
values of the only BR based nanocomposites. So, after the homoge-
neous mixing of SBR with BR in the presence of different nanofil-
lers, the anti-skid property under wet conditions of the BR
vulcanizates was significantly improved. At the same time, rolling
resistance of the SBR/BR based nanocomposites was lowered (low-
er tan d values of the SBR/BR based composites in the temperature
range of 50–60 °C) compared to the rolling resistance of SBR vulca-
nizates. EG/i-MG containing rubber composites in the presence of
CB showed superior storage modulus, antiskid properties and low-
er rolling resistance compared to the only CB loaded rubber com-
posites, which was due to the better interactions and interfacial
adhesion between i-MG sheets and the rubber matrices.
4.7. TGA analysis
Fig. 7a shows the thermo gravimetric curves of the graphite, EG,
o-EG and i-MG flakes. o-EG showed comparably less thermal sta-
bility than the EG, which was due to the degradation of number
of polar groups present on the surface of o-EG. The small weight
loss of o-EG around 200 °C was due to the decomposition of unsta-
ble oxygen containing functional groups present on the surface of
o-EG. Another partial weight loss around 700 °C can be attributed
to the subtraction of more stable oxygen functionalities of o-EG. In
comparison with o-EG, i-MG exhibits a maximum weight loss at
around 300 °C. The TGA curves of the different rubber composites
are represented in the Fig. 7b–d. It can be seen that the incorpora-
tion of nanofillers in the BR matrix, thermal stability of the EG/CB
(total-33 wt%) and i-MG/CB (total-33 wt%) filled BR composites
was increased compared to the thermal stability of the only CB
loaded (40 wt%) rubber composite. EG/i-MG containing SBR based
nanocomposites in the presence of CB showed a considerable
enhancement in the thermal stability compared to the only CB
(40 wt%) filled SBR compound. EG/CB and i-MG/CB filled SBR/BR
 A. Malas et al. / Materials and Design 55 (2014) 664–673
Fig. 4. SEM images of (a) i-MG filler, and (b) BEC, (c) Bi–MC, (d) SEC, (e) Si–MC, (f) SBEC and (g) SBi–MC composites.
composites exhibit an increase in the thermal stability compared
to the controls. EG and i-MG sheets were dispersed properly in
the rubber matrix and act as efficient heat shielders by dissipating
more heat and do not permit the heat to grow-up within the ma-
trix, and thereby prevents oxidation at the early stage of degrada-
tion [36].
4.8. Cure characteristics
Table 2 represents the differences in the cure characteristics of
the different rubber vulcanizates filled with EG and i-MG in the
presence of CB. Minimum torque (ML), maximum torque (MH)
and torque difference (DS) are considered as a measure of viscos-
ity, stock modulus and degree of crosslinking of the rubber com-
posite respectively [37,38]. EG/CB and i-MG/CB containing
different rubber vulcanizates showed an increase in the MH and
DS values compared to the only CB loaded rubber compounds.
EG and i-MG filled rubber composites exhibit reduced scorch and
cure time compared to their respective controls. The better
669
dispersion of i-MG in the different rubber vulcanizates increases
the stiffness and modulus of the rubber composites, which result-
ing in an increase in the MH value of the rubber composites. The
fast curing reaction was activated by the large surface area of
graphite nanoplatelets in the rubber composites and the polar
groups on the surface of i-MG acted as an accelerator to speed
up the ring opening of sulfur (S8) simultaneously.
4.9. Mechanical properties and DIN abrasion study
The effects of EG and i-MG addition with CB on the mechanical
properties of BR, SBR and SBR/BR blends are presented in the
Fig. 8a–f. It was observed that the incorporation of minimum
amount (3 wt%) of EG and i-MG with CB (30 wt%) into the different
rubber matrices, the tensile strength, modulus and tear strength of
the composites were increased compared to the only CB (40 wt%)
loaded rubber composites. It was evident that the tensile strength
of the BEC (BR/EG/CB), SEC (SBR/EG/CB), SBEC (SBR/BR/EG/CB),
Bi–MC (BR/i-MG/CB), Si–MC (SBR/i-MG/CB) and SBi–MC (SBR/BR/
670 A. Malas et al. / Materials and Design 55 (2014) 664–673

Fig. 5. HR-TEM images of (a) BEC, (b) Bi–MC, (c) SEC, (d) Si–MC, (e) SBEC and (f) SBi–MC composites.

Fig. 6. (a and b) Storage modulus vs temperature curves of the rubber composites and (c and d) tan d vs temperature curves of the rubber composites.
 A. Malas et al. / Materials and Design 55 (2014) 664–673 671

Fig. 7. TGA curves of (a) NG, EG, o-EG and i-MG, and (b–d) EG and i-MG filled rubber composites.

Table 2
Cure characteristics of the rubber compounds.

Sample code Min. torque (dN m) Max. torque (dN m) Torque difference (dN m) Scorch time (min) Cure time (min) Cure rate
BC 31.7 74.9 43.2 1.7 3.9 42.2
SC 10.4 46.5 36.1 7.2 20.9 8.7
SBC 24.7 63.5 38.8 3.2 5.9 24.2
BEC 22.7 80.5 57.8 1.6 3.2 68.2
SEC 10.0 63.8 53.8 3.2 15.0 9.1
SBEC 15.1 69.3 54.2 1.8 5.5 27.0
Bi–MC 26.9 81.6 54.7 1.5 3.1 69.1
Si–MC 9.6 66.6 57.0 2.9 13.2 9.7
SBi–MC 19.8 71.3 51.5 1.6 4.6 60.1

i-MG/CB) composites was 9%, 8%, 16%, 74%, 82% and 70% higher
than that of their respective controls (BR/CB, SBR/CB and SBR/BR/
CB compounds) respectively. Tear strengths of the above respective
composites were 20%, 15%, 4%, 30%, 26% and 17% higher than their
respective controls. Moduli at 300% elongation of the respective
composites were 44%, 14%, 11%, 89%, 40% and 51% higher than their
respective controls. As a result of better dispersion of i-MG in the
different rubber matrices (confirmed from both WAXD and HR-
TEM analyses), i-MG imparts better reinforcing effect to the differ-
ent rubber matrices compared to the moderately dispersed EG.
Incorporation of reinforcing nanofiller into the rubber matrix is
generally associated to a significant increase in the wear resistance
of the neat rubber. Addition of reinforcing fillers such as CB and
graphite nanoplatelets improves stiffness and strength of rubber
[39]. Therefore, the wear resistance of the rubber composite was
improved by concealing tearing of the rubber under the sliding
motion of the abrasives. The improvement in the wear resistance
of the EG/CB and i-MG/CB filled rubber composites was due to
the large surface area of the nanofillers and better filler-rubber
interfacial adhesion. Arayapranee et al. investigated the effect of
different fillers and loading on the abrasion resistance of natural
rubber (NR). They observed that the addition of CB and silica
reduces the abrasion loss of NR matrix [40]. Hong et al. studied
the effects of the structure and particle size of different CBs on
672 A. Malas et al. / Materials and Design 55 (2014) 664–673

Fig. 8d. Tear strength of the rubber composites.

Fig. 8a. Tensile strength of the rubber composites.

Fig. 8b. % Elongation at break of the rubber composites.

Fig. 8e. Abrasion resistance of the rubber composites.

Fig. 8f. Shore A hardness of the rubber composites.

Fig. 8c. Modulus of the rubber composites.
 A. Malas et al. / Materials and Design 55 (2014) 664–673
the wear and friction behavior of the loaded NR, SBR and BR. They
noticed that the wear surface of the rubber compounds filled with
CB having smaller particle size exhibited better abrasion resistance
[41]. Wear mechanism also depends on the hardness of the rubber
composites which is an urgent property in determining the
amount of mass removal. In the presence of rigid reinforcing
nanofillers, the potential hardness of the rubber composite which
serves in decreasing the amount of mass elimination is increased.
5. Conclusions
EG/CB and i-MG/CB filled rubber composites based on different
synthetic rubbers were fabricated by melt blending. As a result of
large surface area and the presence of polar groups on the surface
of the nanofillers, the physical interaction and interfacial adhesion
between the nanofillers and the rubber matrices were enhanced,
which resulting in an improvement in the physical, mechanical
and thermo-mechanical properties of the rubber nanocomposites.
Because of the large surface area of the nanofillers, the filled rubber
composites exhibit fast curing reaction, which resulting in a de-
crease in the scorch (TS2) and optimum cure time (Tc90). We have
observed improved storage modulus, lower rolling resistance and
better antiskid properties for the EG/CB and i-MG/CB loaded SBR/
BR blends compared to their respective controls. The different rub-
ber composites show increase in the thermal stability compared to
the controls. EG and i-MG filled BR, SBR and SBR/BR compounds
exhibit an increase in the hardness, which resulting in an improve-
ment in the abrasion resistance of the respective composite.
Because of the higher basal spacing and exfoliated structure of
i-MG sheets than EG flakes, i-MG sheets were uniformly dispersed
in the different rubber matrices in the presence of CB, which result-
ing in a superior mechanical, dynamic mechanical and thermal
properties of the i-MG loaded rubber composites compared to
the EG filled rubber vulcanizates.
Acknowledgement
Authors are deeply grateful to the Council of Scientific and
Industrial Research (CSIR), New Delhi, India for their beneficent
financial support.
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