Acta Materialia 55 (2007) 6372–6382

www.elsevier.com/locate/actamat

Improved mechanical and functional properties of elastomer/graphite

nanocomposites prepared by latex compounding
a,b
Jian Yang , Ming Tian a, Qing-Xiu Jia b, Jun-Hong Shi a, Li-Qun Zhang a,b,*
,
Szu-Hui Lim c, Zhong-Zhen Yu c, Yiu-Wing Mai c,*
a
Key Laboratory for Nano-materials, Beijing University of Chemical Technology, Ministry of Education of China, Beijing 100029, China
b
Key Laboratory on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029, China
c
Centre for Advanced Materials Technology (CAMT), School of Aerospace, Mechanical and Mechatronic Engineering (J07),
The University of Sydney, Sydney, NSW 2006, Australia

Received 21 April 2007; received in revised form 25 June 2007; accepted 26 July 2007
Available online 12 September 2007

Abstract

The facile latex approach has been adopted to finely incorporate graphite nanosheets into elastomeric polymer matrix to obtain high-
performance elastomeric nanocomposites with improved mechanical properties and functional properties. Scanning electron microscopy,
transmission electron microscopy and X-ray diffraction experiments show that the nanostructures of the final nanocomposites exhibit a
high degree of exfoliation and intercalation of graphite in the nitrile-butadiene rubber (NBR) matrix. Mechanical and dynamic-mechan-
ical tests demonstrate that the NBR/graphite nanocomposites possess greatly increased elastic modulus and tensile strength, and desir-
ably strong interfaces. The unexpected self-crosslinking of elastomer/graphite nanocomposites was discovered and then verified by
oscillating disc rheometry and equilibrium swelling experiments. After critically examining various polymer types by X-ray photoelectron
spectroscopy, electron spin resonance and Fourier transform infrared spectroscopy, a radical initiation mechanism was proposed to
explain the self-crosslinking reaction. These NBR/graphite nanocomposites possess significantly improved wear resistance and gas bar-
rier properties, and superior electrical/thermal conductivity. Such versatile functional properties make NBR nanocomposites a promising
new class of advanced materials.
 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Nanocomposites; Elastomers; Graphite; Nanostructure; Latex compounding

1. Introduction
Nanocomposites have been shown to afford remarkable
property enhancements compared to conventional micro-
composites [1–3]. Polymer nanocomposites with layered sil-
icates [4–9] and carbon nanotubes [10–12] have attracted
great interest for the improvement of structural properties
and the development of new materials with different func-
tional properties. Graphite is a layered material with a high
aspect ratio in its exfoliated state; it is also one of the stron-
*
Corresponding authors.
E-mail addresses: zhanglq@mail.buct.edu.cn (L.-Q. Zhang), y.mai@
usyd.edu.au (Y.-W. Mai).
gest materials per unit weight and has unique functional
properties (e.g. good electrical and thermal conductivities,
and good lubricating properties) compared to layered
silicates [13]. In addition, graphite is cheap compared to
carbon nanotubes. Recently, polymer/graphite nanosheet
composites have made a great impact in nanocomposite
research [14–27].
To date, some polymer/expanded graphite (EG) nano-
composites with good electrical conductivity have been
prepared (e.g. via in situ polymerization) [14–22]. But EG
does not significantly enhance the mechanical properties
of the polymers due to poor dispersion of the graphite,
voids trapped in the composites and weak interfacial adhe-
sion [19–26]. Indeed, the functional performance of the

1359-6454/$30.00  2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2007.07.043
 J. Yang et al. / Acta Materialia 55 (2007) 6372–6382
nanocomposites may be curtailed. Polymer/graphite
nanocomposites with both enhanced mechanical and
functional properties derived from the unique multifunc-
tional nature of graphite nanosheets have rarely been
reported, probably because of the great difficulties in simul-
taneously achieving good exfoliation and dispersion of
graphite and strong interfacial adhesion between graphite
and polymer.
Elastomeric compounds are a class of materials widely
used not only in general products, but also in specialized
fields such as aerospace, biomedical, micro-electrome-
chanical systems and shape memory polymers [28–31].
In many of these applications, high strength, superior
electrical and thermal conductivities, and improved tribo-
logical and barrier properties are required. Various types
of filler have been incorporated into rubber matrices in
order to provide reinforcement or functional properties.
However, most of those filled composites do not combine
enhanced mechanical properties with superior multifunc-
tional performance. Thus, graphite may be an ideal nano-
filler to impart these mechanical [32,33] and functional
properties to rubber materials, provided that fine disper-
sion of the filler and strong interfacial interaction between
filler and rubber are achieved. To the best of our knowl-
edge, few papers have been published on elastomer/
graphite nanocomposites.
Even though conventional direct blending techniques
usually provide sufficient force for filler dispersion during
rubber processing, due to the high viscosity of the material,
it cannot ensure satisfactory dispersion of graphite layers.
As most rubbers exist in latex forms, in which latex parti-
cles with sizes of 50 nm are uniformly stabilized in water,
the latex compounding method (LCM), which offers a
good performance/cost ratio, has been developed. Using
this method, we have prepared various rubber nanocom-
posites with layered silicates, fibrillar silicates and starch
[34,35]. Karger-Krocsis et al. have also fabricated nano-
composites via this latex technology [36,37].
By exploiting the ‘‘partially ionic’’ nature of the graphite
layers and the functional groups (epoxide and hydroxyl) on
the exfoliated graphite oxide, as well as the ease of interca-
lating organic compounds [38–42], we firstly modified
in situ graphite layers by introducing sodium dodecylsulfo-
nate (SDS) in an aqueous suspension of graphite to stabi-
lize the material. After mixing the suspension with rubber
latex, SDS began to build bridges between the graphite
nanosheets and rubber macromolecules during the fast
co-coagulation, which prevented the aggregation of graph-
ite nanosheets and led to the rubber-intercalated structure
and nanoscale dispersion. Nitrile-butadiene rubber
(NBR), a widely used elastomer with a polar cyanide group
(C”N), was chosen as the matrix in order to obtain strong
interfacial adhesion between graphite nanosheets and elas-
tomer through the interaction between the C”N group and
polar groups of the nanosheets. It was found that latex
compounding is very effective in achieving the nanoscale
dispersion of graphite in NBR. The graphite nanosheets
6373
are strongly reinforced and the functional properties of
the corresponding NBR nanocomposites become quite
prominent.
More importantly, an unexpected self-crosslinking of
graphite/NBR is found, resulting in strong interfacial inter-
action. Thus, several elastomer-based nanocomposites with
EG were prepared by latex compounding in order to study
the self-crosslinking behavior, which was mainly investi-
gated via oscillating disc rheometry and equilibrium swell-
ing experiments. This self-curing process may help to
establish a desirable covalently bonded interface in the
nanocomposites, hence eliminating the use of conventional
additives such as curing agents, accelerators and activators,
and thereby making it possible to design simple composi-
tions for potential applications.
2. Material and methods
2.1. Materials
Styrene butadiene rubber (SBR) latex (styrene content
23%) was obtained from Jilin Petrochemical Company
(China). Natural rubber (NR) latex was provided by Bei-
jing Latex Factory (China). NBR latex (AN content 24–
26%) was supplied by Lanzhou Petrochemical Company
(China). Graphite oxide was provided by Pingdu Huadong
Graphite Processing Factory (China). Other chemicals and
rubber curing additives were purchased from stores and
used as received.
2.2. Preparation procedure
EG with an expansion ratio along the c-axis of 250
was prepared by microwave irradiation of graphite oxide
for 30 s in a microwave oven (Sanyo EM-183MS1) with
a power of 700 W and a frequency at 2.45 GHz [43]. Then
the EG was mixed and saturated with deionized water with
the aid of the surfactant SDS. In a typical procedure, an
EG/SDS/H2O ratio of 1 g/5 g/1.5 l was used. The mixture
was subjected to ultrasonic irradiation with a power of
100 W for 8 h, which resulted in the formation of a com-
paratively stable aqueous suspension of graphitic nano-
sheets. The NBR latex was added to the suspension
slowly under vigorous stirring, and subsequently treated
with ultrasonic irradiation. CaCl2 aqueous solution
(1 wt.%) was then added to co-coagulate rubber and graph-
ite. In direct blending, which is the commonest rubber
blending technique, EG powder pre-treated with ultrasonic
irradiation was dried and pulverized, and then added
directly into NBR in a Haake mixer.
For regular tests, a sulfur curing system was added. The
NBR/EG compound was further mixed in the mixer with
the curing ingredients according to the recipe in Table 1.
To prepare samples for mechanical tests, the curing time
was determined using an oscillating disc rheometer
(ODR) at 160 C. The compounds were then vulcanized
for testing in a press at a pressure and temperature of
6374 J. Yang et al. / Acta Materialia 55 (2007) 6372–6382
Table 1
Formulation of the sulfur-curing system for NBR/EG compounding
Materials
NBR
Sulfur
ZnO
Stearic acid (SA)
Anti-aging reagent 4010NAb
Accelerator DMc
Graphite
a permeability-measurement apparatus described elsewhere
Parts per hundred rubber parts in weight.
b
N-isopropyl N 0 -phenyl 1,4-phenylenediamine.
c
Dibenzothiazyl disulfide.
15 MPa and 160 C, respectively, using the optimum cure
time (T90) determined from the ODR results.
2.3. Characterization and testing
The morphologies of the freeze-fractured surfaces of the
compounds were determined by scanning electron micros-
copy (SEM) (Philips, The Netherlands). Transmission elec-
tron microscopy (TEM) observations were performed with
a Hitachi H-800 (Japan) at an acceleration voltage of
200 kV. X-ray diffraction (XRD) data were acquired with
a Rigaku D/Max 2500VBZt/PC X-ray diffractometer
(Japan). Expanded graphite was characterized by X-ray
photoelectron spectroscopy (XPS) and electron spin reso-
nance (ESR). The XPS spectra of the samples were
recorded by using an ESCA LAB 250 (VG Scientific
Ltd., UK) and Al Ka radiation (1486.6 eV) was used as
an X-ray source. ESR was conducted at room temperature
with a Bruker ESP300E instrument equipped with a micro-
wave counter (microwave power 10 mW). The Fourier
transform infrared spectroscopy (FT-IR) spectra of the
samples were recorded by a Perkin–Elmer System 2000
FT-IR spectrometer using the attenuated total reflection
(ATR) technique with a resolution of 2 cm1.
The Shore A hardness of the vulcanizates were mea-
sured according to ASTM D2240 using an XY-1 type A
durometer (No. 4 Chemical Machinery Plant of Shanghai
Chemical Equipment Co. Ltd., China) and three different
locations of a sample (>6 mm in thickness) to obtain an
average value. Tensile tests of dumbbell specimens of the
vulcanizates were carried out on a CMT4104 testing
machine (Shenzhen SANS Testing Machine Co. Ltd.,
China) at a speed of 500 mm min1 according to ASTM
D412. Storage modulus, E 0 , and dynamic loss, tan d, were
measured as a function of temperature on a Dynamic
Mechanical Thermal Analyzer DMTA V (Rheometrics
Science Corporation) under tension mode at 1 Hz and
3 C min1.
The crosslinking density, i.e. the elastically active net-
work chain density, Ve (mol cm3), was determined by
the Flory–Rehner equation [44], through equilibrium
swelling experiments using toluene as a solvent at ambient
temperature:
lnð1  V r Þ þ V r þ vV 2r
Ve ¼ ð1Þ
a
V s ðV r1=3  V r =2Þ
Amounts (phr )
100 where Vr is the polymer volume fraction in the vulcanizate
1.5 swollen to equilibrium and Vs is the solvent molar volume
5 (106.5 cm3 mol1 for toluene). v is the rubber–toluene
1 interaction parameter and is taken as 0.435 and 0.446 for
2 NBR and SBR, respectively [45,46].
1.5
Variable Nitrogen permeation tests were performed with a gas
[9]. The thermal conductivity of nanocomposites was mea-
sured by a FOX50 heat flow meter from Laser Comp., Inc.
USA. Bulk electrical conductivity tests were conducted
using a Zheng-Yang Ohmmeter (Model QJ84) with a
four-terminal measurement feature to obtain the bulk
conductivity. Wear properties were evaluated using a
ring-on-disc tester (manufactured by Jinan Shijin Co.,
China) [47,48].
3. Results and discussion
3.1. Morphology of rubber/graphite nanocomposites
Graphite nanosheets were obtained by thermal decom-
position of graphite oxide and subsequent ultrasonic
irradiation [49] (see Fig. 1a). When the graphite nanosheets
were directly mixed with NBR in a Haake mixer, their
dispersion was poor as evidenced by many large EG
aggregates and a large amount of rubber matrix without
graphite filler in Fig. 1b. In contrast, LCM gives a much
finer and more uniform dispersion of graphite nanosheets
in NBR as shown in Fig. 1c–f. It can be seen that the sur-
face dimensions of the dispersed graphite layers are quite
large (several to tens of microns) with nanometer-scale
thickness. This causes some difficulties in clearly observing
the dispersion quality with TEM, especially in distinguish-
ing individual graphite sheets. By comparing Fig. 1d with
Fig. 1b, it can clearly be seen that the interface between
the graphite sheets and NBR is greatly improved using
LCM. This will definitely enhance the reinforcement effi-
ciency of graphite nanosheets.
3.2. XRD analysis of nanocomposite structures
The microstructure of the NBR/EG nanocomposites
prepared by LCM was further studied by XRD, which
reveals the coexistence of intercalated and exfoliated
microstructures (see Fig. 2), as indicated by the shift in
the well-defined (0 0 1) reflections.
Fig. 2a shows the XRD patterns of EG powder before
and after the ultrasonic treatment, with and without surfac-
tant SDS. The original EG displays only one diffraction
peak at 2h = 26.6, corresponding to a basal spacing of
0.335 nm, which is the lamellar characteristic of graphite.
After ultrasonic treatment without SDS, the XRD pattern
of EG powder is unchanged. However, after ultrasonic
treatment with SDS, a new (0 0 1) diffraction peak emerges
 J. Yang et al. / Acta Materialia 55 (2007) 6372–6382 6375

Fig. 1. SEM micrographs showing: (a) EG powder pretreated with ultrasonic irradiation; (b) NBR composite with 5 phr EG prepared by direct blending;
(c,d) NBR nanocomposite with 5 phr EG prepared by latex compounding. (e,f) TEM images of NBR nanocomposite with 5 phr EG prepared by latex
compounding.

at 2h = 2.55, corresponding to a basal spacing of 3.47 nm,
which is due to the intercalation of the SDS surfactant.
However, the peak at 2h = 26.6 still remains, though with
a reduced intensity. The reason is that not all of the carbon
sheets were opened after the thermal expansion of graphite
oxide. However, with ultrasonic treatment, nanometer-
thick graphite sheets could be obtained in the aqueous sus-
pension, and those sheets were covered by surfactant
molecules.
The XRD pattern in the small angle range (0.5–10) of
the EG powder pretreated with ultrasonic treatment and
SDS is shown in Fig. 2 (curve c2), and again displays a
well-defined (0 0 1) diffraction pattern for the SDS
intercalated structure. After adding NBR, the latex parti-
cles enter the sheet network in suspension and graphite
sheets are separated by strong ultrasonic irradiation. Dur-
ing subsequent flocculation, the flocculant causes the NBR
macromolecules and graphite sheets to flocculate simulta-
neously and a nanoscale dispersion of graphite nanosheets
is hence maintained in the NBR matrix. This is similar to
the process of preparing rubber/clay nanocomposites by
LCM [9]. It is noted that there is competition between
the separation of graphite sheets by coagulated rubber
and the re-aggregation of the sheets, which depends on
many factors, such as graphite loading, solid content in
suspension, type of flocculant, surfactant type and content.
After latex compounding, the primary diffraction peak of
graphite at small angles has shifted to a very low angle of
1.02 (Fig. 2, curve c3), indicating that a portion of EG
became intercalated by NBR macromolecules. Another
peak at 2.89 is thought to be due to the change of SDS
intercalation structure during LCM and hot pressing, e.g.
conformational change of SDS molecules between graphite
layers, or contraction of some SDS molecules.
In the wide-angle range, the diffraction of graphite at
2h = 26.6, corresponding to a basal spacing of 0.335 nm,
is much weaker in the nanocomposite prepared by LCM
than that by direct blending with the same loading of
EG, as shown in Fig. 2b. The existence of a peak at
2h = 26.6 for composites prepared by LCM can be
ascribed to both the unopened nanosheets during the
thermal expansion and consequent treatment, and the
restacking of graphite layers during co-coagulation. How-
ever, the thickness of aggregate is generally nanoscale due
to the separation effect of the latex particles [9]. These
observed results indicate that LCM gives a greater extent
of exfoliation, intercalation and separation of graphite in
the NBR matrix.
6376 J. Yang et al. / Acta Materialia 55 (2007) 6372–6382

3.3. Mechanical properties

The effects of EG content on both mechanical and phys-

ical properties are summarized in Table 2. Fig. 3a and b
shows typical tensile stress–strain curves of the vulcanizates
filled with different amounts of EG by LCM, and compar-
isons of reinforcement efficiency of different preparation
routes (i.e. LCM and direct blending) and different fillers
(i.e. carbon black N330, silica) at the same loading of

Table 2
Properties of NBR/EG nanocomposites prepared from LCM
EG content (phr) 0 3 5 10 10a
Shore A hardness 50 61 74 89 56
Modulus at 100% elongation (MPa) 1.1 2.5 5.7 11.5 1.8
Tensile strength (MPa) 4.0 4.6 10.5 11.8 5.8
Elongation at break (%) 410 180 180 110 610
Permanent tensile set (%) 4 4 2 2 10
a
By direct blending.

Fig. 2. X-ray diffraction patterns: (a1) expanded graphite (EG); (a2) EG

powder pretreated with ultrasonic irradiation without adding surfactant
SDS; (a3) EG powder pretreated with ultrasonic irradiation and dried,
with SDS intercalated; (b1) unfilled NBR vulcanizate at wide angle (3–
30); (b2) NBR/EG (5 phr) nanocomposite prepared by latex compound-
ing at wide angle; (b3) NBR/EG (5 phr) composite prepared by direct
blending; (c1) unfilled NBR vulcanizate at small angle (0.5–10); (c2) EG Fig. 3. Mechanical properties: (a) tensile stress vs. strain curves of NBR/
powder pretreated with ultrasonic irradiation with SDS intercalated; (c3) EG nanocomposites prepared by latex compounding with different EG
NBR/EG (5 phr) nanocomposite prepared by latex compounding at small content; and (b) comparisons of efficiency of reinforcement of different
angle. fillers (i.e. carbon black N330 and silica) at the same loading of 10 phr.
 J. Yang et al. / Acta Materialia 55 (2007) 6372–6382 6377

10 phr, respectively. For nanocomposites prepared by

LCM, the tensile strength increases substantially with EG
content in the range 0–10 phr. Also, the stress at small
strain (under 100%) increases more remarkably with
increasing EG, when compared to NBR/EG (10 phr) com-
posites by direct blending (Fig. 3b). The different tensile
properties of NBR/EG vulcanizates prepared by LCM
and direct blending can be attributed to the different dis-
persion quality of graphite sheets. The fine dispersion of
graphite sheets achieved by LCM generates more interfa-
cial interaction, resulting in better reinforcement.
It can be seen from Fig. 3b that NBR/EG (10 phr) nano-
composite prepared by LCM exhibits the highest reinforce-
ment efficiency compared to those of composites reinforced
with other traditional reinforcements for rubbers, such as
carbon black and silica. The high aspect ratio and large
surface areas of graphite nanosheets offer much stronger
reinforcement. In addition, the polar groups on the EG
surface, e.g. –OH and –COOH, might interact physically
and chemically with rubber macromolecules, leading to
strong interfacial interactions, which are further substanti-
ated by the increased glass transition temperatures of the
nanocomposites.

3.4. Dynamic mechanical properties

Fig. 4 shows the temperature dependence of the storage

modulus (E 0 ) and tan d of NBR/EG nanocomposites. It can
be seen that the storage modulus at a given temperature
above Tg increases with increasing EG content, resulting
in an increased E 0 compared with unfilled NBR. In
addition, the glass transition is strongly shifted to higher
temperature as EG content increases, when compared to
the clay-reinforced rubber nanocomposites reported else-
where [50–52], which is attributed to the markedly reduced
mobility of the NBR chains around the EG sheets. Also,
the area of the tan d peak is greatly reduced with increasing
EG content, indicating significantly reduced damping.
Conversely, for NBR/EG composites prepared by direct
blending, Tg changes little with increasing EG content.
The Tg of NBR/EG (10 phr) composite prepared by direct
blending is only 5 C higher than that of neat NBR. Sim-
ilarly, the enhancement of storage modulus in NBR/EG
(10 phr) composite prepared by direct blending is inferior
to that of NBR/EG nanocomposites prepared by LCM.
With 10 phr EG, the storage modulus at 40 C is enhanced
by 1.8 times only in the former composite compared to that
of neat NBR, but the enhancement in the latter nanocom-
posite is 22.4 times.
3.5. Self-crosslinking of nanocomposites
In addition to the dispersion of graphite nanosheets, the
interaction between graphite and rubber should also be
considered in explaining the reduced mobility of rubber
molecules and the strong reinforcement of EG fillers. To
study the nature of the interfacial interaction, XPS was
Fig. 4. Dynamic-mechanical properties: (a) storage modulus and (b) loss
factor of NBR/EG nanocomposites with different EG content.
conducted on the pressed EG sheets: an O/C ratio of about
7–8% was found together with an asymmetric C1s peak cen-
tered at 284.5 eV with a shoulder to higher binding energy
(see Fig. 5a), indicating the existence of epoxide and hydro-
xyl groups on the EG surface [38,39]. The physical interac-
tion between these active polar groups and NBR molecules
(with C”N) would enhance the reinforcement of graphite
sheets and lead to a greatly increased glass transition tem-
perature of the NBR/EG nanocomposites. In addition, the
electron spin resonance (ESR) spectrum of EG (Fig. 5b)
shows one strong, intense signal, indicating the existence
of free radical intermediates [39,53]. After thermal decom-
position of EG precursor or heat treatment in air, free rad-
icals form as a consequence of pyrolytic bond cleavage (e.g.
evolution of CO2, CO), and these can be stabilized either
by the formation of a graphene sheet with free edges or
by the saturation of residual reactive sites, e.g. by O2
chemisorption, as reported previously for carbon species
[39,53–56]. These radicals could react with the C@C bonds
and adjacent a-H of the rubber macromolecules at elevated
temperature, enhancing the interfacial interaction and
facilitating the reinforcement of graphite sheets.
6378 J. Yang et al. / Acta Materialia 55 (2007) 6372–6382

Fig. 6. Curing dynamics of NBR nanocomposites with 5 phr graphite.

the dispersion of EG filler is poor, as in the composite pre-

pared by direct blending without a curing agent, the torque
remains constant with time (curve d), indicating that the
dispersion quality of EG sheets plays a significant role in
establishing effective reactions between EG and NBR mac-
romolecules. For nanocomposites from LCM, the good
dispersion of EG sheets provides a much higher contact
area between EG sheets and rubber molecules, so the active
sites on EG (e.g. the free radicals indicated by ESR analy-
sis) can react with the NBR macromolecules, resulting in
covalent bonding between EG and rubber.

3.6. Temperature dependence of self-crosslinking

Fig. 5. Characterization of EG structures: (a) XPS, using XPSPEAK
software; and (b) ESR.
To further investigate the self-curing effect of the rubber
nanocomposites containing graphite nanosheets, SBR/EG
ODR is a well-established technique for studying the and NR/EG nanocomposites were also prepared using
dynamics of the rubber curing reaction by monitoring the LCM. As shown in Fig. 7, the dispersion quality of graph-
modulus change of rubber composites with time. This ite sheets in these rubber matrices is quite satisfactory. It is
method can also be used to investigate the evolution of also found that the self-curing effect of EG is temperature
interfacial interactions caused by chemical reactions that dependent. Fig. 8 shows the ODR results of the NBR
have occurred at the processing temperature. Therefore,
we performed ODR analysis on compounds without curing
agents (e.g. sulfur). As shown in Fig. 6, the initial torque
(e.g. within the first 1 min) of the NBR/5 phr EG nano-
composite (curve b) is much higher than the torques of
pure NBR (curve a) and directly blended NBR/5 phr EG
composite (curve d). This finding is attributed to the strong
interactions between polar groups of EG sheets and polar
CN groups of NBR macromolecular chains, in addition
to the fine dispersion of EG in rubber matrix. Interestingly,
the torque of the NBR/5 phr EG nanocomposite without
any curing reagents increases rapidly with time (curve b)
at 160 C, clearly confirming that a chemical crosslinking
reaction of NBR, which is very unusual, has occurred. In
contrast, the torques of neat NBR or NBR filled with
5 phr SDS remain almost unchanged (curves a and c).
These results strongly suggest the self-curing effect of Fig. 7. TEM images of (a) SBR and (b) NR nanocomposites with 5 phr of
NBR which is induced by EG. More importantly, when graphite.
 J. Yang et al. / Acta Materialia 55 (2007) 6372–6382
Fig. 8. Temperature dependence of self-curing reaction: (a) NBR/5 phr
graphite nanocomposites, and (b) SBR/5 phr graphite nanocomposites.
and SBR systems at different temperatures. As shown in
Fig. 8a, the torque of NBR/5 phr graphite nanocomposite
increases distinctly and rapidly with time at temperatures
above 120 C, and gradually reaches a steady state. Below
100 C, no crosslinking reaction takes place. At 110 C and
above, the rate of change of torque with time increases
markedly, particularly in the early stage of crosslinking.
Generally, the torque of a rubber compound in an uncross-
linked state decreases with increasing temperature. How-
ever, this tendency is disturbed in NBR/EG system
because the crosslinking reaction induced by EG at higher
temperatures becomes faster, and thus greatly and rapidly
increases the torque of the NBR compound.
The temperature-dependent self-crosslinking behavior
of SBR/graphite nanocomposites is also evident in
Fig. 8b. As the temperature approaches 160 C, the SBR/
EG compound starts to show distinct curing dynamics.
Similarly, pure SBR cannot be cured without a curing
agent. Compared with the NBR system, the self-crosslink-
ing rate of SBR compound is lower but the torque change
in ODR tests increases more quickly with temperature.
However, based on the ODR test, no curing is observed
6379
in NR/graphite nanocomposites in the temperature range
140–190 C (not shown). Hence, the torque of the NR com-
pound normally decreases with increasing temperature.
For self-crosslinked NBR/graphite nanocomposites
(1 h curing at 160 C), we conducted swelling experiments
to measure the crosslink density. The index for crosslinking
density of NBR/graphite nanocomposites is 1.18 · 102
mol cm3, which is very close to that of the same nanocom-
posites cured with sulfur, i.e. 1.22 · 102 mol cm3. This
again confirms the chemical self-crosslinking reaction of
the NBR matrix induced by graphite sheets. When SBR/
graphite nanocomposite was cured at 160 C, it could still
be partially dissolved in toluene. When the curing temper-
ature was higher (i.e. 190 C), the SBR/graphite plate could
no longer be dissolved in toluene, and its crosslinking den-
sity reaches 2.03 · 105 mol cm3. Due to the fact that the
vulcanization of NR/graphite nanocomposites is insuffi-
cient in the temperature range studied, the corresponding
plates dissolve in toluene, although at a much slower rate
than the neat component. This implies the possible forma-
tion of strong interfacial interactions between filler and
matrix.
3.7. Mechanism of self-crosslinking
The crosslinking of rubber/graphite nanocomposites
seems to be very similar to the curing process of rubbers
by peroxide in terms of the curing characteristics. Firstly,
the vulcanization rate is relatively low with a short scorch
time compared with the most widely used process, i.e.
accelerated sulfur vulcanization. Secondly, vulcanization
efficiency strongly depends on the rubber type, which is
similar to crosslinking by peroxide [57].
As indicated by XPS experiments, EG sheets contain C–
O and C–OH groups, which interact strongly with the
polar groups of NBR, but do not seem to result in chemical
bonding at the interface, especially for SBR, which lacks
polar groups. More importantly, this interaction happens
only at the interface and cannot lead to crosslinking of
the whole rubber phase. The curing characteristics of
NBR/graphite and SBR/graphite nanocomposites strongly
suggest that possible radicals or peroxide groups on EG
nanosheets act as initiators for the self-crosslinking behav-
ior of these rubber/graphite nanocomposites.
The radicals, as discussed in the ESR test on the EG fil-
ler, could react with the rubber macromolecules at elevated
temperatures, either through the addition of the radical to
a double bond, or the abstraction of a hydrocarbon atom
in the allylic position. Consequently, crosslinking could
form either by the combination of two polymeric free rad-
icals or by a chain reaction involving the addition of poly-
meric free radicals to double bonds. A chain reaction is
more likely in butadiene rubbers (i.e. NBR and SBR)
because the double bonds are quite accessible and radical
addition gives highly reactive radicals that are easily added
to other polymer chains [57,58]. More significantly, cross-
linking points could be formed without loss of free radicals.
6380 J. Yang et al. / Acta Materialia 55 (2007) 6372–6382

The slower curing rate and lower vulcanization efficiency of

SBR nanocomposites compared with NBR could be caused
by a higher stability of SBR to radicals. In the case of NR
nanocomposites, when the radicals on EG react with rub-
ber, the abstraction route predominates over radical addi-
tion, so that crosslinking occurs mainly via the coupling
of two polymeric radicals [57–59]. However, the abstrac-
tion reaction is quite limited since it happens only at the
contact points of the reactive radicals on EG and allylic
hydrogen atoms on the NR chains. Before two polymeric
radicals can unite, unproductive reactions would happen,
e.g. heterolytic cleavage, rearrangement, transfer, scission,
degradation, to the exclusion of crosslinking [60]. More-
over, even if the coupling does take place, the process
wastes two radicals. Therefore, the curing efficiency of
NR nanocomposites could be quite low, as displayed in
the ODR tests. However, this mechanism may still generate
chemical bonding at the interface between EG and NR,
which is reflected by the swelling experiment results.
More evidence of the self-crosslinking phenomenon is
provided by the strong shift of the glass transition of the
nanocompounds compared with neat rubber, as shown in
Table 3. After flocculation from the latex mixture and dry-
ing in a vacuum oven at 50 C for 24 h, uncured NBR
nanocomposites (before any heat treatment at high temper-
ature) already show higher Tg than neat rubber. This is
because of the fine dispersion of the sheets and the strong
interfacial interaction between the polar groups (C”N) of
NBR and the polar groups of EG sheets, which greatly
restricts the mobility of the rubber chain segments. The
Tg of the SBR and NR compounds does not change much
because no polar groups exist in their polymer chains.
After curing (1 h heat treatment at high temperature), the
Tg of all nanocomposites shifts towards higher tempera-
ture, especially for NBR and SBR compounds. Since the
chemical bonding for the two compounds is established
at the interface, and NBR and SBR matrices are also cross-
linked to a certain extent after curing, the mobility of rub-
ber chain segments is further restricted. For the NR
compound, a widely used sulfur system was introduced
via a two-roll mill in order to obtain necessary crosslinking,
which also partly contributed to the increase in Tg.
The IR spectra of NBR/EG (5 phr) nanocomposites
before and after self-crosslinking are shown in Fig. 9. It
is reasonable to assume that the C”N group on NBR mac-
Table 3
Glass transition temperatures of rubber/graphite nanocomposites by
DMTA
Uncured Rubber/5 phr graphite nanocomposites
pure
Uncured Cured Curing process
rubber
(C) (C)
(C)
NBR 14.1 0.7 3.7 160 C, 1 h, no curing agent
SBR 42.4 41.4 29.5 190 C, 1 h, no curing agent
NR 57.8 56.7 53.0 143 C, 10 min, with curing
agent
Fig. 9. FT-IR spectra of NBR/5phr graphite nanocomposites, before and
after self-curing at 160 C for 1 h.
romolecular chain does not take part in the curing reac-
tions, and the IR peak is at m = 2236 cm1. For the
uncured nanocomposite, the peak at m = 1644 cm1 corre-
sponds to C@C stretch vibration. Compared to the change
in peak at m = 2236 cm1 after self-crosslinking, the inten-
sity of the peak at m = 1644 cm1 is distinctly reduced. This
indicates that part of the C@C participates in the curing
reaction, which is consistent with the previous discussion
on radical curing mechanisms. The absorption peak at
m = 1713 cm1, which usually corresponds to a carboxyl
group in EG, is capable of producing a physical interaction
with the C”N group.
The self-cured nanocomposites also possess better
mechanical properties. For example, NBR/EG (5 phr)
nanocomposite, which is highly crosslinked in the presence
of filler (1 h curing at 160 C), has a tensile strength and an
initial modulus that is respectively 2 and 5 times higher
than that of sulfur-cured gum.
3.8. Functional properties
With a fine dispersion of EG in NBR and a strong inter-
face between EG/NBR by LCM, EG filler should confer
good functional properties on the rubber nanocomposites.
Similar to layered silicates, EG sheets also show superior
gas barrier properties. As given in Table 4, the nitrogen
permeability of NBR/10 phr EG nanocomposite is reduced
by 62% compared to that of unfilled NBR vulcanizate;
however, the permeability of the composite prepared by
direct blending is only decreased by 43%. EG sheets also
offer the advantage over layered silicates, that they make
NBR electrically and thermally conductive. NBR nano-
composites become conductive when the EG loading
reaches 5 phr. The electrical conductivity of the nanocom-
posite with 10 phr EG is even higher than the rubber
composites filled with 30–40 phr conductive carbon
black particles [61,62]. The thermal conductivity of NBR
is substantially improved by the addition of EG. The
 J. Yang et al. / Acta Materialia 55 (2007) 6372–6382 6381

Table 4 (ARC) for the financial support of this project. Z.Z.Y.

Functional properties of NBR/EG nanocomposites prepared from LCM and Y.W.M. are Australian Postdoctoral Fellow and Aus-
EG content (phr) 0 3 5 10 10a tralian Federation Fellow, respectively, supported by the
N2 permeability 3.19 – 1.98 1.21 1.83 ARC and tenable at the University of Sydney.
(1017 m2 Pa1 s1)
Friction coefficientb 1.72 – – 1.36 1.38
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