J Mater Sci (2013) 48:6223–6232
DOI 10.1007/s10853-013-7420-8
Electrical and mechanical properties of PMMA/reduced graphene
oxide nanocomposites prepared via in situ polymerization
Sandeep Nath Tripathi • Parveen Saini •
Deeksha Gupta • Veena Choudhary
Received: 20 February 2013 / Accepted: 29 April 2013 / Published online: 14 May 2013
Ó Springer Science+Business Media New York 2013
Abstract We report the effect of filler incorporation
techniques on the electrical and mechanical properties of
reduced graphene oxide (RGO)-filled poly(methyl meth-
acrylate) (PMMA) nanocomposites. Composites were
prepared by three different techniques, viz. in situ poly-
merisation of MMA monomer in presence of RGO, bulk
polymerization of MMA in presence of PMMA beads/
RGO and by in situ polymerization of MMA in presence of
RGO followed by sheet casting. In particular, the effect of
incorporation of varying amounts (i.e. ranging from 0.1 to
2 % w/w) of RGO on the electrical, thermal, morphologi-
cal and mechanical properties of PMMA was investigated.
The electrical conductivity was found to be critically
dependent on the amount of RGO as well as on the method
of its incorporation. The electrical conductivity of 2 wt%
RGO-loaded PMMA composite was increased by factor of
107, when composites were prepared by in situ polymeri-
zation of MMA in the presence of RGO and PMMA beads,
whereas, 108 times increase in conductivity was observed
at the same RGO content when composites were prepared
by casting method. FTIR and Raman spectra suggested the
presence of chemical interactions between RGO and
PMMA matrix, whereas XRD patterns, SEM and HRTEM
studies show that among three methods, the sheet-casting
Electronic supplementary material The online version of this
article (doi:10.1007/s10853-013-7420-8) contains supplementary
material, which is available to authorized users.
S. N. Tripathi
D. Gupta
V. Choudhary (&)
Centre for Polymer Science and Engineering, Indian Institute of
Technology Delhi, Hauz Khas, New Delhi 110 016, India
e-mail: veenach1951@gmail.com; veenac@polymers.iitd.ac.in
P. Saini
Polymeric and Soft Materials Section, CSIR-National Physical
Laboratory, Dr. K.S. Krishnan Road, New Delhi 110 012, India
method gives better exfoliation and dispersion of RGO
sheets within PMMA matrix. The superior thermal,
mechanical and electrical properties of composites pre-
pared by sheet-casting method provided a facile and logical
route towards ultimate target of utilizing maximum fraction
of intrinsic properties of graphene sheets.
Introduction
Since its discovery in 2004 by Novoselov et al. [1–3],
graphene has drawn enormous scientific attention due to its
unique properties and wide range of dependent applications
[4, 5]. In particular, exceptionally high surface area along
with exceptional electrical, thermal and mechanical prop-
erties makes graphene an ideal nano-filler for functional
nanocomposites. The interesting attributes of graphene as
compared with CNTs includes high thermal conductivity,
mechanical strength and superior electron transport prop-
erties. In fact, single layer graphene with Young’s modulus
of *1.0 TPa and tensile strength of *130 GPa, is the
strongest material ever discovered [6]. However, to utilize
its full potential, graphene needs to be dispersed in a
suitable matrix to form composites. Recently, interest has
grown significantly in polymer/graphene nanocomposites
[7–9], e.g. Ruoff et al. [10] have reported polystyrene/
graphene composites, whereas, Wang et al. [11–13] have
synthesized graphene-filled nanocomposites with various
polymer matrices, (e.g. polystyrene (PS), poly(vinyl alco-
hol) and low density polyethylene (LDPE)) and using
number of strategies, viz. in situ polymerization, solution
mixing and melt blending, respectively. Many dedicated
attempts have also been made to formulate poly(methyl
methacrylate) [PMMA]/GO nanocomposites using tech-
niques such as solution casting, self-assembly, layer by
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layer method [14–17], in situ polymerization [18–20], etc.,
due to specific advantages of PMMA, e.g. low cost, ther-
mal/melt processing, mouldability into any shape, optical
clarity and good physico-mechanical properties. In partic-
ular, Goncalves et al. [21] have synthesized surface-mod-
ified graphene and PMMA nanocomposites using atom
transfer radical polymerization (ATRP). Very recently,
Nishino et al. [22] have reported an ecological approach for
the synthesis of GO reinforced PMMA nanocomposites
with enhanced thermal, mechanical and oxygen barrier
properties. Some studies also highlighted the effect of
polymerization techniques on the properties of PMMA/
graphene nanocomposites, e.g. Jang et al. [18] have
employed macroazoinitiator (MAI) having poly(ethylene
oxide) (PEO) segment intercalated between the gallery of
GO for the polymerization of MMA and to exfoliate GO.
Pramoda et al. [23] have reported the preparation of
covalently bonded PMMA/graphene NCs by functionali-
zing GO with octadecylamine (ODA) followed by reaction
with methacryloyl chloride to incorporate polymerizable
–C=C– functionality at the surface of nanographene
platelets. Wang et al. [24] have first synthesized graphene
nanosheet (GNS)/PMMA nanocomposites by in situ sus-
pension polymerization, and subsequently reduced incor-
porated GO phase using hydrazine hydrate and ammonia,
resulting in significant enhancement of electrical,
mechanical and thermal properties of resultant NCs. Lee
et al. [25] have used ATRP of MMA for the preparation of
PMMA/graphene NC by growing polymers chain directly
from the surface of GO. Nandi et al. [26] have used ATRP
to prepare PMMA-functionalized graphene sheet (MG)
from GO by reduction using hydrazine hydrate. Subse-
quently, the MG sheets were used to prepare MG/
poly(vinylidine fluoride) (PVDF) NCs useful for biomedi-
cal application. Similarly, Fang et al. [27, 28] also
employed the ATRP to prepare the polystyrene/graphene
composites where the initiator molecules were covalently
attached to graphene surface via diazonium addition.
Recently, Yang et al. [29] have used emulsion polymeri-
zation to prepare PMMA/graphene composite based on the
self assembly between graphene sheet and cationic PMMA
emulsion particles. Similarly, Chung et al. [30] also used
the emulsion technique with an environment friendly
approach by self assembly of positively-charged PMMA
latex particles and negatively-charged GO sheet through
electrostatic interaction, followed by in situ reduction using
hydrazine hydrate. Despite so much progress, no detailed
study is available in the literature which reports the effect
of filler incorporation techniques on the electrical and
mechanical properties of RGO/PMMA NCs along with
exploration of structure–property relationship.
In this study, we have prepared PMMA/RGO compos-
ites by three methods using bulk polymerization technique
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to investigate the effect of RGO sheet on the properties of
PMMA. In our first method, we have in situ-polymerized
MMA in the presence of RGO, in second method the
polymerization has been carried out in the presence of
RGO and commercial PMMA beads [31] and the third
method involves the preparation of composite sheet
directly from pre-polymer syrup (i.e. 20–30 % in situ
polymerized PMMA/RGO) by casting in a homemade
mould at 70 °C. The obtained composites were character-
ized for their electrical conductivity, thermal and mor-
phological properties. The detailed structural and
mechanical analysis was also performed to establish
structure–property correlation. These composites are
expected to find diverse applications such as in antistatic
formulations, EMI-shielding/microwave-absorbing materi-
als, structurally strong members, gas barrier coatings and
strain sensors, etc.
Experimental procedures
Raw materials
Graphite powder (CDH, India), sodium nitrate (Fischer
scientific), potassium permanganate (Fischer scientific),
PMMA (LG, IG-840) and azobisisobutyronitrile (CDH,
India) were used as received. MMA monomer (CDH,
India) was purified by washing with sodium hydroxide
solution (5 %) followed by washing with water till neutral
and dried over anhydrous sodium sulphate followed by
vacuum distillation to obtain purified MMA.
Synthesis of graphene oxide (GO) and reduced
graphene oxide (RGO)
Natural graphite powder was oxidized to GO using modi-
fied Hummers method [32, 33]. In a typical synthesis, 5 g
of graphite and 5 g of sodium nitrate (NaNO3) were added
into 200-mL concentrated H2SO4 (in an ice bath) followed
by the gradual addition of 30 g of KMnO4, and during the
addition, the temperature was kept below 30 °C (since
reaction is exothermic). Afterwards, the reaction mixture
was placed under stirring at room temperature for 18 h,
forming a thick paste. Subsequently, the paste was gradu-
ally poured into 400-mL deionized water. After 20 min,
another 1 L of deionized water was added to the mixture,
followed by the dropwise addition of 30 mL of 30 % H2O2
solution to reduce the excess KMnO4. The solution turns
light brown after the addition of H2O2, it was decanted and
centrifuged followed by washing with deionized water till
pH 7, and dried at room temperature under vacuum for
24 h to obtain GO solid.
J Mater Sci (2013) 48:6223–6232
Reduced graphene oxide was obtained by chemical
reduction of GO using hydrazine hydrate as a reducing
agent at 100 °C for 24 h. In a typical procedure, 500 mg
of GO was dispersed in 500 mL of deionized water and
then exfoliated by ultrasonication (100 W) for 1 h. Sub-
sequently, 5 mL of 99 % hydrazine hydrate was added,
and the solution was heated in an oil bath at 100 °C under
a water-cooled condenser for 24 h. After heating at
100 °C, the solution turns from brown to black precipi-
tate. The product was cooled and filtered, and washed
with copious amount of deionized water and dried at
60 °C under vacuum overnight to obtain RGO solid
which was characterized by FTIR, XRD, AFM, EDX (for
elemental analysis), SEM and HRTEM (see supporting
information).
Preparation of RGO–PMMA composites
Reduced graphene oxide and poly(methyl methacrylate)
composites with RGO loadings ranging from 0 to 2 wt%
were synthesized by bulk polymerization technique of
MMA using three different methods. The schematic rep-
resentation for the preparation of nanocomposite is illus-
trated in Fig. 1.
Fig. 1 PMMA/RGO nanocomposites manufacturing method. 1 In situ, 2 in presence of PMMA beads, 3 sheet casting
6225
In situ polymerization of MMA in presence of RGO
Here, monomer MMA was polymerized in the presence of
calculated amounts of RGO (according to desired RGO
weight percentage, i.e. 0, 0.1, 0.5, 1.0, 1.5 and 2.0 wt%, with
respect to PMMA matrix). In a typical synthesis, 100 mg of
RGO was dispersed in MMA (10 mL) in a glass reactor and
sonicated for 1 h followed by the addition of initiator AIBN
(0.5 wt%) and purging nitrogen gas into the system. The
reaction mixture was then heated in a water bath at 70 °C for
4 h and in an air oven at 100 °C overnight for completion of
polymerization (method 1). From the weight of the final
product, weight % of RGO was found to be 1 wt%. Similarly,
RGO–PMMA composites with lower and higher RGO
loadings (0.1, 0.5 and 1.5, 2.0 wt%, respectively) were pre-
pared following the same procedure. Afterwards, the RGO–
PMMA composite lumps were crushed into small particles
and samples were prepared by compression moulding at
200 °C and 10 MPa pressure for 10 min.
In situ polymerization of MMA in presence of RGO
and PMMA beads
In this case, same procedure was followed to prepare the
RGO–PMMA composite, the only difference was the
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addition of PMMA beads. Desired amount (100 mg) of
RGO was dispersed in 10 mL of MMA monomer and
sonicated for 1 h to get uniform dispersion of filler, and
then nitrogen was purged followed by the addition of ini-
tiator AIBN (0.5 wt%), and the mixture was heated in a
water bath at 70 °C for polymerization. During the pro-
gress of polymerization (i.e. after *20 min of the reaction
when RGO-MMA mixture started developing viscosity),
10 g of PMMA beads were added to the reaction mixture,
the reaction was continued at 70 °C for another 4 h and
dried in an air oven at 100 °C overnight. Addition of
PMMA beads at *20 % conversion would result in
swelling of the PMMA beads and due to that dispersion of
some RGOs might occur inside the beads (method 2). The
RGO–PMMA composite was removed from the flask and
crushed to small particles and samples were prepared by
compression moulding at 200 °C and 10 MPa pressure for
10 min.
In situ polymerization of MMA in presence of RGO
followed by sheet casting using pre-polymer syrup
The RGO/PMMA composite sheets were directly prepared
by bulk polymerization technique using pre-polymer
PMMA/RGO syrup. The prepolymer syrup, prepared by
bulk polymerization of MMA in the absence or presence of
varying amounts of RGO (i.e. 0–2 wt%) initiated by AIBN
(0.5 wt%). The reaction was carried out at 70 °C and
arrested at low conversion (*20–30 %) by quench cooling
the reaction mixture in an ice bath. The syrup was deaer-
ated by applying vacuum, and then it was poured into a
mould made up of two toughened glass plates and rubber
gasket of diameter 3 mm. The filled mould was kept in a
preheated water bath at 70 °C for 6 h and then for over-
night at 100 °C in an air oven for complete polymerization,
then it was allowed to cool and sheet was removed for
further characterization (method 3). PMMA sheets having
0, 0.5, 1.0, 1.5 and 2.0 wt% RGO were prepared by using
the casting method.
Characterization and measurements
Infrared spectra (FTIR) were recorded on a Thermo Sci-
entific Nicolet 6700 FTIR spectrometer using KBr as a
background. Wide angle X-ray diffraction (WAXD) pat-
terns were recorded on a PANalytical instrument, model
number PW3040/60 X’pert PRO (Netherlands), using Ni-
filtered Cu Ka radiation (k = 0.154 nm). The voltage and
the current of X-ray tubes were 40 kV and 30 mA,
respectively. The samples were scanned at a rate of 2°/min
from 5° to 50° of 2h. Samples obtained after compression
moulding were used for recording X-ray diffraction
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patterns. Renishaw inVia Raman microscope was used for
recording Raman spectrum of samples. These spectra were
recorded using diode laser at 785 nm excitation with
Raman shift between 500 and 3000 cm-1. The bulk con-
ductivity of the composite samples (rectangular strips of
dimensions (13 9 7 9 1.5 mm3) at room temperature was
measured by four probe method using Keithley 4200
semiconducting characterization system. Thermal stability
of PMMA in presence of varying amounts of graphene was
evaluated by recording thermogravimetric (TG)/derivative
thermogravimetric (DTG) traces in nitrogen atmosphere.
Perkin-Elmer Pyris 6 TGA was used for recording TG/
DTG traces. A heating rate of 20 °C/min and 5 ± 1 mg
were used in each experiment. Morphological character-
ization was performed using EVO-50 scanning electron
microscope (SEM) and Techanai G2 20 high resolution
transmission electron microscope (HRTEM). For SEM,
manually fractured compression moulded samples were
used. The samples were coated first with silver and then
micrographs were taken. HRTEM images were recorded at
an accelerating voltage of 200 kV. For HRTEM images,
the samples were prepared by dispersing GO/graphene or
nanocomposites in DMF at a concentration of 0.5 mg/mL,
and a drop of solution after sonication was placed on a
copper grid. The tensile properties were measured on
Zwick Universal Tester Model-Z010 at room temperature.
The samples (dimensions 110 9 15 9 0.4 mm3) were
tested in accordance with ASTM D 882-10 test procedure
at a crosshead speed of 5 mm/min and gauge length of
50 mm.
Results and discussion
FTIR analysis
Figure 2 shows the FTIR spectra of graphite, graphene
oxide, graphene, PMMA and PMMA/graphene composite.
The FTIR-spectra of graphene oxide represents the char-
acteristic peaks corresponding to the oxygen functional-
ities, i.e. C–O–C, C=O and C–OH at 1202, 1718 and
1030 cm-1, respectively, and the peak at 3440 and
1396 cm-1 corresponds to hydroxyl (–OH) groups and the
broad range from 2500 to 3500 cm-1 confirms the pres-
ence of carboxylic (–COOH) group. The reduction of
graphene oxide was also confirmed by FTIR where there is
no oxygen functionality except –OH group which may be
due to incomplete reduction of GO as shown in spectra at
3470 cm-1. After the in situ bulk polymerization, the IR
spectra of graphene/PMMA composite show all the peaks
corresponding to PMMA (2998 and 2952 cm-1 for C–H
stretching, 1725 cm-1 for C=O stretching, 1200 and
1148 cm-1 for C–O stretching) as well as O–H stretching
J Mater Sci (2013) 48:6223–6232
Fig. 2 FTIR spectra of a graphite, b graphene oxide (GO), c graphene
(RGO), d PMMA and e PMMA/graphene composite (1 wt%)
peak at 3500 cm-1, which is due to incomplete reduction
of GO. These results show that there may be some chem-
ical interaction among graphene and PMMA. It has already
been reported in case of CNT/PMMA composites [13] that
the radicals of AIBN not only initiate the polymerization of
MMA, but also opens the p-bond of CNT, resulting in the
bonding between CNT and polymer chains. Graphene
possesses similar physical properties but large surface area
compared with CNTs which makes the above mentioned
chemical interaction highly probable.
X-ray diffraction analysis
Figure 3 shows the XRD patterns of graphite, graphene
oxide, graphene and composites which confirms that the
oxidation of graphite affecting its crystal structure.
Accordingly, GO shows a less intense peak at 2h = 10.1°
compared with graphite which display a strong sharp peak
at 2h = 26.5° due to the (002) planes which clearly indi-
cates that the d-spacing between the layers increased from
3.4 to 8.7 Å during oxidation process that can be ascribed
to the creation of new functional groups on the surface of
graphene. Further, the reduction of GO was carried out in
the presence of hydrazine hydrate and was confirmed by
the extremely low intensity broad peak at 2h = 24.7°. The
6227
Fig. 3 XRD patterns of graphite, GO, graphene (RGO), PMMA–
RGO (2 wt%), PMMA–RGO (1 wt%) and PMMA
above observation suggests that the chemical oxidation of
graphite was successfully carried out followed by reduction
to obtain graphene (RGO). The results also show that pure
PMMA possess broad peaks at 2h = 15° and 35° whereas,
incorporation of GO (e.g. composite with 2.0 wt% GO)
leads to appearance of characteristic peak of GO suggest-
ing that the loading is sufficient to show the diffraction
through the dilution effect of polymer and decreases the
diffraction intensity. In comparison, for RGO-loaded
PMMA composite, only the diffraction peak of PMMA was
observed and RGO hump was suppressed (Fig. 3). The
above results demonstrate that GO and RGO sheets are
fully exfoliated and dispersed in the polymer matrix.
Raman spectroscopy
The Raman spectrum for RGO displays characteristic ‘D’
and ‘G’ bands at 1310 and 1585 cm-1, respectively
(Fig. 4). The D-band is related to the sp3 state of carbon
and can be used as a proof of disruption of the aromatic
p-electrons (sp2 hybridized) of RGO sheet. For RGO, the
intensity ratio of these two bands (i.e. ID/IG ratio) is found
to be 1.01. In comparison, the D-band for GO is more
intense than G-band (ID/IG * 1.5) which shows there are
more sp3 hybridized carbons (formed due to generation of
–OH, –COOH and epoxide groups during oxidation) than
sp2 hybridized carbons. It is important to point out that,
after incorporation of RGO in the matrix, the ID/IG ratio
display an increase from 1.01 to 1.40 which indicates that
sp2 state carbons have been converted to sp3 state carbons.
This can be attributed to oxidant induced chemical
attachment of PMMA chains to the surface of RGO sheets.
Such interactions are extremely important for maintaining
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Fig. 4 Raman spectra of a graphite, b GO, c RGO, d PMMA–RGO
(1 wt%) and e PMMA–RGO (2 wt%)
filler-matrix adhesion, good mechanical properties and
desirable electrical/thermal properties.
Electrical conductivity
Figure 5 shows the variation of electrical conductivity of
PMMA at different loadings of RGO. Neat PMMA like
other acrylic polymer is very insulating and display con-
ductivity of *10-11 S/cm. The electrical conductivity of
PMMA was found to increase, on addition of RGO, such
that a sharp increase in conductivity of the composite was
observed between 0.1 and 0.5 % (w/w) of RGO loading
which can be attributed to the formation of electrically
conducting percolation networks throughout the PMMA
matrix. In particular, for a given filler matrix system, the
percolation threshold concentration is indirect measure of
the level of filler dispersion and agglomeration. Again, the
de-agglomeration and dispersion of filler in a given matrix
is closely related to the processing technique.
It can be seen that for a given RGO content, three
samples (i.e. in situ polymerized, in situ in presence of
PMMA beads and in situ polymerized followed by sheet
casting) gives different electrical conductivity highlighting
importance of compounding method. For example, con-
ductivity of above composites at 0.5 wt% RGO was
3.8 9 10-6 S/cm (for in situ polymerized) and 4.1 9
10-6 S/cm (for in situ polymerized in presence of PMMA
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J Mater Sci (2013) 48:6223–6232
Fig. 5 Effect of RGO content on the electrical conductivity of
PMMA/RGO nanocomposites
beads) which is *5-order higher than neat PMMA and
sufficient for antistatic applications [34, 38]. In compari-
son, the conductivity of corresponding sheet casted sample
was found to be 9.5 9 10-5 S/cm (i.e. 6-orders higher than
PMMA) reflecting the best filler dispersion and orientation
can be achieved compared with previous methods. The
results also indicate that conductivity increases at relatively
slow rate after percolation such that at 2 wt% RGO loading
in situ polymerized, in situ polymerized in presence of
PMMA beads and in situ polymerized followed by sheet
casting, gives conductivity value of 9.9 9 10-5,
1.8 9 10-4 and 1.7 9 10-3 S/cm, respectively. From
these results, we can conclude that preparation of in situ
nanocomposites followed by sheet casting gives better
conductivity among the three methods. Again, it is
important to note that the conductivity of [0.1 wt% RGO-
loaded composites satisfies the antistatic criteria and can be
used for electrostatic dissipation (ESD) [34, 35]. Further,
the conductivity of 2 wt% sheet-casted composite is near
the specified range [4, 36, 37] for displaying acceptable
microwave absorption making them potential candidate for
electromagnetic radiation shielding material.
Thermal stability
Figure 6a shows the TG traces of graphite, GO and RGO.
It can be seen that graphite is quite stable, although the
GO show mass loss even below 100 °C which may be
due to the pyrolysis of labile oxygen functional groups
such as –COOH, –OH, etc. After chemical reduction,
these functional groups got removed from the graphene
surface leading to improvement in thermal stability. Fur-
ther, the incorporation of RGO within PMMA matrix
enhances the thermal stability of the resultant composite.
J Mater Sci (2013) 48:6223–6232
Figure 6 also shows the thermogravimetric traces of set of
compositions prepared by incorporating varying amounts
of filler using different methods, viz. in situ polymerized
(Fig. 6b), in situ polymerized in the presence of PMMA
beads (Fig. 6b) and sheet-casting method (Fig. 6c). In all
the samples, two step degradation was observed; there-
fore, thermal stability was compared (Table 1) by com-
paring the mass losses in the temperature range of 50–250
and 250–450 °C and char yield at 700 °C. From the table,
it is clear that on incorporation of RGO in the PMMA
matrix, the thermal stability enhances in each cases, but
the first step degradation which may be due to the weak
interaction, e.g. head to head linkage, van der Waals
interaction, etc. was decreased in case of sheet casting as
compared with other two methods. Thus, we can conclude
that the sheet-casting method is better among the three
methods which were also supported by the electrical
conductivity studies.
Fig. 6 TG traces of a graphite, graphene oxide (GO) and RGO, b RGO and PMMA/RGO composites (in situ method), c RGO and PMMA/RGO
composites (in presence of PMMA beads), d RGO and PMMA/RGO composites (sheet-casting method)
6229
Morphological characterization
In order to investigate the morphology of RGO, PMMA and
PMMA/RGO composites, and to look into finer (nanoscopic)
details of the system, SEM and HRTEM have been performed.
Figure 7 shows the SEM image of RGO, PMMA and PMMA/
RGO composites (1 % w/w RGO) prepared by three methods.
The RGO (Fig. 7a) shows a typical lamella structure which are
wrinkled and crumpled due to strong van der Waals interaction
between graphene sheets. In comparison, neat PMMA not
having any microstructure (Fig. 7b) and exhibits a relatively
smooth surface. The fracture surface of in situ composite
shows a fish scaly of RGO sheets which indicate nonuniform
dispersion of RGO in the composite (Fig. 7c). However, the
composite prepared in the presence of PMMA beads exhibits
some ‘pull out’ appearance of RGO sheets, which may be due
to the poor dispersion in the area occupied by the PMMA
beads. From the enlarged image (Fig. 7f) of the composite
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Table 1 Results of TG traces

Method of Sample designation/ % Mass loss in the temperature range of % Char yield
of GO, RGO and PMMA/RGO
incorporation RGO (wt%) at 700 °C
nanocomposites in N2 50–250 °C 250–450 °C
atmosphere
GO 9.5 49.5 41.00
RGO 5.0 5.5 84.50
In situ 0.0 6.1 93.7 0.00
0.5 2.9 97.6 0.26
1.0 2.7 93.1 0.90
1.5 2.8 94.0 1.48
2.0 2.9 94.9 2.03
In presence 0.0 7.0 90.8 0.00
of PMMA beads 0.5 4.8 93.4 0.27
1.0 2.9 96.6 0.90
1.5 2.7 93.9 1.58
2.0 2.9 94.9 2.20
Sheet casting 0.0 6.1 93.7 0.00
0.5 6.0 91.3 0.26
1.0 2.7 93.4 0.83
1.5 1.4 92.7 1.30
2.0 2.1 93.1 2.02

Fig. 7 SEM images of a RGO, fracture surface of b PMMA, PMMA/RGO composite (1 wt%) c in situ d in presence of PMMA beads, e sheet
casting and f enlarged region of (e)

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Fig. 8 HRTEM images of a RGO, PMMA/RGO composite (1 wt%), b in situ, c in situ at different resolution, d sheet casting

prepared by sheet casting, it is clear that RGO sheets exhibits Table 2 Mechanical properties of PMMA/RGO composites
good dispersion and adhesion to the PMMA matrix. It is
Method RGO Young’s Tensile Strain at
expected that pouring of prepolymer syrup with dispersed loading modulus strength break (%)
RGO sheets into mould and application of pressure result in (wt%) (MPa) (MPa)
particle orientation of RGO sheets in the casted sheet’s plane,
0.0 750 ± 40.1 24.2 ± 1.6 2.8 ± 0.5
leading to improvement in electrical/thermal properties. Such
In situ 1.0 865 ± 39.4 23.0 ± 4.5 2.6 ± 0.9
orientation is also expected to improve the mechanical prop-
2.0 850 ± 45.6 14.2 ± 6.0 1.5 ± 0.4
erties in the plane of sheet. The morphological characterization
further proves that dispersion of graphene is better in case of PMMA beads 1.0 775 ± 38.2 26.0 ± 5.0 2.2 ± 0.3
samples prepared by casting. Better improvement in the 2.0 890 ± 39.8 13.0 ± 2.0 1.5 ± 0.2
properties observed in case of samples prepared by casting is Sheet casting 1.0 963 ± 56.0 28.4 ± 4.0 2.2 ± 0.3
further supported by the morphology. 2.0 1054 ± 55.0 26.6 ± 2.5 1.7 ± 0.1
Figure 8 shows the HRTEM image of RGO and PMMA/
RGO composites. The images were taken by dissolving a method on the properties and to establish the structure–
very small amount of the composite and RGO in DMF at property relationship. Table 2 shows the Young’s modulus,
concentration of 0.5 mg/mL and putting just one drop on tensile strength and strain a break as a function of pro-
the carbon grid. The HRTEM image of RGO and in situ cessing method and RGO-loading level. It can be seen that
composite (Fig. 8a, b, c) shows that there is no particle-like addition of RGO leads to improvement of modulus which
material except flexible and wrinkled sheet of RGO dis- indicate the increase in stiffness of the composite. Further,
persed in the PMMA matrix. However, one can observe the tensile strength of the composites show that addition
some heterogeneous regions, which shows some double or beyond 1 wt% loading of RGO, leads to deterioration of
even single layer RGO sheet. Whereas, the HRTEM image mechanical strength that can be attributed to the filler
of sheet-casting composite (Fig. 8d) shows that RGO agglomeration effect and poor stress transfer characteris-
sheets are better dispersed in the matrix to yield an exfo- tics. The elongation decreases with increasing RGO con-
liated PMMA/RGO composite. tent indicating brittle fracture of composites. It can also be
seen that in situ composites show deterioration of strength
Mechanical properties (lower than neat PMMA *24 MPa) even at 1 wt% RGO
loading that reflect extremely poor dispersion and high
The mechanical properties of PMMA/RGO composites agglomeration of graphene sheets within PMMA matrix. In
have been measured to study the effect of processing comparison, 2 wt% RGO-loaded sheet casted composite

123
6232
shows almost same strength as 1 wt% in situ/PMMA bead
composite which indicate the better dispersion and good
filler/matrix interaction in the former. These results are 5.
well complemented by FTIR, Raman, SEM/HRTEM and
electrical conductivity results. 6.
7.
8.
Conclusions
9.
In conclusions, the PMMA/RGO composites were suc- 10.
cessfully prepared by three methods. FTIR results show 11.
that there may be some chemical interaction among
graphene and PMMA that was well complemented by 12.
Raman spectra. XRD patterns indicate that GO and RGO
13.
sheets were fully exfoliated and dispersed in the PMMA
matrix, whereas, SEM and HRTEM morphological inves- 14.
tigations show that among three methods, the sheet-casting
method gives better exfoliation and dispersion of RGO 15.
16.
sheets. The electrical conductivity results also suggest that
sheet-casting method gives conductivity value of the order 17.
of 10-3 S/cm at the RGO loading of 2.0 wt% that could be
utilized for EMI-shielding applications. The enhancement 18.
in the thermal stability of PMMA was observed in the 19.
composite samples prepared by all the methods, but it was 20.
slightly more prominent in samples prepared by sheet- 21.
casting method. The mechanical properties were found to
22.
be dependent on filler content and processing method. It
was found that 2 wt% of RGO-loaded sheet casted com- 23.
posite show almost same strength as 1 wt% in situ/PMMA
bead composite which indicate the better dispersion and 24.
good filler/matrix interaction in the former, which is sup- 25.
ported by FTIR, Raman and SEM/TEM results. The
superior thermal, mechanical and electrical properties of 26.
composites prepared by sheet-casting method make this a
27.
preferred method for antistatic, microwave absorbing and
packaging applications. 28.
Acknowledgements The authors thank the University Grant Com- 29.
mission (UGC) for providing financial assistance to one of the authors
Mr. Sandeep Nath Tripathi and IIT Delhi for providing all the facil- 30.
ities. The authors also thank the Director CSIR-National Physical
Laboratory for extending the electrical characterization facilities. 31.
32.
33.
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