Research Article

Received: 30 September 2011

Revised: 13 January 2012

Accepted: 24 February 2012

Published online in Wiley Online Library: 12 June 2012

(wileyonlinelibrary.com) DOI 10.1002/pi.4263

A facile route to develop electrical conductivity

with minimum possible multi-wall carbon
nanotube (MWCNT) loading in poly(methyl
methacrylate)/MWCNT nanocomposites
Nilesh K Shrivastava, Prativa Kar, Sandip Maiti and Bhanu B Khatua
Abstract
Today, we stand at the threshold of exploring carbon nanotube (CNT) based conducting polymer nanocomposites as a new
paradigm for the next generation multifunctional materials. However, irrespective of the reported methods of composite
preparation, the use of CNTs in most polymer matrices to date has been limited by challenges in processing and insufficient
dispersability of CNTs without chemical functionalization. Thus, development of an industrially feasible process for preparation
of polymer/CNT conducting nanocomposites at very low CNT loading is essential prior to the commercialization of polymer/CNT
nanocomposites. Here, we demonstrate a process technology that involves in situ bulk polymerization of methyl methacrylate
monomer in the presence of multi-wall carbon nanotubes (MWCNTs) and commercial poly(methyl methacrylate) (PMMA) beads,
for the preparation of PMMA/MWCNT conducting nanocomposites with significantly lower (0.12 wt% MWCNT) percolation
threshold than ever reported with unmodified commercial CNTs of similar qualities. Thus, a conductivity of 4.71 105 and
2.04 103 S cm1 was achieved in the PMMA/MWCNT nanocomposites through a homogeneous dispersion of 0.2 and 0.4 wt%
CNT, respectively, selectively in the in situ polymerized PMMA region by using 70 wt% PMMA beads during the polymerization.
At a constant CNT loading, the conductivity of the composites was increased with increasing weight percentage of PMMA beads,
indicating the formation of a more continuous network structure of the CNTs in the PMMA matrix. Scanning and transmission
electron microscopy studies revealed the dispersion of MWCNTs selectively in the in situ polymerized PMMA phase of the
nanocomposites.
c 2012 Society of Chemical Industry


Keywords: conductivity; matrix; MWCNT; nanocomposites; PMMA

INTRODUCTION

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A number of thermoplastics, such as poly(methyl methacrylate) (PMMA),8 polystyrene,9 polyethylene,10 polycarbonate11 and
others,12,13 have been used to prepare polymer/CNT nanocomposites with improved electrical properties. PMMA is of great research
interest due to its application in the electronics industry, packaging etc. A considerable amount of research has been carried
out on the electrical properties of PMMA/CNT composites prepared by various methods.14 32 For instance, Du et al.14 reported
DC conductivity of 2.4 108 S cm1 at 0.5 wt% single-wall
carbon nanotube (SWCNT) loading in PMMA/SWCNT composites prepared by a coagulation method. Clory et al.15 prepared
PMMA/multi-wall carbon nanotube (MWCNT) composites by melt
mixing that showed DC conductivity of 107 S cm1 at 1 wt%
MWCNT loading. Haggenmueller et al.16 used a method that involved a combination of solvent casting and melt mixing for
the preparation of PMMA/SWCNT films. The composites showed
DC conductivity of ca 1.18 105 and 1.15 103 S cm1 with

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Correspondence to: Bhanu B Khatua, Materials Science Centre, Indian Institute

of Technology Kharagpur, Kharagpur-721302, India.
E-mail: khatuabb@matsc.iitkgp.ernet.in
Materials Science Centre, Indian Institute of Technology Kharagpur, Kharagpur721302, India

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Electrically conducting polymer/nanoparticle composites are

currently of great interest because of their wide range of
applications in, for example, electronics, aerospace, the military,
electromagnetic induction shielding, electrostatic dissipation and
sensors. Intensive research is being carried out for cost-effective
production of these materials by effective dispersion and low
loading of conducting particles. A considerable amount of research
on polymer/carbon nanotube (CNT) nanocomposites has revealed
the potential of CNTs as an electrically conductive filler that
provides electrical conductivity in an insulating polymer matrix at
very low loading compared with conventional conductive fillers
such as carbon black.1 3 The exceptionally superior performance
of CNTs in polymer composites can be achieved by optimizing
their dispersion and distribution in the polymer matrix. However,
it is quite difficult to achieve a homogeneous dispersion of CNTs
in the polymer matrix as CNTs aggregate due to strong van der
Waals forces originating from their small size and large surface
area.4 Chemical modification or functionalization of the CNTs
increases their compatibility with the polymers, which helps in
better dispersion and interfacial adhesion of the CNTs in the host
polymers.5 7 However, it creates surface defects which reduce the
conductivity of the CNTs.

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1.3 and 6.6 wt% SWCNT loading, respectively. In another study,

Sung et al.17 reported DC conductivity of 3.1 104 S cm1 and
1.4 102 S cm1 at 1 wt% and 5 wt% MWCNT loading, respectively, in solution cast PMMA/MWCNT composites. Du et al.18
reported DC conductivity of 104 S cm1 at 2 wt% CNT loading
in PMMA/SWCNT composites prepared by a coagulation method.
Benoit et al.19 reported DC conductivity of 5 107 S cm1 with
critical exponent t = 2.1 at 0.33 wt% SWCNT loading for solution cast PMMA/SWCNT composites. A report on the electrical
properties of PMMA/SWCNT composites by Du et al.20 indicated
DC conductivity ca 1 103 S cm1 at 2 wt% CNT loading in
the composites and critical exponent t = 2.3. Skakalova et al.21
prepared PMMA/SWCNT composites by solution casting, using
SOCl2 doped highly purified SWCNTs. The composites exhibited
very high conductivity (ca 10 S cm1 ) at 10 wt% doped SWCNT
loading compared with that (ca 2 S cm1 ) with undoped SWCNTs
at similar loading. Kim et al.22 in their study showed a DC conductivity of ca 1 S cm1 at 10 wt% CNT loading in solution cast
PMMA/MWCNT composites with critical exponent value t = 2.3.
Schmidt et al.23 reported DC conductivity ca 2 101 S cm1 at
1.5 wt% CNT loading in solution cast PMMA/MWCNT composites. Dai et al.24 observed DC conductivity ca 1 103 S cm1
and ca 1 106 S cm1 along the alignment and perpendicular to the alignment, respectively, in solution cast PMMA/SWCNT
stretched fiber composites at 7 wt% SWCNT loading. Regev et al.25
prepared PMMA/MWCNT composites by latex technology and
observed a DC conductivity of 1 103 S cm1 with critical
exponent t = 2.0 at 1.5 wt% MWCNT loading in the composites. Weghkowska et al.26 used SOCl2 functionalized highly pure
SWCNTs to prepare transparent and conducting PMMA/MWCNT
composites and found a DC conductivity of ca 4.7 101 S cm1
at 0.5 wt% CNT loading. Sundaray et al.27 used the electrospinning method to prepare PMMA/MWCNT composite fibers (CNTs
oriented along the fiber axis) that showed a DC conductivity of ca
1 104 S cm1 at 1 wt% MWCNT loading. A comparative study
by Yuen et al.28 revealed higher DC conductivity (8 106 S cm1 )
in in situ polymerized PMMA/MWCNT composites than in those
prepared by the ex situ method at 0.75 wt% MWCNT loading. Logakis et al.29 observed DC conductivity of ca 5 104 S cm1 at 1
wt% MWCNT loading in melt-blended PMMA/MWCNT composites.
Shang et al.30 reported a higher DC conductivity (5 106 S cm1 )
in microemulsion polymerized PMMA/MWCNT (5 wt%) composites than that (1 107 S cm1 ) obtained with solution casting
at similar CNT loading. Lahelin et al.31 found a DC conductivity of
1 105 S cm1 at 3 wt% CNT loading in PMMA/MWCNT composites prepared via the in situ emulsion and emulsion/suspension
polymerization methods. Kim et al.32 obtained a DC conductivity of ca 5 104 S cm1 in solution blended PMMA/MWCNT
composite thin films at 3 wt% CNT loading. Lee et al.33 showed
that DC conductivity of 1 105 S cm1 could be achieved at 1.5
wt% MWCNT loading in melt-extruded PMMA/styrene acrylonitrile
(SAN)/MWCNT composites.
In summary, reports on PMMA/CNT composites revealed that
development of electrical conductivity in the PMMA matrix at a
very low percolation threshold of MWCNTs is a major concern
without chemical modification of the CNT. This provides scope for
developing an easy method that leads to lowering the percolation
threshold of the CNTs in polymer/CNT conducting composites.
Here, we demonstrate a simple, industrially scalable and environmentally safe process (no solvent, no liquid waste/solvent
effluent is generated) that involves in situ polymerization of methyl
methacrylate (MMA) monomer in the presence of MWCNTs and

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commercial PMMA beads for the preparation of PMMA/MWCNT

composites, which overcomes the challenges of reducing the
percolation loading in the PMMA matrix without any CNT functionalization. The key to this study was to create a continuous
network of CNTs through selective regions (in situ polymerized
PMMA phase) in the matrix, while the major portions (PMMA
beads) of the matrix, free from the CNT dispersion, behave like
excluded volume in the composites.

EXPERIMENTAL
Materials
MMA monomer used in this study was of synthesis grade and
procured from Loba Chemie Pvt. Ltd, Mumbai, India. Benzoyl
peroxide, used as polymerization initiator, was obtained from
Sigma-Aldrich Inc., USA. General purpose, non-crosslinked PMMA
(grade Gujpol-876G with Mw 105 000 g mol1 , specific gravity
1.19, melt flow index (MFI) 6 g/10 min at 230 C and 1.2 kg load)
pellets (average diameter ca 2.35 mm and length ca 2.70 mm)
were procured from Gujarat State Fertilizers and Chemicals Ltd,
Gujarat, India. Micron-sized spherical PMMA beads (PMMA-s
beads) (diameter 80120 m; MFI 11.2 g/10 min at 230 C and
1.2 kg load) were prepared by suspension polymerization of MMA.
Industrial grade MWCNTs (NC 7000 series; average diameter 9.5 nm
and length 1.5 m; surface area 250300 m2 g1 ; 90% carbon
purity) were purchased from Nanocyl S.A., Belgium. The MWCNTs
were used as received, without any chemical modifications.
Preparation of PMMA/MWCNT composites through bulk
polymerization
MMA (250 mL) was placed in a 500 mL separating funnel and
20 mL of 5 wt% NaOH aqueous solution was added. The mixture
was shaken for 15 min and the purified MMA was decanted into a
250 mL beaker. This process was repeated five times. Finally, after
washing with deionized water, the purified MMA was collected.
The desired amount (0.25 g) of MWCNTs was dispersed in
40 mL purified MMA in a 250 mL round-shaped three-neck glass
reactor. The MWCNT/MMA mixture was ultrasonicated for 2 h
at room temperature using a probe type ultrasonic processor
(OSCAR Model PR-250; ultrasonic power 250 W, frequency 25 kHz,
probe tip diameter 6 mm). Then the reactor, connected with a
refluxing condenser and nitrogen inlet to one of the three necks,
was immediately placed on a hot plate magnetic stirrer. The
required amount (1 wt%) of benzoyl peroxide, as polymerization
initiator, was added to the MWCNT/MMA dispersion in the reactor
under constant stirring and the reactor temperature was gradually
increased to ca 85 C. During the progress of polymerization
(after ca 30 min of the reaction when the MWCNT/MMA mixture
started developing viscosity), 20 g of commercial PMMA beads
were added into the reactor. Addition of the PMMA beads to
the MMA monomer in the initial stage of polymerization would
result in swelling of the PMMA beads and thus dispersion of some
CNTs inside the beads. The reaction was continued for 1 h under
a nitrogen atmosphere with constant temperature and stirring.
The PMMA/MWCNT composites thus obtained through in situ bulk
polymerization of MWCNT/MMA in the presence of PMMA beads
was air dried and finally dried in an air oven at 60 C for 24 h. From
the weight (ca 50 g) of the final product, the calculated loadings of
CNTs and PMMA beads in the PMMA/MWCNT composites were 0.5
and 40 wt%, respectively. PMMA/MWCNT composites with various
CNT loadings (0.1, 0.2, 0.3, 0.4, 0.7 and 1.0 wt%) and higher amounts

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Figure 1. Schematic representation of the composite manufacturing process.

of PMMA beads (50, 60, 70 and 80 wt%) were also prepared

through the same polymerization route, by varying the amount of
MMA, MWCNTs and PMMA beads during polymerization. Through
gel permeation chromatography the weight-average molecular
weight (Mw ) of the bulk polymerized neat PMMA was ca 32 600.
The MFI values for bulk polymerized PMMA and (30/70 w/w) bulk
polymerized PMMA/PMMA beads at 230 C and 1.2 kg load were
10.8 and 7.6 g/10 min, respectively. A schematic representation
for the preparation of the PMMA/MWCNT composites is illustrated
in Fig. 1.
Molding of the PMMA/MWCNT composites
The bulk polymerized PMMA/MWCNT composites with various
amounts of PMMA beads and CNT loadings were compression
molded for 10 min at 210 C in a hot press under constant pressure
(10 MPa) and the molded parts were air-cooled to room temperature for further characterization. During compression, melt
flow of the highly viscous PMMA beads (Mw 105 000 g mol1 )
inside the mold was expected to be significantly less than for bulk
polymerized PMMA (Mw 32 600 g mol1 ).

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ac = 0  tan

(1)

where is 2f (f is the frequency) and 0 is the dielectric constant

of a vacuum. The dielectric constant  was determined using the
equation
Cp
 =
(2)
C0
where Cp is the observed capacitance of the sample (in parallel
mode) and C0 is the capacitance of the cell. The value of C0 was
calculated using the area (A) and thickness (d) of the sample,
following the relation
0 A
C0 =
(3)
d
Optical microscopy
A high resolution optical microscope (HROM, Carl Zeiss Vision
GmbH) was used to investigate the distribution/localization of the
MWCNTs and PMMA beads in the composite matrix. Images of the
compression molded samples were taken in monochromatic light
at different resolutions.
Transmission electron microscopy (TEM)
The extent of dispersion of the MWCNTs in the PMMA matrix
was studied by TEM (JEM-2100, JEOL, Japan) operating at an
accelerating voltage of 200 kV. The PMMA/MWCNT composite
sample was ultra-microtomed under cryogenic conditions to a
thickness of 5080 nm. Since the CNTs have a much higher
electron density than the polymers, they appear dark in the TEM
images.
Field emission scanning electron microscopy
The phase morphology of the PMMA/MWCNT composites was
studied with a field emission scanning electron microscope (Carl
Zeiss-SUPRATM 40) operated at an accelerating voltage of 10 kV.
The specimens were carefully broken under a liquid nitrogen
atmosphere. The fractured surface of the samples was coated with
a thin layer of gold to avoid electrical charging, and SEM images
were taken of the fracture surface.

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Characterization
Electrical conductivity
DC conductivity measurements were done on compression
molded specimen bars of dimensions 30 10 3 mm3 . The
electrical conductivity of the conducting composite was measured
with a two-probe technique. A minimum of five tests was
performed for each sample and the average data are reported.
AC electrical conductivity and dielectric properties of the
composite (disc-type sample with thickness 0.3 cm and area
1.88 101 cm2 ) were obtained using a computer-controlled
precision impedance analyzer (Agilent 4294A) on application of
an alternating electric field across the sample cell in the frequency
range 40 Hz to 3 106 Hz. All scanning was done at room
temperature. The parameters such as dielectric constant ( ) and
dielectric loss ( ) were obtained as a function of frequency. The
AC conductivity ( ac ) was calculated from the dielectric data using

the relation

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Dynamic mechanical analyzer
Thermomechanical properties of the composites were measured
with the compression molded bar sample by using a dynamic
mechanical analyzer (DMA 2980 model, TA Instruments Inc., USA).
Experiments were done in the cantilever mode at a constant
vibration frequency of 20 Hz in the temperature range 30150 C
at a heating rate of 5 C min1 in a nitrogen atmosphere. The
dimensions of the specimen (bar) were 35 12.7 3 mm3 .

RESULTS AND DISCUSSION

Electrical properties
Figure 2(a) represents the room temperature DC conductivity of
the PMMA/MWCNT composites containing 0.2 wt% CNTs with
various amounts (4080 wt%) of PMMA beads. It should be
noted that the in situ polymerized PMMA/MWCNT composites
without any PMMA beads did not show any electrical conductivity
at 0.2 wt% CNT loading. Interestingly, a DC conductivity of
7.1 106 S cm1 was achieved in composites at similar (0.2
wt%) CNT loading when the composites was prepared by in situ
polymerization of MMA in the presence of MWCNTs and 40
wt% PMMA beads. As can be seen, the DC conductivity of
the composites gradually increased with increasing PMMA bead
content (wt%) in the composites, and a combination of 70 wt%

PMMA beads and 30 wt% in situ polymerized PMMA/MWCNTs in

the composites showed the maximum conductivity.
We assume that the presence of PMMA beads increased the effective concentration of the CNTs in the in situ polymerized PMMA
phase of the composites and enhanced the conductivity through
increasing the CNTCNT contact points and entanglements although the overall CNT loading in the composites remained the
same. The PMMA beads in the matrix can be regarded as excluded volume in which the CNTs cannot penetrate (as is evident
from the optical micrograph in Fig. 8(a), later), raising the CNT
concentration in the in situ polymerized continuous PMMA phase
adjacent to the PMMA beads. A decrease in electrical conductivity
of the composites above 70 wt% of PMMA beads could be due
to blockage of conducting paths as a result of an increase in
non-conducting PMMA bead content in the matrix.
If the above assumption for the role of the beads as excluded
volume in the matrix is true, then one would expect higher
conductivity of the composites with micron-sized PMMA beads
(high surface area) than that obtained with larger PMMA beads
at a similar weight percent of the beads. To check this possibility,
we prepared the composites through bulk polymerization of
MMA in the presence of MWCNTs and suspension polymerized
PMMA-s beads (diameter of the beads 80120 m). As is evident
(Fig. 2(b)), the composites with 25 wt% PMMA-s beads showed
DC conductivity of ca 5.05 106 S cm1 at 0.2 wt% CNT loading,
which was comparable with that (ca 7.1 106 S cm1 ) obtained
with 40 wt% PMMA beads at similar CNT loading. Interestingly, the
composites with 40 wt% PMMA-s beads showed DC conductivity
of ca 3.4 105 S cm1 at 0.2 wt% CNT loading, which was almost
half an order of magnitude larger than that obtained with 40
wt% PMMA beads at similar CNT loading. However, at higher
bead content (above 50 wt%), the conductivity of the composites
showed a decreasing tendency. This might be due to the blockage
of conducting paths as a result of an increase in non-conducting
PMMA bead content in the composite. With micron-sized PMMA
beads, although the population (number of PMMA-s beads) of
the excluded volume in the matrix will be more at a higher
weight percent of the beads, it will lead to the formation of a
continuous phase of PMMA-s beads due to molten PMMAPMMA
bead contact during compression molding (as shown in Fig. 8(f),
later). Thus, the conductivity of the composites started decreasing
above 50 wt% PMMA-s beads.
Figure 3 shows the variation of DC conductivity with increasing
MWCNT loading in the PMMA/MWCNT composites in the presence
of 70 wt% PMMA beads. A drastic increase in conductivity by
several orders of magnitude, from 1011 to 104 S cm1 , can be
observed on varying the CNT content between 0.02 and 0.3 wt%.
This radical increase in the electrical conductivity indicated the
formation of a continuous network structure of MWCNTs in the
composites, which is well known as a percolation network. Thus,
the percolation threshold of the MWCNTs in the composites was in
the range 0.020.3 wt% of the CNT loading. On further addition of
CNTs, a slow but gradual increase in conductivity of the composites
was observed. The conductivity of the PMMA/MWCNT composites
with 70 wt% PMMA beads was measured to be 4.3 102 S cm1
at 1 wt% CNT loading. To estimate the percolation threshold
concentration (pc ), the experimental data were fitted using a
power law equation for the composite conductivity near the
percolation threshold:20

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Figure 2. DC conductivity of PMMA/MWCNT composites with the weight

percent of (a) commercial PMMA beads and (b) micron-sized PMMA-s
beads in the PMMA matrix at various MWCNT loadings.

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DC (p pc )t
DC (p pc )

for p > pc
for p < pc

(4)
(5)

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Figure 3. DC conductivity of PMMA/MWCNT composites with MWCNT

loading. Inset: loglog plot of DC versus p pc for the same composites.
The straight line in the inset is a least-squares fit to the data using Eqn (4),
giving the best fit values pc = 0.12 and t = 2.76.

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where DC is the composite conductivity, p is the volume fraction

of MWCNTs, pc is the percolation threshold and s and t are
critical exponents. Figure 3 (inset) shows the plot of log DC versus
log(p pc ). By assuming pc = 0.12 wt%, the critical exponent t
was calculated and found to be t = 2.76 with a standard deviation
of 0.094 from the slope of the fitted straight line. The p pc
values obtained by assuming pc = 0.12 wt% gave an excellent
fit to the conductivity of the PMMA/MWCNT composites. This
result is in good agreement with the percolation behavior given
in Eqn (4) and indicates an extremely low percolation threshold
at 0.12 wt% MWCNT loading in the PMMA matrix. With excellent
dispersion and individualization of high aspect ratio MWCNTs in
the PMMA matrix. The value t = 2.76 for the CNT composites is
consistent with the theoretical value of t 2.0 for a percolation
network in three dimensions.34
It has been reported that the calculated critical exponent t in
three-dimensional network systems is between 1.6 and 2.0, but
experimentally obtained t values vary between 1.3 and 3.1.35 In
our work, the value of t 2.76 obtained is in good agreement
with the theoretical and experimental values in the literature.
According to three-dimensional percolation theory, values of the
critical exponent t lower than the universal value indicate that
percolation takes place in a network displaying more dead ends
(ends of CNTs which are not connected with at least two other
CNTs in a continuous path) and increase in t could be associated
with a reduction in the number of dead ends in the network. As
the critical exponent t depends on the microstructural properties
(i.e. the length and diameter of CNTs, carbon purity, structure etc.)
of the composites, researchers have found different t values.
By using Eqn (4), extrapolation of p 100 gives a conductivity
of 1.09 101 S cm1 , which is far lower than the conductivity (50 S cm1 ) of pure MWCNTs, consistent with previous
reports.36 38 The decrease in conductivity is due to coating of
the individual nanotubes with insulating polymer, which resulted
in poor electrical contact between the nanotubes and hence a
large contact resistance.39 In general, electron transfer from one
electrode to another becomes restricted through the insulating
polymer due to the existence of an energy barrier. However, when
the distance between neighboring electrodes is sufficiently small,
under applied voltage the shape of the energy barrier is changed

and there is a driving force for the electrons to move across the
barrier by tunneling, resulting in a small current flow. The electrons
in the polymer composites are tunneling one by one from one
MWCNT electrode to the nearest MWCNT electrode thus forming
an MWCNT-polymer pathway. This induces resistance and limits
the conductivity of the composite. In the range of CNT loading
0.020.3 wt%, the conductivity of the PMMA/MWCNT composites was drastically increased by several orders of magnitude (from
1011 to 104 S cm1 ). At a CNT loading of 0.51 wt%, the conductivity of the composites stabilized at around 103 S cm1 , which
is quite a high conductivity value for PMMA/MWCNT composites
at this low level of MWCNT loading with unaligned, unmodified,
commercially available MWCNTs.
Figure 4(a) compares the conductivity of the PMMA/MWCNT
composites under investigation with the published data for
PMMA/CNT composites.27 29,31 33 The PMMA/MWCNT composites prepared by our method showed a higher conductivity at the
lowest CNT loading in comparison with the previously reported
data. This exceptionally low percolation threshold of ca 0.12 wt%
MWCNT loading in the composites, prepared by in situ bulk polymerization of MMA in the presence of MWCNTs and PMMA beads,
can be explained by assuming an excluded volume of the beads in
the matrix which the CNTs could not (or could hardly) penetrate.
This resulted in raising the neighboring CNT concentration very
high in the in situ polymerized continuous PMMA phase, adjacent
to the PMMA beads.
Figure 4(b) compares the electrical conductivity of the
PMMA/MWCNT composites prepared by our new method with
those obtained by conventional solution blending and melt mixing
methods with different weight fractions of MWCNTs. It is noteworthy that the conductivity of the solution blended composites
at 1 wt% and 3 wt% CNT loadings were ca 6.26 105 S cm1
and 1.4 103 S cm1 , which are comparable to the conductivity
(4.71 105 S cm1 and 2.04 103 S cm1 ) of the composites
achieved with this new method even at 0.2 wt% and 0.4 wt%
CNT loadings, respectively, in the presence of 70 wt% PMMA
beads during polymerization of MMA/MWCNT. Nonetheless, the
composites prepared by the melt mixing method showed a conductivity of ca 8.23 105 S cm1 at 2.7 wt% CNT loading, which
is ca 14 times higher CNT loading than that of composites with
similar conductivity obtained by the proposed new method of
composite preparation. The high electrical conductivity of the
PMMA/MWCNT composites prepared by this new method can be
explained in terms of the excluded volume of the beads in the
PMMA matrix. Thus, the CNTs are becoming concentrated in a
small region (in situ polymerized PMMA phase) of the composites,
which decreases the average distance between the nanotubes.
This enhances physical contacts between the CNTs or electron
tunneling through the polymer, leading to higher conductivity,
even at low CNT loading, than solution blended and melt mixed
PMMA/MWCNT composites.
Figure 5(a) shows the variation of AC conductivity with
frequency at room temperature for 0.2 wt% MWCNT loaded
composites with various proportions of PMMA beads. As can
be seen, the conductivity of neat PMMA increased with increasing
frequency, resembling the general trend of insulating materials.
The conductivity of the composites gradually increased with
increase in the content of PMMA beads keeping CNT loading
constant. This was due to the formation of a more continuous
network structure of CNTs with increasing PMMA bead content.
Up to a critical frequency, the AC conductivity remained almost
constant showing a plateau region. Beyond the critical frequency,

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Figure 4. Comparison of (a) our results with published electrical conductivity data for PMMA/MWCNT composites and (b) the DC conductivity of
PMMA/MWCNT composites prepared by different methods in our study.

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the conductivity of all the composites increased with further

increase in frequency. The critical frequency was shifted to a
higher region with increase in the proportion of PMMA beads. This
might be due to the increase in effective concentration of MWCNTs
with increasing weight percent of PMMA beads that led to the
formation of a higher number of network structures. This result is
in agreement with previous reports where the critical frequency
shifted to a higher frequency region with increase in conducting
filler loading.40,41
Figure 5(b) shows the frequency dependence of AC conductivity
of the composites with variation of CNT loading, keeping the PMMA
bead content constant (70 wt%). As can be seen, the composites
with 0.1 wt% CNT loading had slightly higher conductivity than that
of pure PMMA. However, the conductivity of the PMMA/MWCNT
(0.1 wt%) composites progressively increased with frequency,
similarly to that of pure PMMA. The conductivity of the composites
was increased drastically in the presence of 0.2 wt% CNT loading
into the PMMA matrix. However, beyond this (0.2 wt%) loading, a
slight variation in the CNT loading (up to 1 wt%) gradually increased
the conductivity of the composites, although the rate of increase
was small. This could be due to the formation of a few dead
ends along with the creation of conducting paths beyond 0.2 wt%
CNT loading. The conductivity of the PMMA/MWCNT composites
with 0.2 wt% CNT loading remained constant up to the critical

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Figure 5. AC conductivity of the PMMA/MWCNT composites versus

frequency at (a) various weight percent of PMMA beads at 0.2 wt% CNT
loading and (b) different MWCNT loadings at constant PMMA bead content.

frequency, and then an increase in the conductivity was apparent

with frequency. At higher CNT loading (0.5 wt%), a slight increase
in conductivity of the composites was evident at higher frequency.
Interestingly, the conductivity of the composites with 1 wt% CNT
loading was more or less constant with change in frequency
throughout the entire frequency range. This is the behavior of a
highly conducting composite where the flow of current is due to
electron transfer and is not related to the polarization.
The room temperature frequency dependence of the dielectric
constant ( ) of neat PMMA and the PMMA/MWCNT composites
at constant CNT (or PMMA bead) loading with increasing weight
percent of PMMA beads (or CNTs) is shown in Fig. 6. The dielectric
constant of neat PMMA has a low value, which decreased
marginally with increasing frequency. In both cases, all the
composites showed higher dielectric constant at low frequency.
For instance, the PMMA/MWCNT composites with 40 wt% PMMA
beads at 0.2 wt% CNT loading showed a significantly higher (ca
400 times higher than PMMA) dielectric constant at low frequency
(Fig. 6(a)). It was interesting to observe that a further increase (ca
10 times) in dielectric constant of the composites was evident
when the PMMA bead content was increased to 50 wt%. However,
beyond this proportion of beads, the composites showed lower

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Electrical conductivity with minimum CNT loading

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Figure 6. Dielectric constant of PMMA/MWCNT composites (a) with variation of PMMA bead loading at constant CNT loading and (b) with variation
of CNT loading at constant PMMA bead loading.

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dominates at higher frequency, the value of the relative dielectric

constant decreases with increase in the frequency. A similar result

for the dielectric response was found by Potschke

et al.43 where
the dielectric constant decreased with increasing frequency in
polycarbonate/MWCNT composites.
Figure 6(b) shows an increase in dielectric constant of the
PMMA/MWCNT composites with increasing content of CNTs at
constant bead content (70 wt%). Above the percolation point the
dielectric constant increases at a much faster rate and exhibits
an abrupt change.44 At low frequencies, the very high values
of dielectric constant for the composites above the percolation
threshold could be due to the higher concentration of MWCNTs
that increased the number of dead ends, forming microcapacitors
of various length scales. The charge between polymer and CNTs
increased in the dead ends. Thus, the overall capacitance was
increased, which in turn increased the dielectric constant of the
composites.
Figure 7 shows the variation in dielectric loss ( ) with frequency
at room temperature for the PMMA/MWCNT composites with
various PMMA bead and CNT contents. In both cases, all the
composites showed a decrease in dielectric loss with increase in
frequency. This behavior may be attributed to dipole relaxation
phenomena, where movement of the electric dipoles cannot be
in phase with the frequency of the applied electric field.

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1689

dielectric constant than that obtained with 40 wt% PMMA beads

at similar CNT loading.
The high dielectric constant (permittivity) of the composites
with 40 and 50 wt% PMMA beads was reached because of the
space charge built up at the interface between the polymer phase
and the conducting fillers (MWCNTs) due to their difference in
conductivity.42 As a result, the migrating charge carriers become
trapped at the interface of these heterogeneous systems and
the electric field distortion caused by the accumulated charges
increases the overall capacitance of the material and hence the
dielectric constant. Higher loading of PMMA beads (60 wt% and
more) increased the effective concentration of the CNTs in the
in situ polymerized PMMA phase of the composites. This increased
the CNTCNT contact points (highly extended network structure)
and entanglements, enhancing the conductivity, which led to a
decrease in both the space charge built up and the dielectric
constant.
However, all the composites showed a sharp decrease in
dielectric constant with increasing frequency. The high value
of the dielectric constant of composites at low frequency might
be due to the combination of different types of polarization
at room temperature. At higher frequency a relaxation process
took place that led to a drastic drop in the dielectric constant
with increase in frequency. Since only electronic polarization

Figure 7. Dielectric loss (a) with variation of PMMA bead content at

constant CNT loading (0.2 wt% CNTs) and (b) with variation of CNT content
at constant PMMA bead loading (70 wt% PMMA beads).

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NK Shrivastava et al.

Figure 8. (a) Transmission optical micrograph, (b), (c) field emission SEM micrographs at different magnifications, and (d) TEM micrograph of
PMMA/MWCNT (0.2 wt%) composites containing 70 wt% PMMA beads. Field emission SEM micrographs of PMMA/MWCNT (0.2 wt%) composites
containing (e) 25 wt% PMMA-s beads and (f) 60 wt% PMMA-s beads.

It can be seen (Fig. 7(a)) that the dielectric loss ( ) of the
composites was increased with the increase in PMMA bead content
(wt%) at constant CNT loading (0.2 wt%). In the lower frequency
region, dielectric loss was increased with increase in PMMA bead
loading, while a marginal effect was found at higher frequency. It
has already been reported that, with increase in conducting filler
loading, dielectric loss increases at lower frequency.40,41 Here,
the effective concentration of the CNTs in the in situ polymerized
PMMA phase was increased on increasing the PMMA bead content
in the composites. This result is also supported by the dielectric
loss values shown in Fig. 7(b), which represents the variation in
dielectric loss with frequency at room temperature with increasing
CNT loading. As observed, the dielectric loss of the composites
increased with increasing CNT loading, keeping the loading (70
wt%) of PMMA beads constant, similarly to that with increasing
bead content at constant CNT loading in the composites.

1690

Morphology
Figure 8 presents micrographs of the PMMA/MWCNT composites
with 0.2 wt% CNT loading in the presence of PMMA beads. Trans-

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mittance optical micrographs of the PMMA/MWCNT composites

containing 70 wt% PMMA beads and 0.2 wt% CNTs clearly indicated the selective distribution of CNTs in certain regions (dark
zones) of the PMMA matrix (Fig. 8(a)). The deformation in shape of
the PMMA beads in the composites was due to the melting and
flowing of the beads during compression molding. This morphology suggested that CNTs formed a continuous network structure
in the in situ polymerized PMMA regions (dark zones), outside the
PMMA beads, leaving the PMMA beads (white zones) free from the
CNT dispersion. The PMMA beads in the matrix phase where the
CNTs failed to penetrate can be considered as excluded volume.
This led to an increase in the effective concentration of the CNTs
in the in situ polymerized PMMA matrix, and thus increased the
probability of forming more conducting paths in the composites.
The field emission SEM image of the cryogenic fractured,
compression molded PMMA/MWCNT composites containing 0.2
wt% CNTs and 70 wt% PMMA beads at low magnification
(Fig. 8(b)) revealed the dispersion of CNTs in selective regions
of the composites and penetration of a small amount of the
CNTs in the PMMA bead regions during molding. The extent of

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Electrical conductivity with minimum CNT loading

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dispersion of the CNTs in selective regions (marked in Fig. 8(b)) of

the composites is shown in the field emission SEM image at higher
magnification (Fig. 8(c)). From the image, quite a high level of
dispersion of the CNTs is evident, leading to an important network
structure formation even at extremely low CNT loading in the
in situ polymerized PMMA phase of the composites.
The selective dispersion of the CNTs in the in situ regions of the
PMMA/MWCNT composites consisting of 70 wt% PMMA beads
and 0.2 wt% CNTs can be visualized by TEM observations, as
shown in Fig. 8(d) in which the CNTs are shown in black and the
background is the PMMA matrix. As can be seen, the continuous
network structure of the MWCNTs was formed through dispersion
of the CNTs in selective regions (in situ polymerized PMMA phase)
of the PMMA matrix in the composites. The TEM image of a
selective region (marked in Fig. 8(d)) at higher magnification (inset
of Fig. 8(d)) clearly showed a high level of dispersion of the CNTs
in the in situ bulk polymerized PMMA phase.
An in-depth analysis of the absolute morphology of the
composites was carried out with the PMMA/MWCNT composites
prepared by bulk polymerization of MMA in the presence of
MWCNTs and suspension polymerized PMMA-s beads (diameter
80120 m). Figure 8(e) displays the field emission SEM image of
compression molded PMMA/MWCNT composites containing 0.2
wt% CNTs and 25 wt% PMMA-s beads. At low magnification, the
presence of PMMA-s beads in the in situ polymerized PMMA phase
was evident in the image. The retention of the spherical shape
of the beads in the molded sample might be due to the micron
size of the beads, which in the melt state during molding acted as
micron-sized droplets/particles. Thus, under compression without
applying any shear force (mixing rpm), the molten PMMA-s beads
suspended in the molten in situ polymerized PMMA/MWCNT phase
could flow as droplets without much deformation in shape. The
field emission SEM image of the matrix phase (selected region in
Fig. 8(e)) at high magnification clearly showed the individualization
and formation of a highly structured network of CNTs mostly in
the in situ polymerized PMMA phase (inset of Fig. 8(e)), and the
CNTs could hardly penetrate inside the PMMA-s beads of the
composites. However, the presence of a higher content (60 wt%)
of PMMA-s beads in the composites resulted in the formation of
a smaller amount of continuous network of CNTs due to fusing of
the PMMA-s beads, as shown in Fig. 8(f).

Polym Int 2012; 61: 16831692

the amount (70 wt%) of PMMA beads constant. A sharp increase

in room temperature storage modulus of the PMMA/MWCNT (0.2
wt%) composites with 70 wt% PMMA beads can be noticed when
the CNT content was increased to 0.4 wt% and 0.7 wt%. This
observation led us to assume that the CNTs could not impart a
reinforcing property at very low CNT loading (0.2 wt%) in the
PMMA/MWCNT composites at constant PMMA bead content.

CONCLUSIONS
For the first time, we demonstrate a simple method that gives rise
to electrically conducting PMMA/MWCNT composites at much
lower CNT loading than those reported to date with unmodified
MWCNTs of similar quality. The presence of commercial PMMA
beads during the polymerization of MMA/MWCNT acted as an
excluded volume, leading to an increase in local concentration
of the CNTs selectively in the in situ polymerized PMMA phase,
outside the PMMA beads in the composites. Thus, formation of
a highly continuous network structure of CNTs at a considerably
lower CNT loading was possible that could bring the percolation
threshold of the unmodified CNTs in the PMMA matrix down to
0.12 wt%. It was noteworthy that melt-mixed composites in our
study showed electrical conductivity in the range ca 105 S cm1
at 2.7 wt% CNT loading whereas the composites prepared by
polymerizing MMA/MWCNT in the presence of 70 wt% PMMA

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1691

Dynamic mechanical properties

Figure 9(a) shows the temperature dependence of the storage
modulus of PMMA/MWCNT (0.2 wt%) composites with various
(40, 60 and 70 wt%) amounts of PMMA beads. As observed, the
PMMA/MWCNT (0.2 wt%) composites with 40 wt% PMMA beads
showed a storage modulus similar to that of the system without
any CNT loading in the entire temperature region (35150 C).
However, the storage modulus of the PMMA/MWCNT composites
at constant CNT loading (0.2 wt%) was marginally improved with
increasing PMMA bead content in the composites. This slight
but gradual increase in storage modulus of the PMMA/MWCNT
composites might be due to the increasing amount of high
molecular weight PMMA beads in the composites. Thus, the
reinforcing property of the MWCNTs in these composites was not
reflected at this (0.2 wt%) low level of CNT loading.
The storage modulus of PMMA/MWCNT composites with 70
wt% PMMA beads and various (0.2, 0.4, 0.7 and 1.0 wt%) amounts
of CNTs is shown in Fig. 9(b). A gradual and significant increase in
storage modulus of the PMMA/MWCNT composites was evident
with increasing CNT content (wt%) in the composites, keeping

Figure 9. Storage modulus versus temperature plot for PMMA/MWCNT

composites (a) with variation of PMMA bead content at 0.2 wt% MWCNT
loading and (b) with variation of MWCNT loading at 70 wt% PMMA bead
content.

www.soci.org
beads revealed similar conductivity even at 0.2 wt% CNT loading,
which is ca 14 times lower CNT loading than that of the meltmixed composites. A further investigation through careful control
of the MMA/PMMA bead ratio, as well as the bead size and time
of addition of the beads during the polymerization, may lead to
a phenomenal shift in the percolation threshold of unmodified
MWCNTs to an exceptionally low value in the PMMA matrix.

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