Composites: Part A 49 (2013) 5157

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Thermally reduced graphene oxide acting as a trap for multiwall carbon

nanotubes in bi-ller epoxy composites
Swetha Chandrasekaran a,, Gabriella Faiella a, L.A.S.A. Prado a, Folke Tlle b, Rolf Mlhaupt b, Karl Schulte a
a

Technische Universitt Hamburg-Harburg, Institute of Polymers and Composites, Denickestrasse 15, 21073 Hamburg, Germany
Freiburg Materials Research Center (FMF), Freiburg Institute for Advanced Studies (FRIAS) and Institute for Macromolecular Chemistry of the Albert-Ludwigs University
Freiburg, Stefan-Meier-Strasse 31, D-79104 Freiburg, Germany
b

a r t i c l e

i n f o

Article history:
Received 19 July 2012
Received in revised form 11 February 2013
Accepted 15 February 2013
Available online 26 February 2013
Keywords:
A. Polymer matrix composites (PMCs)
B. Rheological properties
B. Electrical properties

a b s t r a c t
The effect of thermally reduced graphene oxide (TRGO) on the electrical percolation threshold of multi
wall carbon nanotube (MWCNT)/epoxy cured composites is studied along with their combined rheological/electrical behavior in their suspension state. In contrast to MWCNT and carbon black (CB) based
epoxy composites, there is no prominent percolation threshold for the bi-ller (TRGOMWCNT/epoxy)
composite. Furthermore, the electrical conductivity of the bi-ller composite is two orders of magnitude
lower (1  105 S/m) than the pristine MWCNT/epoxy composites (1  103 S/m). This result is primarily due to the strong interaction between TRGO and MWCNTs. Optical micrographs of the suspension
and scanning electron micrographs of the cured composites indicate trapping of MWCNTs onto TRGO
sheets. A morphological model describing this interaction is presented.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Recent advancements in the eld of carbon based composites
focuses on the two-dimensional form of carbon sheet called graphene [1,2]. Graphene, like carbon nanotubes (CNTs) and fullerenes,
is an allotropic form of carbon, which is constituted solely by
sp2-hybridised carbon atoms. Since its rst synthesis, the exceptional properties of graphene (mechanical properties, electrical
and thermal conductivity) became very attractive for the development of novel polymer composites [3,4]. There are several literatures on graphene, production methods of graphene or graphene
oxide and their usage as a ller material in composites [5]. One
such method is a top-down process where functionalized graphene
(FG) is prepared by exfoliation of graphite through the formation of
graphite oxide (GO) [6,7]. This layered graphite oxide is exfoliated
further to get individual sheets through ultra-sonication in a solvent to yield graphene oxide. Graphite oxide which is an insulator
by nature due to the oxygen functionalities, can be reduced either
thermally or chemically to form an electrically conductive FG [8].
Among the different reduction methods, thermal reduction of GO
results in a FG-material called thermally reduced graphite oxide
(TRGO). This thermal procedure does not need toxic reducing
agents like hydrazine and yields a ne graphene powder that can
be used without further purication. Most of the graphene nanosheets used in the composites are prepared by the reduction of
Corresponding author. Tel./fax: +49 (0) 40 42878 4504.
E-mail address: Swetha.chandrasekaran@tuhh.de (S. Chandrasekaran).
1359-835X/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.compositesa.2013.02.008

GO [9,10]. At present, a chemical procedure for the production of

graphene is most suited for the large scale production needed for
the preparation of composites.
One of the potential areas for this new carbon ller is in the eld
of polymer nanocomposites, where nanoparticles are incorporated
in a polymeric matrix. Dispersion of nanollers in the polymer matrix is a main factor which determines the nal properties of the
nanocomposites. For example, in CNT/polymer composite, the
effectiveness of the ller in terms of strength is achieved only by
well dispersed CNTs by preventing slippage of CNTs and their
agglomeration [11]. On the other hand, for electrical properties,
CNT re-agglomeration during the curing process aids in achieving
lower percolation in the composite [12]. When compared with carbon nanotubes, graphene and FG sheets have less entanglement
and large specic surface area making them an ideal candidate
for mechanical reinforcement in the matrix. The remnant functionalities in the FG result in better dispersion of this ller in the matrix and thereby improve the strength of the nanocomposite [13].
Ramanathan et al. showed 30% increase in Tg and in storage modulus for PMMA based composite [14]. The addition of TRGO to
polymer matrices (high density polyethelene) provides composites
with lower electrical conductivity [15]. Incorporation of 0.125 wt.%
of TRGO in epoxy seems to increase the fracture toughness of the
epoxy by 115% and also improves the fatigue performance
[16,17]. Epoxy based nanocomposites with commercially available
graphene nanoplatelets (GNP) are no exception in terms of
mechanical properties. Higher ller loadings of 6 wt.% of GNP the
modulus increases by 24% [18].

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S. Chandrasekaran et al. / Composites: Part A 49 (2013) 5157

The need for multi-functional polymer composite led to combine several nanoparticles of different geometry, in order to
achieve synergetic effects in so-called multi-ller composites
[19,20]. Graphene and FG are also utilized in multi-ller based
composites and its combination with CNT or carbon black (CB)
showed synergy in terms of tensile strength, thermal conductivity
and also on super-capacitance [21,22]. The development of multiller polymer nano-composites is an effective procedure for the
preparation of materials with improved mechanical and thermal
properties [23,24]. On the other hand, the llerller interactions
play also a key role on the nal properties of the composite. It
was seen that there is a reduction in the CNTs effective aspect ratio
due to the formation inter-connects between the tubes which leads
to decreasing mechanical properties at higher ller loadings [25].
Partial replacement of mono-dimensional ller like carbon nanotubes (MWCNT) by carbon black (CB) spherical nanoparticles enabled the production of highly conducting epoxy/MWCNT/CB. It
was proposed by the authors that the CB shortcuts some parts of
MWCNT network and thereby increases the electrical conductivity
with lower loadings of MWCNT. A conductivity of 5  104 S/m at
0.2 wt.% with 50 phr of CB and 50 phr of MWCNT nano-composites
was observed at very low CNT concentration [26].
In this study, we describe the properties of a bi-ller epoxy
based composite containing nanotubes and thermally reduced
graphene oxide, starting from the rheological behavior of the suspension until the electrical properties of the cured composites. The
results provided by combined rheological/electrical measurements
together with the investigation of the percolation behavior of the
cured composites, gave a wide range of information on the
MWCNTTRGO interactions and on their effect on the nal electrical properties.

2. Experimental
2.1. Preparation of nanocomposite
In this study, two different nano-ller suspensions namely
TRGO/epoxy and MWCNT/epoxy suspensions were prepared using
the three-roll-milling technique. All the composites were produced
using diglycidyl ether of bisphenol A epoxy resin (Araldite LY 556)
as matrix, cured using an anhydride (Aradur CH917) and an imidazole accelerator (DY070) (100:90:1 phr) all supplied by Huntsman. The llers used were multi walled carbon nanotubes (NC
7000, supplied by Nanocyl S.A.) and thermally reduced graphene
oxide (TRGO) from Freiburg University [27]. The TRGO used in this
method is prepared from graphite via GO synthesized by Hummers method [28]. The GO was reduced in a tube furnace at
750 C in a nitrogen atmosphere. The lateral dimensions of the
TRGO sheets vary from 1.4 to 4.6 lm with a specic surface area
of 413 m2/g and have some 12 wt.% of oxide content (elemental
analysis). Raman spectra, thermo-gravimetric analysis (TGA) and
elemental analysis for the llers used are provided in Supporting
information (Figs. S1 and S2). Composite suspensions were produced using three-roll-mill (EXAKT 120E). Appropriate amounts
of nanoller and epoxy were mixed inside the glove box and were
milled using the EXAKT three-roll-mill by varying the distance between the rolls. To this suspension 90 parts of hardener and 1 part
of accelerator were added and mixed manually for 10 min. The
mixture was then degassed under vacuum at 50 C to remove air
bubbles. The nal mixture was poured into the curing mold and
cured in the oven for 80 C for 4 h and 140 C for 8 h [23]. The
weight percentage of TRGO in TRGO/epoxy suspension was xed
to 0.02 wt%, as this suspension was below its electrical percolation
threshold. A master batch of 0.1 wt% of MWCNT/epoxy was prepared by 3-roll-mill and diluted using epoxy to 0.01 wt%,

0.02 wt%, 0.05 wt%, and 0.07 wt% respectively. To this diluted suspension 50 phr of 0.02 wt% of TRGO/epoxy suspension was added
and then the bi-ller suspension was milled again using the same
condition. A higher concentration of 0.57 wt% MWCNT/epoxy and
0.57 wt% TRGO/epoxy was also prepared and mixed using the
three-roll-mill in 1:1 ratio to measure the electrical conductivity.
The study at such a concentration of TRGO (0.57 wt%) well above
the electrical percolation threshold will give more insight on the
electrical conductivity by addition of TRGO to MWCNT/epoxy
composite.
2.2. Electro-rheological measurements of nanocomposite suspension
Combined rheological and electrical measurements were carried out on the freshly prepared suspensions using a modied
stress-controlled rheometer (StressTech HR, Rheological Instruments), in order to evaluate the agglomeration behavior of the
bi-ller system under shear. It must be noted that the time between measurement and sample preparation was less than 24 h.
This ensured that there were no effects on the agglomeration or
sedimentation and in turn on the conductivity from the storage
time. Optical, electrical and rheological in situ measurements were
possible with this test setup [29]. Shear rate step tests were carried
out, by shearing at a constant rate for 10 min and simultaneously
measuring the electrical conductivity. The shear rates were changed from 100 s1 to 0.1 s1 [30,31]. Measurements were carried
out at 60 C for better resolution of the data.
2.3. Electrical conductivity of cured nanocomposite
The second part of the experimental work aimed to study the
electrical conductivity of the TRGOMWCNT/epoxy cured composite, in order to make a comparison with MWCNT/epoxy composites
properties. This study will give information about the effect of
TRGO on MWCNT/epoxy cured composite due to temperature induced agglomeration [32]. Therefore, the electrical conductivity of
the cured composite for both TRGOMWCNT/epoxy and the
MWCNT/epoxy systems were measured using Hewlett Packard
impedance analyzer (HP4284A LCR) using two-point contact. Circular shaped samples of diameter 15 mm and thickness of 2 mm
coated with silver paint on both sides were used for this test.
3. Results and discussion
3.1. Combined electrical and rheological measurements of suspension
The electrical conductivity of different weight percentage of
MWCNTs in epoxy suspension as function of shear rate is shown
in (Fig. 1a and b). The electrical conductivity for both mono-ller
(MWCNT/epoxy) suspensions and bi-ller (TRGOMWCNT/epoxy)
suspensions are plotted in the same graph for the ease of
comparison.
It is visible from the above graph, (Fig. 1a and b) that the electrical conductivity increases as the shear rate is decreased for both
bi-ller and mono-ller suspensions. At higher shear rates (e.g.
100 s1) the ller particles cannot agglomerate, since the energy
input by the shearing is enough to separate the particles from each
other. As the shear rate is decreased, the ller particles are expected to build up agglomerates and their contact giving rise to
an electrically conductive network. However, the electrical
conductivity of the TRGOMWCNT/epoxy suspensions does not
increase at low shear rates unlike mono-ller MWCNT/epoxy
suspensions.
Unlike MWCNT suspensions, the bi-ller (TRGOMWCNT/
epoxy) suspensions seem to have a less pronounced tendency to

S. Chandrasekaran et al. / Composites: Part A 49 (2013) 5157

53

Fig. 1. Electrical conductivity at different shear rates for the MWCNT/epoxy and TRGOMWCNT/epoxy suspensions (a) at lower concentration of ller and (b) at very high
ller concentration respectively. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

form agglomerates under shear. The rst agglomerates of MWCNT

start to connect already at 0.02 MWCNT wt.%, whereas the rst
agglomerates form only at 0.07 wt% of MWCNT for bi-ller suspension (0.02 TRGO0.07 MWCNT wt.%/epoxy). The suspension containing 0.02 TRGO0.05 MWCNT wt.%/epoxy also shows the
formation of the conducting agglomerates at 0.1 s1 shear rate,
but these agglomerates are not stable under shear. Only at
0.02 TRGO0.07 MWCNT wt.%/epoxy, stable agglomerates can be
formed at a shear rate of 0.1 s1. At this percentage of the nanotubes (0.07 wt%), the electrical conductivity of the mono-ller
epoxy suspension is at least two orders of magnitude higher than
the corresponding suspension containing TRGO and MWCNT. A
similar trend is also observed at 0.57 TRGO0.57 MWCNT wt.%/
epoxy suspensions (Fig. 1b) which indicates that the effect of TRGO
on MWCNT/epoxy suspension is same irrespective of the ller content. The conductivity decreases by 1 order of magnitude at low
shear rates (0.1 s1) and by three orders for higher shear rate
(100 s1) in the case of 0.57 TRGO0.57 MWCNT wt.%/epoxy suspension (Fig. 1b). Adding high content of TRGO also seems to reduce the electrical conductivity of MWCNT/epoxy system. An
in situ optical microscopy analysis of the ller structure formed
under shearing at lower concentration is shown in (Fig. 2).
It is evident from the optical micrographs (Fig. 2) that the size of
the agglomerates of MWCNT/epoxy suspension is bigger than that
of the TRGOMWCNT/epoxy suspension. In fact, the suspension at
0.02 MWCNT wt.% forms already connected agglomerates (Fig. 2i)
at 0.1 s1, the corresponding one containing TRGO does not show
any connected network (Fig. 2c), which is in line with the insulating behavior of the suspension all over the range of applied shear
rates. A clearly visible agglomerated network can be observed for
the 0.05 MWCNT wt.%/epoxy suspension (Fig. 2m and n), while a
less connected structure is present in the corresponding suspension containing TRGO (Fig. 2e and f). The shear induced agglomeration behavior of the suspension containing only 0.02 TRGO wt.%/
epoxy was investigated as well, and no network formation during
shear was appreciated both by electrical measurements and morphological observations. Findings are in Supporting information
(Figs. S3 and S4). The electrical conductivity measured for bi-ller
suspension of 0.02 TRGO0.07 MWCNT wt.%/epoxy suspension is

mainly due to the presence of MWCNTs at high content, which is

sufcient enough to form connected network of agglomerates.
The ller agglomeration observed in TRGOMWCNT/epoxy suspension is mostly due to tendency of MWCNTs to form percolated
network structure. Graphene oxide akes conne the MWCNT in
nite and restricted regions within the resin, hindering their
agglomeration and consequent contact and thereby reducing the
electrical conductivity. These rst results on the study of the shear
induced agglomeration behavior of TRGOMWCNT suspensions
show that addition of TRGO lowers the conductivity of MWCNT/
epoxy suspension by hindering the formation of shear induced percolated network.
3.2. Electrical conductivity of cured nanocomposite
It must be noted that the amount of the ller used in rheological
experiments are with respect to LY556 epoxy (i.e., prior to the
addition of anhydride and imidazole components), whereas, for
the cured composite the weight percentage of the ller is halved
due to the addition of hardener and accelerator. For better understanding, electrical conductivity of pristine TRGO/epoxy cured
composite and bi-ller TRGOMWCNT/epoxy cured composite as
a function of weight percentage of the ller are summarized in
(Fig. 3a and b).
In Fig. 3a the electrical conductivity of TRGO/epoxy composites
as a function of weight percentage is shown. Comparing Fig. 3a
with b (denoted by circle and line symbol), it can be concluded that
TRGO/epoxy composites are less conductive than MWCNT/epoxy
composites. When the two llers are combined, the bi-ller composites exhibit neither synergy nor obey the rule of mixtures but
instead an opposite of the synergetic effect is observed. Essentially,
addition of TRGO decreases the electrical conductivity of MWCNT/
epoxy composite. The same was measured for higher concentration of ller and the electrical conductivity of 0.57 TRGO
0.57 MWCNT wt.%/epoxy cured composite is 3  103S/m which
is one order of magnitude lesser than the mono-ller 0.57 wt%
MWCNT/epoxy cured composite (7.8  102 S/m).
On comparing the conductivity of the bi-ller (TRGOMWCNT/
epoxy) cured composite to that of MWCNT/epoxy cured composite,

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S. Chandrasekaran et al. / Composites: Part A 49 (2013) 5157

Fig. 2. Optical micrographs of 0.02 TRGO0.02 MWCNT wt.%/epoxy (ac), 0.02 TRGO0.05 MWCNT wt.%/epoxy (df), 0.02 MWCNT wt.%/epoxy (gi) and 0.05 MWCNT wt.%/
epoxy (ln).

Fig. 3. (a) Electrical conductivity of TRGO/epoxy cured composite at different weight percentage and (b) comparison of the electrical conductivity between bi-ller TRGO
MWCNT/epoxy and pristine MWCNT/epoxy cured composites respectively. (For interpretation of the references to color in this gure legend, the reader is referred to the web
version of this article.)

there seems to be a decrease in the conductivity of the composite

due to the addition of TRGO. This decrease in conductivity of the
bi-ller cured composite is about two orders of magnitude for lower concentration of ller content (0.01 TRGO0.01 MWCNT wt.%/
epoxy) and is about one order of magnitude for higher ller content (0.01 TRGO0.035 MWCNT wt.%/epoxy). The addition of TRGO
affects more the conductivity of MWCNT/epoxy cured composite at
lower concentrations of MWCNT. As the ller content increases,
agglomeration of the tubes due to high concentration dominates
the electrical transport behavior, which does not depend much
on the type of ller added, but rather only on an increase of conductive llers coming in contact. When a steep increase in electrical conductivity is observed for the cured MWCNT/epoxy
composites, a less signicant change in the conductivity is found
in the TRGOMWCNT epoxy composites, thus a steep increase in

electrical conductivity cannot be appreciated at any ller concentration. Clearly, the minimum optimal amount of MWCNT for percolation threshold requires not a homogenous dispersion but an
adequate dispersion, sufcient enough to form conduction pattern
along the matrix. This is possible in MWCNTs in epoxy at even lower loadings due to the high dispersive surface energy which produces spontaneous re-agglomeration.
The same phenomenon is also observed in carbon black lled
epoxy systems where the network formation depends on particle
particle interaction which in turn is controlled by the shear forces
or ionic interaction of the resin [33]. From these ndings it is very
clear that TRGO reduces the electrical conductivity of CNT composites by hindering the agglomeration of the carbon nanotubes. This
effect seems to be independent whether the agglomeration of
MWCNT is by shear (Fig. 1a and b) or by temperature (Fig. 3b).

S. Chandrasekaran et al. / Composites: Part A 49 (2013) 5157

3.3. Morphological characterization of the cured composite

To better understand this nding scanning electron micrographs of cured composite containing 0.035 MWCNT wt.%/epoxy
and 0.01 TRGO0.035 MWCNT wt.%/epoxy are shown in (Fig. 4).
The distribution of the MWCNT agglomerate and dense MWCNT
agglomerates can be seen in (Fig. 4a) and the formation of percolated conducting network by connecting two MWCNT agglomerates are additionally conrmed in (Fig. 4b). When TRGO is added
to the MWCNT/epoxy system, the distribution of MWCNT agglomerates is affected to a great extent. First, the agglomerates are sparsely distributed and appear to be less dense when compared to
mono-ller MWCNT/epoxy composite. The question is where do
the rest of the CNTs disappear? (Fig. 4c) shows an agglomerate of
TRGO with MWCNT (0.01 TRGO0.035 MWCNT wt.%/epoxy). A closer examination on this gure shows some MWCNT in the vicinity
of the TRGO sheets and the agglomerate of TRGO is more threedimensional. More micrographs as in (Fig. 4d and e) show the hindrance of CNT network by a TRGO sheet both parallel and in perpendicular to the CNT network.
This morphology of the TRGOMWCNT bi-ller composite explains the lower conductivity when compared to mono-ller
MWCNT/epoxy composite. The TRGO sheets attract the carbon
nanotubes and thereby hinders the formation of percolated conductive networks. The MWCNT within or on the TRGO can be
entangled within these walls or disentangled. The remaining
MWCNTs that are not affected by the presence of TRGO sheets
form percolated networks which give rise to an increase of the

55

electrical conductivity. However, the MWCNTs that are trapped

by the TRGO sheets do not contribute to the conductive path;
hence a higher amount of tubes is needed to reach appreciable
levels of conduction. Scanning electron micrographs of
0.01 TRGO wt.%/epoxy (Fig. S5) given in Supporting information
shows the agglomeration of only TRGO sheets in epoxy. From the
images, the depth of agglomerates of TRGO sheets is lesser when
compared to TRGOMWCNT agglomerate in epoxy. This may be
due to the presence of MWCNT agglomerates in-between the TRGO
sheets.

3.4. Proposed theory for reduced conductivity of bi-ller

nanocomposite
Based on this a hypothesis a morphological model is proposed
to explain the experimental results as shown in the schematic in
(Fig. 5).
The schematic shows both the cross-sectional view of this
TRGOMWCNT agglomeration and their top view. The SEM of pristine TRGO sheets which is provided in Supporting information
(Fig. S6) show a much wrinkled surface (top view) which arises
from the thermal reduction and exfoliation of the sheets by the release of gases. The cross-sectional view of the TRGO sheets have an
accordion like structure and from the image the gap between the
sheets are more than 1 lm. This gap is sufcient enough for
MWCNT to accommodate themselves in. This morphology was
very clearly seen at higher concentration of bi-ller composites

Fig. 4. Scanning electron micrographs of 500 nm thin slices of composite deposited on Si substrate. (a and b) SEM of mono-ller MWCNT/epoxy (0.035 MWCNT wt.%/epoxy)
cured composite; (ce) SEM of bi-ller TRGOMWCNT/epoxy (0.01 TRGO0.035 MWCNT wt.%/epoxy) cured composite.

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S. Chandrasekaran et al. / Composites: Part A 49 (2013) 5157

Fig. 5. Morphological model for TRGOMWCNT/epoxy cured composite; (a) cross-sectional view and (b) top-view respectively. (For interpretation of the references to color
in this gure legend, the reader is referred to the web version of this article.)

(0.57 TRGO0.57 MWCNT wt.%/epoxy) when the cryo-fractured

surface was investigated for ller distribution.
The cryo-fractured surface of high concentration bi-ller composite exhibits morphology where the MWCNT agglomerates are
trapped by the TRGO sheets/agglomerates (Fig. 6a), also the
MWCNTs are in the vicinity of the TRGO sheets. This again is an
indication of strong llerller interaction through pp interaction
between the MWCNTs and TRGO sheets. Another interesting
morphological feature observed on the cryo-fractured surface is
the pinning/trapping of MWCNTs on/between the TRGO sheets
(Fig. 6b).
Thus, the wavy topography of the sheets also aids to pin the
MWCNT to their surface [34]. Also the TRGO sheets have around
12 wt.% of strong oxygen functionalities which was determined
from elemental analysis. Recent literatures are available about
GO acting as a dispersing agent for MWCNT [35]. We believe that
the oxygen functionalities play a vital role in attracting the
MWCNT to their surface. The oxygen functionalities are decorating
the edges of the graphene sheets and also form oxide rich regions
like nano-islands on the basal plane. These oxide rich nano-islands
are hydrophilic in nature and the regions in the graphene basal
plane free of oxide groups are hydrophobic in nature as in
(Fig. 7). The MWCNT are attracted through pp interaction by
those areas in the GO sheets where there are no oxygen groups
in the basal plane [36]. Hence the path of electron mobility on

Fig. 7. Schematic representation of graphene oxide (GO) sheets showing both

hydro-phobic (blue domain) and hydro-philic (red domain). (For interpretation of
the references to color in this gure legend, the reader is referred to the web version
of this article.)

the TRGO sheet is already restricted because of oxygen functionalities on the basal plane; in addition to this the MWCNT are attracted by the p conjugated nano-islands. All these effects make
the whole aggregate an insulator; it acts as a barrier for electron
transport [35]. Adding to this, the specic surface area of the sheets
is 413 m2/g which is greater than or equal to that of MWCNT and
hence the inuence of van der Waals force exerted by the sheets
on MWCNTs are much higher. The attraction of carbon particles

Fig. 6. Scanning electron micrograph of cryo-fractured surface of bi-ller 0.57 TRGO0.57 MWCNT wt.%/epoxy cured composite in in-lens mode: (a) MWCNT agglomerates
are surrounded by TRGO agglomerates and (b) MWCNTs pinned onto the TRGO sheets respectively.

S. Chandrasekaran et al. / Composites: Part A 49 (2013) 5157

by the TRGO sheets was observed not only with MWCNT but also
for carbon black particles (not presented here). The presence of
functional groups makes the TRGO partially polar which makes it
well dispersed in the matrix and their tendency to agglomerate
is low. When mixing with MWCNTs, the sheets act as a barrier
reducing the mobility of CNT in the matrix. The pp interaction between the TRGOMWCNT is not the only contributing factor for
the observed behavior, the viscosity of the resin along with the dispersive shear forces could also contribute to this MWCNTTRGO
interaction.
4. Conclusion
The effect of addition of small amounts of TRGO (0.02 wt%) to the
MWCNT/epoxy system was investigated under combined rheological and electrical measurements. The electrical conductivity of the
cured composites was also measured, which includes inuence of
temperature on the agglomeration. The experimental results show
that the addition of TRGO reduces the electrical conductivity of
MWCNT/epoxy composites by two orders of magnitude. Based on
the structural characterization, a morphological model for this biller system is proposed. It can be seen that TRGO sheets hinders
the agglomerate formation by trapping the MWCNTs between them.
Author contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the nal version of
the manuscript.
Acknowledgements
The authors would like to acknowledge Adan Hernandz and
Jana Schlutter for their support in sample production and characterization. We would like to acknowledge DAAD-SIEMENS A/10/
71620, German Federation of Materials Science and Engineering
(BV MatWerk) and German Research Foundation (DFG) for their
nancial support.
Appendix A. Supplementary material
The Supporting information consists of the electrical conductivity of pristine 0.02 TRGO wt.%/epoxy suspensions which can be
used for comparison with the bi-ller TRGOMWCNT/epoxy system. Optical micrographs of the suspension (0.02 TRGO wt.%/
epoxy) at different shear rates are also provided. Scanning electron
micrographs of pristine TRGO sheets both top and cross-sectional
view is available which helps to visualize better the proposed morphological model. Supplementary data associated with this article
can be found, in the online version, at http://dx.doi.org/10.1016/
j.compositesa.2013.02.008.
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