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Convenient preparation of tunably loaded

chemically converted graphene oxide/epoxy
resin nanocomposites from graphene oxide
sheets through two-phase extraction
Article in Journal of Materials Chemistry November 2009
DOI: 10.1039/b915228h

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www.rsc.org/materials | Journal of Materials Chemistry

Convenient preparation of tunably loaded chemically converted graphene

oxide/epoxy resin nanocomposites from graphene oxide sheets through
two-phase extraction
Huafeng Yang, Changsheng Shan, Fenghua Li, Qixian Zhang, Dongxue Han and Li Niu*
Received 27th July 2009, Accepted 18th September 2009
First published as an Advance Article on the web 15th October 2009
DOI: 10.1039/b915228h
We report a facile method to create the chemically converted graphene oxide/epoxy resin
nanocomposites from graphene oxide sheets through two-phase extraction. Great improvements in
mechanical properties such as compressive failure strength and toughness have been achieved for the
chemically converted graphene oxide/epoxy resin for a 0.0375 wt% loading of chemically converted
graphene oxide sheets in epoxy resin by 48.3% and 1185.2%, respectively. In addition, the loading of
graphene is also conveniently tunable even to 0.15 wt% just by increasing the volume of the graphene
oxide dispersion.

1. Introduction
Nanocomposites have been heralded1 as a radical alternative to
conventional filled polymers or polymer blends, especially in the
fields of transportation and electronics. Ideally, polymer-based
nanocomposites will provide materials that possess the ease of
processing inherent to plastics but with dramatically improved
and even multifunctional properties, opening the way to
completely new applications of polymers.
Of the carbon-based nanofillers, CNTs have attracted
considerable attention due to their intrinsic mechanical and
electrical properties. Improvements in modulus and strength of
30% and 15% have been reported for 1 wt% loading of functionalized single-walled carbon nanotubes (SWNTs) in epoxy,2
and electrical percolation was observed at loadings as low as 0.1
wt%.3 However, the use of CNTs in nanocomposites to date has
been limited by challenges in processing and dispersion, and their
prohibitively high cost.
In recent years, graphene has attracted numerous investigations due to its unique physical, chemical, and mechanical
properties,410 opening up a new research area for materials
science. The remarkable properties of graphene reported so far
include high values of its fracture strength (125 Gpa),11 thermal
conductivity (5000 W m1 k1),12 mobility of charge carriers
(200 000 cm2 g1),13and specific surface area (calculated value,
2630 m2 g1).14 Derived from these remarkable properties, the
graphene sheets may hold considerable potential as a new
carbon-based nanofiller. It has recently been demonstrated that
incorporation of well-dispersed graphene-based sheets into
polymers at extraordinarily low filler content resulted in

State Key Laboratory of Electroanalytical Chemistry, Changchun Institute

of Applied Chemistry, Graduate University of the Chinese Academy of
Sciences, Chinese Academy of Sciences, Changchun 130022, P. R. China
Electronic supplementary information (ESI) available: Details of the
synthesis procedure of GO and water-soluble chemically converted
graphene nanosheets; C1s XPS, FTIR, AFM, TGA, SEM, and TEM
analysis of GO; photos of the resulting monoliths. See DOI:
10.1039/b915228h

8856 | J. Mater. Chem., 2009, 19, 88568860

remarkable impact on the mechanical properties of the polymer.15 In order to efficiently affect the properties of the host
matrix, two important processing issues had to be addressed: the
homogeneous dispersion of graphene into the matrix, and the
strong interfacial interactions required between the graphene and
the matrix.16 However, challenges remaining to achieve good
dispersion of graphene pose significant obstacles to these goals.
Graphene oxides (GO) containing many oxygen groups result
in an enhanced mechanical interlocking with the polymer chains
and, consequently, in better adhesion.15 Thus, the graphenebased composite can be created from GO as precursor. Recent
studies have shown that graphene can be dispersed throughout
a polymeric or inorganic matrix17 to make graphene-based
composites and paper-like materials with excellent mechanical
properties.9,15,1820 The traditional procedure to create the graphene-based materials includes three steps as follows: firstly,
hydrophilic GO sheets were prepared; secondly, a functionalization process was carried out to change the surface properties of
GO, leading to good dispersibility of these resulting graphene
sheets in organic solvent9, 2124 or a thermal exfoliation was performed at high temperature giving rise to dispersible graphene
sheets;25 finally, the resulting graphene sheets homogeneously
dispersed together with organic materials in the same solvent,
especially with conjugated polymers.26 Such a typical process of
creation of the graphene-based materials is relatively inconvenient, since the second step is necessary for the traditional
procedure. Whether a new and facile method can be developed to
prepare the graphene-based nanocomposites remains an important question.
The GO sheets which have been suggested to contain many
epoxy groups23 should be able to make an ideal filler of epoxy
resin which also contains epoxy groups, based on the principle of
dissolution in a similar material structure. Here, we develop
a facile and feasible method to obtain economically viable graphene oxide/epoxy resin nanocomposite materials directly from
GO dispersion through a two-phase extraction. Skilfully, the
chemically converted graphene oxide/epoxy resin nanocomposites are obtained during the solidification procedure of
This journal is The Royal Society of Chemistry 2009

the GO/epoxy resin nanocomposite with the amine curing agent.

In addition, the mechanical properties of the resulting chemically
converted graphene oxide/epoxy resin nanocomposites were also
investigated.

experiments, 10 g of neat epoxy resin monolith was prepared

with 5 g of amine hardener by a similar way. Then the final
mixtures were added into cylindrical molds (H 8.34 mm and
D 11.18 mm) and cured at 150  C for 2 h. Photos of the
resulting monoliths are shown in Fig. S5 (ESI).

2. Experimental
2.1.

Materials

Graphite powders (spectral pure) were obtained from Shanghai

Chemicals, China.; epoxy resin (NPEL-128, a liquid resin) which
is manufactured from bisphenol-A and epichlorohydrin was
obtained from Huili Chemicals, China; amine hardener (H-1618)
was obtained from Huili Chemicals, China; all other reagents
and solvents were purchased from commercial suppliers and used
as received. Dialysis membrane (Mw 800014 000) was
purchased from Beijing Tingguo Biology Chemicals Company.
All aqueous solutions were prepared with ultra-pure water
(>18 MU) from a Milli-Q Plus system (Millipore).
2.2. Preparation of homogenous dispersion of GO in epoxy
resin
10 g of epoxy resin was mixed with 1.5, 3.75, and 7.5 mL of
as-prepared GO dispersion (0.5 mg mL1) in three 50 mL
glass vials, respectively and the weight ratios were 0.0075 wt%,
0.01875 wt%, and 0.0375 wt%, respectively. The mixtures were
vigorously shaken or stirred for 4 h in an oil bath (50  C), and
then allowed to stand for several hours to separate into two
layers. From Fig. 1A, the upper layer of water is colorless and
transparent, indicating that the GO sheets in water have been
completely extracted into the epoxy resin phase as expected. To
obtain homogenous GO/epoxy resin composites, the mixtures
were subjected to being shaken and stirred for several additional
hours in an oil bath, completely removing water. Finally,
homogenous composites were obtained.

2.4.

Measurements and characterizations

X-Ray photoelectron spectroscopy (XPS) analysis was carried

on an ESCALAB MK II X-ray photoelectron spectrometer.
Fourier transform infrared spectroscopy (FTIR) was recorded
on a CaF2 substrate containing the target materials in the solid
state with a Bruker Tensor 27 Spectrometer (4 cm1). Thermogravimetric analysis (TGA) was measured under a nitrogen
atmosphere with a Perkin Elmer Thermal Analyzer at a heating
rate of 5  C min1. Scanning electron microscopy (SEM)
measurements were conducted with an XL30 ESEM FEG field
emission scanning electron microscope. Transmission electron
microscopy (TEM) pictures were imaged by JEOL 2000 transmission electron microscope operating at 200 kV. Atomic force
microscope (AFM) images were obtained by a Digital Instruments Nanoscope IIIa (Santa Barbara, CA). The sample was
prepared through drop-casting on freshly cleaved mica surface.
Compressive tests were performed using an Instron 1121 with
a crosshead speed of 0.1 mm min1.

3. Results and discussion

10 g of the resulting homogenous dispersion of GO in epoxy resin

at different GO weights (0.0075 wt%, 0.01875 wt% and 0.0375
wt%) was mixed with 5 g of amine hardener. In control

Scheme 1 illustrates the synthesis process of chemically converted

graphene oxide/epoxy resin nanocomposite monoliths. The
studied GO sheets were prepared by oxidizing natural graphite
powder based on the literature27,28 (see ESI). Finally, as-purified
GO powders were distributed in water to create a homogenous
yellow-brown dispersion (0.05 wt%) ready for use. The resulting
GO sheets have been characterized by combined methods (see
ESI). It is clear that the CO epoxy/ether group be in the
majority, which was proved by XPS (see ESI, Fig. S1) and
FTIR (see ESI, Fig. S2) measurements. Moreover, the wellexfoliated samples of GO sheets were imaged using AFM
(see ESI, Fig. S3). On average, the interlay space of the GO
sheets is ca. 0.96 nm, indicating that exfoliation of graphite down

Fig. 1 Photos of the two-phase extraction process: (A) GO dispersion in

water and (B) graphene dispersion in water extracted by epoxy resin
(lower layer) after stirring for several hours, respectively.

Scheme 1 Procedures to create the chemically converted graphene

oxide/epoxy nanocomposite monoliths.

2.3.

Preparation of bulk monoliths

This journal is The Royal Society of Chemistry 2009

J. Mater. Chem., 2009, 19, 88568860 | 8857

Fig. 2 Photos of (A) epoxy resin, (B) dispersion of GO sheets in water

(0.5 mg mL1), and (C) homogenous dispersion of GO in epoxy resin
matrix at 0.0375 wt% GO sheets.

to individual GO nanosheets was indeed achieved.29 Finally,

TEM and SEM measurements (see ESI, Fig. S4) have also been
performed. Distortions caused by the oxygen groups and the
extremely small thickness of the resulting GO sheets lead to
a wrinkled topology as shown in the SEM and TEM images. The
surface roughness will also result in an enhanced mechanical
interlocking with the epoxy resin and, consequently, in better
adhesion.15
All the results demonstrate that the well peeled-off GO
nanosheets with many epoxy groups have been obtained
successfully in this work. Subsequently, we skilfully transferred
the resulting GO sheets into an epoxy resin matrix from a water
phase through extraction and obtained a mixture (see Fig. 1A,
lower layer). After completely removing the water in the mixture,
the homogenous dispersion of GO in epoxy resin was achieved as
expected (see Fig. 2C). In a control experiment, the water-soluble
chemically converted graphene sheets were extracted with epoxy
resin in a similar way. After vigorously being shaken or stirred
for 4 h, the layer of water is still black and the layer of epoxy resin
is gray owing to the presence of water (Fig. 1B), indicating that
the graphene sheets without any surface treatment can not be
directly transferred into the epoxy resin from water phase. In
order to conveniently observe the dispersibility of the GO sheets
in epoxy resin matrix, a colorless and transparent liquid epoxy
resin (NPEL-128) was used in this work.
In a typical solidification procedure of an epoxy resin, a curing
agent is required. As GO sheets have been suggested to contain
many reactive epoxy groups, its reaction with amine materials
should easily occur.22 In our previous work, chemically-converted graphene oxides with silanes30 and ionic liquids,31 based
on the reaction of the amino groups and epoxy groups, have been
reported. So a colorless and transparent amine hardener
(H-1618) was used in this procedure of solidification. The curing
agent not only solidified the GO/epoxy resin nanocomposites but
also chemically converted GO sheets encapsulated in epoxy resin
matrix into chemically converted graphene oxide through the
reaction between epoxy groups of GO and amine units of the
curing agent. In short, the chemically converted graphene oxide
sheets were simultaneity obtained during the process of the
solidification of the GO/epoxy resin composites. The chemically
converted graphene oxide/epoxy resin nanocomposite monoliths
were obtained successfully from as-prepared homogenous
dispersion of GO in epoxy resin as the precursor. The resulting
composite monoliths are black not yellow-brown owing to the
8858 | J. Mater. Chem., 2009, 19, 88568860

restoration of electronic conjugation of graphene sheets23

brought about during the interaction between GO sheets and
amine curing agent.
Compressive tests were carried out to investigate how the
chemically converted graphene oxides impact on mechanical
properties of the epoxy matrix. The neat epoxy resin monolith
and chemically converted graphene oxide/epoxy resin monolith
for 0.0375 wt% loading were chosen for compressive tests. Fig. 3
shows stressstrain curves. The control sample exhibited typical
compressive behavior of epoxy resin. However, the chemically
converted graphene oxide/epoxy resin nanocomposite monolith
at 0.0375 wt% (dotted) showed a clear change in their compressive behavior with a remarkable increase in compressive failure
strength and toughness (the area under the stressstrain curve)
by 48.3 and 1185.2%, respectively. The complete results of
mechanical properties were summarized and illustrated in Fig. 3
(inset a, b and c). The remarkable influence on the properties of
epoxy resin at extraordinarily low filler content can be attributed
to two main reasons. First, distortions caused by the oxygen
functionalization and the resultant defects during thermal
treatment of the precursor graphene oxide/epoxy resin, as well as
the extremely small thickness of the chemically converted graphene oxide sheets, lead to a wrinkled topology at the nanoscale.
This nanoscale surface roughness can result in an enhanced
mechanical interlocking with the polymer chains and, consequently, better adhesion.15 Second, graphene oxide contains
pendant oxygen-containing groups across the surfaces which
may form covalent bonds with epoxy component. Together with
the high surface area and nanoscale surface roughness of

Fig. 3 Stressstrain curves of neat epoxy resin monolith (solid) and

chemically converted graphene oxide/epoxy resin nanocomposite
monolith (dotted), and summarized mechanical properties of monoliths
(a) compressive failure stress (b) strain, and (c) toughness. Inset: photographs of monolith columns for the compressive tests. From left to right:
neat epoxy resin monolith and chemically converted graphene oxide/
epoxy resin nanocomposite monolith.

This journal is The Royal Society of Chemistry 2009

Fig. 4 SEM images of the fractured sections of (A) the neat epoxy
resin and (B) the chemically converted graphene oxide/epoxy resin
nanocomposite. Inset: images at high magnifications.

chemically converted graphene oxides which were encapsulated

into the epoxy matrix, this surface chemistry reaction leads to
stronger interfacial interactions with epoxy resin and thus
substantially larger influence on the properties of the host polymer.
To get more information concerning the interfacial interaction
between the matrix and chemically converted graphene oxide
sheets, fractured sections of the monoliths after compressive tests
were further investigated by SEM. As shown in Fig. 4, most
graphene sheets were well dispersed and embedded into the
epoxy resin monolith matrix (Fig. 4B), and no obvious chemically converted graphene oxide sheets can be observed to be
pulled out, indicating that chemically converted graphene oxide
sheets had stronger covalent interfacial bonding with the matrix
in virtue of the covalent interaction between graphene oxide
sheets and resin matrix. Moreover, a flake-like morphology of
the chemically converted graphene oxide sheets dispersed in
epoxy resin matrix was also observed (inset in Fig. 4B). This
indicated that these chemically converted graphene oxide sheets
in epoxy resin matrix remained well as flakes. Finally, the
thermal analysis data (TGA) to further examine the interaction
of graphene oxide and polymer matrix could be obtained in
Fig. S6 (ESI). The TGA was performed on GO (solid), epoxy
resin (dashed), and chemically converted graphene oxide sheets/
epoxy resin (dotted) and heated to 1000  C at a heating rate of
5  C min1 under N2. As shown in Fig. S6 (ESI), the thermal
stability of chemically converted graphene oxide/epoxy resin
nanocomposite monolith at 0.0375 wt% graphene (dotted) have
slightly improved, compared with the neat epoxy resin.

4. Conclusion
In summary, we have successfully developed a simple and
feasible method to obtain economically viable chemically
converted graphene oxide/epoxy resin nanocomposites directly
from the dispersion of GO sheets in water through a two-phase
extraction. Owing to the homogeneous dispersion and stronger
interfacial interactions with the epoxy resin matrix, as well as the
high surface area, great improvements in mechanical properties
have been achieved for chemically converted graphene oxide/
epoxy resin at 0.0375 wt% chemically converted graphene oxide
sheets (based on GO weight). The compressive failure strength
and the toughness have been improved by 48.3% and 1185.2%,
respectively. In general, high strength and high toughness are
difficult to achieve at same time for common materials but the
chemically converted graphene oxide/epoxy resin nanocomposites with strong interfacial linkages do exhibit this unique
property well. In addition, the loading of graphene in an epoxy
This journal is The Royal Society of Chemistry 2009

resin is also conveniently tunable even to 0.15 wt% just by

increasing the volume of the graphene oxide dispersion.
This new method to create the chemically converted graphene
oxide/epoxy resin nanocomposite is facile, feasible, and
economical, compared with recently reported procedures. This
method can bypass the second step which is necessary for the
traditional process. Additionally, the new method allows graphene oxide sheets to be intimately mixed with various organic
polymers similar to epoxy resin, facilitating the synthesis of
graphene-based polymer composites.
In short, this method may make broad applications of graphene
in the realms of physics and chemistry, and mechanical
improvement come true. Moreover, graphene-based polymers
similar to epoxy resin will provide materials which possess ease of
processing inherent to polymers, but with dramatically improved
and even multifunctional properties, opening a way to completely
new applications of graphene and polymer composites.

Acknowledgements
The authors are most grateful to the NSFC, China (No.20673109
and 20827004) for the financial support.

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