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Cite this: J. Mater. Chem., 2011, 21, 4222

www.rsc.org/materials PAPER
In situ polymerization of graphene nanosheets and polyurethane with
enhanced mechanical and thermal properties
Xin Wang,a Yuan Hu,*ab Lei Song,a Hongyu Yang,a Weiyi Xinga and Hongdian Luc
Received 30th October 2010, Accepted 15th December 2010
DOI: 10.1039/c0jm03710a

Polyurethane (PU) composites reinforced with graphene nanosheets (GNSs) were prepared by in situ
polymerization. Graphene nanosheets, which were derived from chemically reduced graphite oxide
(GO) nanosheets, were characterized by solid-state 13C MAS NMR, XRD and FTIR. A morphological
study showed that, due to the formation of chemical bonds, the GNS was dispersed well in the PU
matrix. With the incorporation of 2.0 wt% of GNSs, the tensile strength and storage modulus of the PU
increased by 239% and 202%, respectively. The nanocomposites displayed high electrical conductivity,
and good thermal stability of PU was also achieved. The facile and rapid technique presented here will
provide an effective and promising method of preparing graphene-based polymer composites.

Introduction interface between the GNSs and appropriate polymers. Poly-

Since graphene nanosheets (GNSs) were first reported in 2004,1
extensive research into their applications has been carried out in
various fields due to their unique electronic,2–5 thermal,6 and
mechanical properties7,8 arising from the strictly two-dimen-
sional (2D) atomic carbon sheet structure composed of
sp2-hybridized carbon atoms in a hexagonal lattice. Usually,
GNSs are produced by the chemical reduction of readily avail-
able exfoliated graphite oxide (GO) with reducing agents such as
hydrazine and dimethylhydrazine, which is a promising strategy
in the large-scale production of graphene.9
Very recently, GNSs have been further used to fabricate
polymer nanocomposites with integrated performance. Using
graphene nanosheets to reinforce polymers has generated a great
deal of interest.10–12 Manufacturing such reinforced composites
requires that GNS should be incorporated and homogeneously
distributed into polymer matrices. Cai et al.13 reported a simple
method to fabricate fully exfoliated functionalized graphene
sheets (FGSs) in an organic solvents. With this method in hand,
the barrier for well-dispersion of the graphene sheets in poly-
meric matrix can be easily removed.
Functional groups attached to the graphene nanosheets could
provide active sites to form chemical bonds, acting as an ideal
a
The State Key Lab of Fire Science, University of Science and Technology
of China, Hefei, Anhui, 230026, China. E-mail: yuanhu@ustc.edu.cn; Fax:
+86-551-3601664; Tel: +86-551-3601664
b
The Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute for
Advanced Study, University of Science and Technology of China, Suzhou,
Jiangsu, 215123, China
c sulfuric acid (98%), sodium nitrate, potassium permanganate,
Department of Chemical and Materials Engineering, Key Laboratory of
Powder and Energy Materials, Hefei University, Hefei, Anhui, 230022,
China
urethane (PU) is such a polymer, as it can form chemical bonds
with GNSs by reaction between the isocyanate groups at the end
of the PU chains and hydroxyl groups on the GNSs. Kim et al.14
reported exfoliated graphene-reinforced thermoplastic poly-
urethane (TPU) nanocomposites with improved gas barrier and
electrical conductivity. Lee et al.15 prepared nanocomposites of
waterborne polyurethane (WPU) with FGSs by an in situ
method; however, the thermal stability and tensile strength of the
nanocomposites deteriorated. For many applications, the poly-
urethane materials are expected to show enhanced properties.
The discovery in previous work16 convinces us that the graphene
sheets are able to make polymeric coatings much stronger and
more protective. In this study, we report a facile and rapid
preparation of graphene nanosheets/polyurethane (GNS/PU)
nanocomposites by in situ polymerization of monomer and
GNSs, which provides a path to obtain a new class of graphene-
based materials and use them in a variety of applications.
Experimental
Raw materials
Graphite powder (Spectrum Pure) was purchased from Sino-
pharm Chemical Reagent Co. LtdS (Shanghai, China).
4,40 -Diphenylmethane diisocyanate (MDI) and poly(tetra-
methylene glycol) (PTMG, molecular weight: 2000) were
supplied by Anhui ANLI Artificial Leather Co. Ltd. (Hefei,
China) and dried at 90  C under vacuum for 3 h. Concentrated
30% H2O2 solution, hydrochloric acid, ethylene glycol (EG),
hydrazine hydrate (85%) and N,N-dimethylformamide (DMF)

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were all reagent grade and provided by Sinopharm Chemical Table 1 Formulations of GNS/PU composites and their tensile prop-
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Reagent Co. LtdS (Shanghai, China). erties and electrical conductivity

Tensile
Preparation of the GNS/PU composites GNS strength Elongation Conductivity
Sample (wt%) (MPa) at break (%) (S cm1)
The procedure for fabricating graphene nanosheet functionalized
polyurethane is presented in Scheme 1. The typical process PU-0 0 10.8  0.8 195  19 1.13  1011
PU-1 0.1 12.5  1.1 291  24 1.02  1010
includes three steps: (1) synthesis of GO powders from graphite PU-2 0.5 16.4  0.9 386  32 6.24  1010
by Hummers’ method,17 (2) chemical reduction of the aqueous PU-3 1.0 23.2  1.6 448  28 3.06  109
GO nanosheet dispersion by hydrazine to generate a GNS PU-4 2.0 36.3  2.0 535  35 2.15  108
suspension,18 (3) in situ polycondensation of MDI and PTMG in
the presence of graphene sheets. Briefly, the preparation of the
sample GNS/PU-0.1 was as follows: 60.0 mg of GNS powder was
microscopy (AFM) observation was performed on a DI Multi-
dispersed in 60.0 g of DMF with the assistance of sonication at
mode V in tapping-mode. The aqueous GO nanosheet suspen-
room temperature. Then, 20.0 g of MDI was introduced into the
sion and DMF suspension of GNSs were spin-coated onto
above GNS suspension at 70  C for 2 h in a four-necked flask
freshly cleaved mica surfaces. Wide-angle X-ray diffraction
protected by N2. Afterwards, 35.6 g of PTMG and 3.7 g of EG
patterns of the samples were recorded on an X-ray diffractometer
were added into the flask and the mixture was stirred at 80  C for
(Rigaku Dmax/rA, Japan), using Cu-Ka radiation (l ¼
another 8 h. Two days of drying at 50  C was the last step for the
0.15418 nm) at 40 kV and 20 mA. Solid-state 13C NMR spectra
preparation of the GNS/PU composites. Other samples con-
were collected using a Bruker AV400 NMR spectrometer (400
taining 0.5 wt%, 1.0 wt% and 2.0 wt% GNS were synthesized by
MHz). The Fourier transform infrared (FTIR) spectra were
the same procedures. The formulations of GNS/PU composites
recorded using a Nicolet 6700 spectrophotometer in KBr pellets.
are presented in Table 1.
The tensile properties of GNS/PU composites were measured by
a universal testing machine (WSM-20KB type). At least five
Characterization
samples were tested to obtain average values according to GB/T
High-resolution transmission electron microscopy (HRTEM) 16421-1996. The surface electrical conductivity at room
analysis was conducted using a JEOL JEM-2100 instrument with temperature was measured with a ZC36 high resistance meter.
an acceleration voltage of 100 kV. The GNS/PU composties were Measurements were repeated on three different areas of the
dropped on a copper grid for directTEM imaging. Atomic force composite films to ensure sample uniformity and their averages

Scheme 1 Synthesis of polyurethane-functionalized graphene nanosheets.

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Fig. 1 Digital photos of different samples at a concentration of 1 mg
ml1: (a) GO in deionized water, (b) GNS in deionized water, and
(c) GNS in DMF after sonication.
are reported. Thermogravimetric analysis (TGA) of samples was
carried out with Q5000 thermal analyzer (TA Co., USA) from
50  C to 800  C at a heating rate of 10  C min1 in N2 atmosphere
(flow rate of 100 ml min1). Dynamic mechanical analysis
(DMA) was performed on a PerkinElmer Pyris Diamond DMA
from 80  C to 150  C at a heating rate of 5  C min1, at
a frequency of 1 Hz in the tensile configuration.
Results and discussion
The digital photos of different samples at a concentration of 1 mg
ml1: (a) GO in deionized water, (b) GNS in deionized water, and
(c) GNS in DMF after sonication are shown in Fig. 1. As is well
known, an important property of GO is its easy exfoliation in
aqueous media. As a result, GO readily forms stable colloidal
suspensions of thin sheets in water.19,20 After suitable ultrasonic
Fig. 2 AFM images of (a) GO nanosheets dispersed in water and (b) GNSs redispersed in DMF.
4224 | J. Mater. Chem., 2011, 21, 4222–4227
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treatment, such exfoliation can produce stable dispersions of
very thin graphene oxide sheets in water.9,18 However, significant
precipitation is observed in deionized water because of the
hydrophobic nature of graphene and its strong tendency to
agglomerate in water.7 GNS subjected to sonication can be well
suspended in a strongly polar medium, such as DMF, which
paves the way for easy fabrication of the GNS-based nano-
composites in DMF suspension.
In order to illustrate the complete exfoliation of GO and GNS
suspensions, AFM observations were conducted. The tapping-
mode AFM images of GO (dispersed in deionized water) and
GNSs (dispersed in DMF) are presented in Fig. 2. From the
cross-section analysis, we found that both GO nanosheets and
GNSs are typically a few to several hundred nanometres in size.
Furthermore, GNSs have a height of around 1.16 nm, corre-
sponding well with the reported thickness found in the litera-
ture.14 It should be noted that the thickness of GNSs is slightly
lower than that of GO nanosheets dispersed in water (1.186 nm,
Fig. 2a), which has been suggested to be attributable to the
removal of oxide groups.21
Solid-state 13C MAS NMR spectra were employed to explore
the structural change between GO and GNS induced by the
chemical reduction. Fig. 3 displays the solid-state 13C MAS
NMR spectra of (a) GO and (b) GNS. In the spectrum of GO,
the peaks at 58 and 68 ppm are attributed to the 13C nuclei in
the epoxide and hydroxyl groups, respectively.22–24 The peak at
132 ppm belongs to the un-oxidized sp2 carbons of the gra-
phene network. As for the 13C spectrum of the GNS, the peaks
from the oxygenated and the carbonyl carbons cannot be
observed, which results from the chemical reduction of epoxide
and carbonyl groups. In addition, plentiful sp2 carbon atoms
are introduced after chemical reduction, as indicated by the
single peak at 117 ppm, suggesting the formation of graphene-
based materials.
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Fig. 5 HRTEM images of the GNS/PU composites: (a) PU-1, (b) PU-4
(at high magnification) and (c) PU-4 (at low magnification).

facilitate their uniform dispersion in appropriate organic media,

but also make their exfoliation into individual sheets available.11
The performance of nanocomposites depends strongly on the
dispersion state of nanofillers in the polymer matrix. Therefore,
to evaluate the dispersion of graphene in the PU matrix,
HRTEM was employed to investigate the morphology of the
samples. Fig. 5 shows the HRTEM images of (a) PU-1, (b) PU-4
(at high magnification) and (c) PU-4 (at low magnification). As
can ve seen from Fig. 5(a), the exfoliated graphene sheets are
finely dispersed in the matrix of PU. Part of GNSs are obscure
due to the very thin nature of GNS, whereas others are clear,
Fig. 3 Solid-state 13
C MAS NMR spectra of (a) GO and (b) GNS probably attributable to the stacked structure. Fig. 5(b) displays
powders. a TEM image showing that the GNSs are dispersed in the PU
matrix with the form of not only a single sheet but also in stacks.
However, the stacked GNSs are still at the nanometre scale. The
TEM images of the PU-4 nanocomposites (Fig. 5c) distinctly
reveal that polyurethane microspheres are attached to the surface
of graphene sheets, which suggests good compatibility between
GNS and PU.
FTIR spectra of GO, GNS, PU and GNS/PU composite are
presented in Fig. 6. The absorption band of GO at around 1730
cm1 is ascribed to carboxyl groups. The absorption of GNSs at
this range is not observable, likely due to the overlapping of the

Fig. 4 XRD patterns of GO and GNS powders.

To further confirm the structures, the XRD patterns of GO

and GNS powders are presented in Fig. 4. The XRD trace of GO
powders exhibits a sharp diffraction peak at 9.6 (corresponding
to interlayer spacing of about 0.92 nm), whereas that of the GNS
powders presents no visible peak. Although this does not
necessarily mean that all stacking is lost, it does indicate the
disordered stacking structure of the GNS powders.11,25 The weak
van de Waals interactions of the GNS powders should not only Fig. 6 FTIR spectra of GO, GNS, PU and the GNS/PU composite.

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Fig. 7 Plots of storage modulus vs. temperature for PU and GNS/PU
composites.
strong absorption of graphene sheets in this region.26 For the
control PU, the stretching vibrations of the N–H groups occur at
3320 cm1, which together with the carbonyl bands at 1706 cm1
are indicative of the presence of urethane moieties. The strong
absorption band at around 1110 cm1 is attributed to –C–O–C–
group in PTMG. Because the GNS shows no obvious absorption
at the infrared range, there is no visible change in the FTIR
spectra of PU-4 after incorporating the GNS into PU.
Graphene sheets have been applied to reinforce composites in
previous research.27,28 According to the tensile properties of PU
and GNS/PU composites, which can be seen in Table 1, the
reinforcing effect of GNSs is rather significant: the 2.0 wt% GNS
incorporation leads to a 239% increase in tensile strength and
a 174% raise in elongation at break. The resultant homogeneous
dispersion of GNS in composites by in situ polymerization is
ascribed to the enhancement of the interfacial interaction with
matrix. Table 1 also shows the surface resistance of PU con-
taining GNS. Incorporation of GNS could effectively increase
the electrical conductivity of the PU films (reduced resistance).
This reinforcement is also attributed to the in situ polymerization
method, in which covalently grafted PU chains on GNS surface
cannot hinder direct contact between graphene sheets. Fig. 7
illustrates that the storage modulus (E0 ) of the PU composite
containing 2.0 wt% GNS is about 202% higher than that of the
PU at 75  C. Moreover, E0 is generally improved by the
Fig. 8 (a) TGA and (b) DTG thermograms for GO, GNS and GNS/PU composites.
4226 | J. Mater. Chem., 2011, 21, 4222–4227
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addition of GNS at all temperature ranges, which shows that
GNS effectively reinforces the PU, similar to the results of the
tensile properties. Undoubtedly, the excellent reinforcement of
graphene can be attributed to the good dispersion of graphene
sheets in composites and the strong interaction between the
graphene and PU matrix.
Fig. 8 shows the (a) TGA and (b) DTG curves of GO, GNS
and GNS/PU composites under nitrogen atmosphere. GO is
thermally unstable and starts to lose weight upon heating even
below 100  C, which is due to the release of water contained in
the samples. The major mass loss (about 50%) occurs below 250

C, presumably assignable to the decomposition of the oxygen-
contained functional moieties such as epoxy and hydroxyl.12 The
thermally labile oxygen functional groups are removed by
chemical reduction, which gives rise to much increased thermal
stability for the GNS. Apart from a slight weight loss below 100

C, which can be attributed to the release of adsorbed water, no
significant mass loss is observed when the GNS is heated up to
800  C. As for GNS/PU composites, the incorporation of GNS
induces thermal stabilization: with the load of 2.0 wt% GNSs, the
temperature for 5% weight loss of PU increases by about 40  C.
This corresponds well with recent research results.29,30 This
improvement in thermal stability can be attributed to the so-
called ‘‘tortuous path’’ effect of GNSs, which delays the escape of
volatile degradation products and also char formation.11
Furthermore, the residual weight percentages above 600  C
indicate that the amount of graphene in composites increases
with the feed content of GNS.
Conclusion
In this article, we have reported an efficient method to prepare
graphene nanosheets reinforced polyurethane composites by
in situ polymerization. The graphene nanosheets were success-
fully synthesized by the chemical reduction of graphite oxide.
The hydroxyl functional groups on the GNS are well suited to
form composites with polyurethane via chemical bonding. The
special two-dimensional morphology of the exfoliated graphene
nanosheets, and the functionalized surface of GNS, provide
homogeneous dispersion, high contact area, and reduced inter-
facial electrical resistance with the PU matrix. The strong
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interaction between graphene and PU imparts superior
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mechanical and highly improved thermal properties to the host
polymer, at relatively low loadings. The in situ polymerization
technique presented herein provides a promising and facile
approach to prepare graphene-based nanocomposites of poly-
mers with enhanced performances.
Acknowledgements
The work was financially supported by the National Natural
Science Foundation of China (No. 51036007), the joint fund of
the National Natural Science Foundation of China (NSFC) and
the Civil Aviation Administration of China (CAAC) (No.
61079015), the joint fund of NSFC and Guangdong Province
(No. U1074001) and the Opening Project of National Synchro-
tron Radiation Laboratory of USTC.
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