Research Article

Received: 21 July 2008 Revised: 23 October 2008 Accepted: 25 November 2008 Published online in Wiley Interscience: 26 February 2009

(www.interscience.wiley.com) DOI 10.1002/pi.2549

Morphological and physical properties of a

thermoplastic polyurethane reinforced with
functionalized graphene sheet
Duc Anh Nguyen,a Yu Rok Lee,a Anjanapura V Raghu,a Han Mo Jeong,a∗
Cheol Min Shinb and Byung Kyu Kimc

Abstract
BACKGROUND: Functionalized graphene sheet (FGS) was recently introduced as a new nano-sized conductive filler, but little
work has yet examined the possibility of using FGS as a nanofiller in the preparation of polymer nanocomposites. In particular,
there are currently no published papers that evaluate polyurethane/FGS nanocomposites. The purpose of this study was to
prepare a polyurethane/FGS nanocomposite and examine the morphological and physical properties of the material.

RESULTS: A cast nanocomposite film was prepared from a mixture of thermoplastic polyurethane (TPU) solution and FGS
suspended in methyl ethyl ketone. The FGS dispersed on the nanoscale throughout the TPU matrix and effectively enhanced
the conductivity. A nanocomposite containing 2 parts of FGS per 100 parts of TPU had an electrical conductivity of 10−4 S cm−1 ,
a 107 times increase over that of pristine TPU. The dynamic mechanical properties showed that the FGS efficiently reinforced
the TPU matrix, particularly in the temperature region above the soft segment melt.

CONCLUSION: Our results show that FGS has a high affinity for TPU, and it could therefore be used effectively in the preparation
of TPU/FGS nanocomposites without any further chemical surface treatment. This indicates that FGS is an effective and
convenient new material that could be used for the modification of polyurethane. It could also be used in place of other
nano-sized conductive fillers, such as carbon nanotubes.

c 2009 Society of Chemical Industry

Keywords: functionalized graphene sheet; thermoplastic polyurethane; nanocomposite; conductivity; mechanical properties

INTRODUCTION since they are composed of stacks of parallel lamellae with a 1 nm

Electrically conducting composites made of polymers and con-
ducting fillers, such as natural graphite, carbon black and metal
powders, have been extensively investigated in the past few
decades. These materials can be utilized in antistatic coatings,
electromagnetic shielding and corrosion-resistant coatings, as
well as in various other applications.1 – 4 However, these compos-
ites often contain as much as 15 wt% filler, since a large amount
of conventional micrometer-scale conducting filler is required to
achieve an electrical conductivity of 10−4 S cm−1 . This high level
of filler results in poor mechanical properties, poor processability
and high density.5
Nanocomposites are composed of polymer matrices with
reinforcements less than 100 nm in size. These materials have
attracted considerable attention, because many of the physical
properties of matrix polymers, such as their electrical, mechanical,
barrier, and flame-retarding properties, can be substantially
enhanced using a very small amount of reinforcement as compared
to conventional composites.6,7 Since the unique properties of
polymer nanocomposites stem from the maximized interfacial
contact between the polymer matrix and the reinforcement, the
most commonly utilized fillers have a high surface-to-volume ratio.
412
thickness and a high aspect ratio.8 – 11
Graphite has been widely used as a filler in conducting polymer
composites for two main reasons: it is a naturally abundant, cheap
material and it has good electrical conductivity in the region of
104 S cm−1 . Graphite consists of layered graphene, which is a one-
atom-thick sheet of hexagonal carbon rings. The typical interlayer
spacing between graphene layers is 3.35 Å, and they are weakly
bonded to each other by van der Waals forces. Each graphene
sheet has a high aspect ratio, high modulus, high surface area and
excellent electrical and thermal conductivity along the graphene
plane. It follows then that if these layers could be separated
down to a nanometer thickness, they could effectively reinforce a
∗
Correspondence to: Han Mo Jeong, Department of Chemistry, University of
Ulsan, Ulsan 680-749, Korea. E-mail: hmjeong@mail.ulsan.ac.kr
a Department of Chemistry, University of Ulsan, Ulsan 680-749, Korea
b Research Center, N-Baro Tech Co., 974-1, Goyeon-ri, Ungchon-myon, Ulju-gun,
Ulsan 689-871, Korea
c Department of Polymer Science and Engineering, Pusan National University,

For example, layered silicates like montmorillonite are often used Busan 609-935, Korea

Polym Int 2009; 58: 412–417 www.soci.org

c 2009 Society of Chemical Industry
Properties of a TPU reinforced with FGS
polymer matrix and create an uninterrupted conducting network
for electrons within the polymer.12 – 14
The weak interplanar forces allow for a wide range of atoms,
molecules and ions to insert themselves into the interplanar
spaces of graphite to form graphite intercalation compounds
(GICs). Expanded or partially exfoliated graphite can be prepared
from various GICs by intense, rapid heating with a flame,
microwaves, laser irradiation or inductively coupled plasma. When
the intercalate is suddenly volatilized, a very large unidirectional
expansion takes place and the graphite flakes off.15,16 A number
of studies have been conducted on expanded graphite-reinforced
conductive polymer nanocomposites. This is because the graphite
nanoplatelets obtained by partial exfoliation, while being cheap,
also have a high aspect ratio, and they form a conductive network
at low concentrations.17 – 21
Graphite oxide (GO), prepared from the oxidation of graphite, is a
compound with a layered structure. Each layer consists of randomly
distributed unoxidized aromatic regions and six-member aliphatic
regions with polar groups attached. These polar groups, such as
hydroxyl, epoxide, ether and carboxylate groups, are the result
of oxidation.22 – 25 It has been reported recently that GO can be
exfoliated into single sheets if it is sufficiently oxidized. In this case,
the inter-graphene spacing associated with the native graphite is
completely eliminated in the oxidation stage used for exfoliation.
In addition, adequate pressure (from CO2 gas evolved by the
decomposition of functional groups) must also be built up at the
gallery between the GO sheets during the rapid heating.26,27 This
completely exfoliated GO, in which the inter-graphene spacing
associated with GO and the graphite is completely excluded after
thermal expansion, has an affinity for polar solvents and polymers,
as well as good conductivity. These properties stem from the
fact that the completely exfoliated GO is composed of single
functionalized graphene sheets (FGSs) that still contain the polar
functional groups that remain after thermal treatment.28,29
Thermoplastic polyurethanes (TPUs) are unique polymeric ma-
terials with a wide range of physical and chemical properties.
Because a wide range of monomeric materials are now com-
mercially available, and because tailor-made properties can be
obtained from well-designed combinations of these monomeric
materials, TPUs can be tailored to meet the highly diversified
demands of modern technologies.30 This versatility allows TPUs
to be utilized in various applications where electrical conductivity
is critical, and therefore many researchers have studied conduc-
tive TPU nanocomposites.31 Most of these nanocomposites have
carbon nanotubes as conducting filler after additional surface
treatment.32 – 37
In the study reported here, we focused on the preparation of
a new conductive TPU nanocomposite using FGS as a nanofiller
without further surface treatment. The conductivity and other
physical properties of the material are discussed.
EXPERIMENTAL
Materials
Natural graphite (HC-908) with an average particle size of
8 µm was purchased from Hyundai Coma Co. Ltd, Korea.
Polycaprolactone (PCL) diol (2000 g mol−1 ; Solvay SA, Brussels,
Belgium) was dried and degassed at 80 ◦ C under vacuum for
3 h. 4,4 -Methylenebis(cyclohexyl isocyanate) (H12 MDI; BASF),
1,4-butanediol (BD; BASF), dioctyltin dilaurate (DOT; CNA Co.
Ltd, Chungnam, Korea), methyl ethyl ketone (MEK; Aldrich),
concentrated H2 SO4 (96%; Matsunoen Chemicals Ltd, Osaka,
Polym Int 2009; 58: 412–417

c 2009 Society of Chemical Industry
www.soci.org
Japan), fuming HNO3 (Matsunoen Chemicals Ltd) and KClO3
(Samchun Pure Chemical Co. Ltd, Seoul, Korea) were used as
received.
Preparation of FGS
GO was prepared using the Staudenmaier method.26,38 A 500 mL
round-bottom flask containing 10 g of graphite powder and
270 mL of a concentrated H2 SO4 /fuming HNO3 mixture (2/1 v/v)
was cooled to 0 ◦ C and agitated. KClO3 (110 g) was slowly added
to the reaction mixture, taking care that the temperature of the
mixture remained below 20 ◦ C. The reaction mixture was allowed
to reach room temperature and stirred for 120 h. Then the mixture
was poured into 10 L of deionized water. The GO was filtered and
washed with distilled water until the pH reached 6.5. The resulting
GO was dried at 80 ◦ C, and then pulverized and screened with a
100 mesh sieve to obtain fine particles. Elemental analysis showed
that the composition of the GO was C10 O3.68 H2.48 .
In order to obtain the FGS, the dried GO was placed in a
quartz tube, and the tube was flushed with argon for 10 min. The
quartz tube was then quickly inserted into a furnace preheated
to 1100 ◦ C. The tube was left in the furnace for 5 min while
the evolution of CO2 split the GO into individual sheets.26 – 29
The apparent specific volume of the FGS was 410 cm3 g−1 , and
elemental analysis showed that the composition of the FGS was
C10 O0.50 H0.51 .
Preparation of TPU/FGS nanocomposite
A 500 mL round-bottom, four-necked separable flask was
equipped with a mechanical stirrer, a nitrogen inlet, a thermome-
ter and a condenser with a drying tube. TPUs were prepared via
solution polymerization in MEK under a dry nitrogen atmosphere.
That is, PCL diol (0.01277 mol), H12 MDI (0.02554 mol) and DOT
(0.03 phr based on total solid) were added to the round-bottom
reactor, and the reaction was allowed to continue for 1 h at 50 ◦ C.
BD (0.01277 mol) was then added and the reaction proceeded for
another 3 h at 80 ◦ C. As the reaction progressed, the increasing
viscosity of the mixture was controlled by adding MEK. Upon
completion of the reaction, the solid content of the polymer so-
lution was about 45%. The number-average and weight-average
molecular weights of the TPU as measured by gel permeation
chromatography relative to polystyrene standards were 24 300
and 59 200, respectively. Recipe calculations placed the soft PCL
segment content of the TPU at 70 wt%.
The FGS was immersed in MEK and sonicated for 3 h. This
sonicated mixture, about 1 wt% solid content, was fed into the
polymer solution and agitated at 80 ◦ C for 3 h to obtain the
TPU/FGS nanocomposite solution.
Nanocomposite films were cast on polypropylene plates at
25 ◦ C for 24 h, and then at 60 ◦ C for 24 h. The sample designation
codes in Table 1 provide information regarding the amount of FGS
included in the TPU samples. For example, TPUN-5 contains 5 parts
of FGS per 100 parts of polymer.
Measurements
The molecular weights of the TPU samples were evaluated at
43 ◦ C by gel permeation chromatography (Waters M510) using
tetrahydrofuran as an eluent.
XRD patterns were obtained with a Rigaku RAD-3C X-ray
diffractometer using Cu Kα radiation (λ = 1.54 Å) as the X-ray
source. The diffraction angle was scanned from 2◦ at a rate of 1.2◦
413
min−1 .
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Table 1. Thermal properties of TPU/FGS nanocomposites

Soft segment Hard segment

Sample Tg (◦ C) Tms (◦ C) Hms (J g−1 ) Tmh (◦ C) Hmh (J g−1 )

TPUN-0 −45.2 41.8 25.8 103.2 1.3

Intensity
TPUN-0.5 −42.9 41.8 25.3 104.5 1.7
TPUN-1 −45.2 42.2 22.0 101.6 2.0 Graphite
TPUN-2 −44.5 42.5 21.5 99.7 1.4
TPUN-3 −46.0 40.9 21.1 107.0 1.0 GO
TPUN-4 −45.5 41.0 21.1 105.4 1.5
TPUN-5 −48.4 40.8 6.3 126.7 1.0 FGS
TPUN-7 −47.6 41.7 5.2 111.9 2.1

5 10 15 20 25 30
2θ (°)
DSC was carried out with a Mettler Toledo DSC 823e instrument
at heating and cooling rates of 10 ◦ C min−1 with 7 mg of sample. Figure 1. XRD patterns of graphite, GO and FGS.
The samples were loaded at 30 ◦ C and cooled to −60 ◦ C, and the
thermal properties were measured in a subsequent heating scan.
TGA was performed with a Mettler Toledo SDTA 851e instrument TPUN-0
at a heating rate of 10 ◦ C min−1 under nitrogen atmosphere with
22 mg of sample in a platinum crucible.
The morphology of the nanocomposites was examined using
transmission electron microscopy (TEM; Hitachi H-8100). In
order to obtain samples for TEM observations, cast films
of the nanocomposites were cryogenically pulverized. The TPUN-3
nanocomposite powder was then mixed with epoxy resin and
cured at 70 ◦ C for 24 h in a vacuum. The cured material was
Exotherm

microtomed into slices. A layer of carbon was subsequently

deposited onto each slice, being on 200 mesh copper net. The
TEM acceleration voltage was 200 kV.
The dynamic mechanical properties of cast films 0.5 mm thick
were analyzed using dynamic mechanical analysis (DMA; DMA-
Q800, TA Instruments). Testing was performed in bending mode
at 1 Hz and a heating rate of 5 ◦ C min−1 .
Tensile testing was performed using an OTU-2 tensile tester
(Oriental TM Co., Korea). Cast films were cut into micro-tensile
specimens 25 mm in length, 5 mm in width and 0.5 mm in
thickness. The specimens were elongated at a rate of 200 mm
min−1 at 25 ◦ C.
Direct current conductivity at room temperature across a 0.5 mm
thick cast film was measured with a picoamperometer (Keithley
237). Circular silver electrodes measuring 0.28 cm2 were attached
at both surfaces of the specimen. Silver paste was used to ensure
good contact between the specimen surface and the electrode.
RESULTS AND DISCUSSION
XRD and thermal properties
Figure 1 shows the wide-angle XRD patterns of the graphite, GO
and FGS specimens. The diffractogram of graphite shows a very
intense and narrow peak at 2θ = 26.5◦ , which corresponds to the
X-ray reflection on the (002) planes of well-ordered graphenes.
This indicates that the interlayer spacing, Ic , between the well-
ordered graphenes is 3.35 Å. GO has a broad peak at 2θ = 14.1◦ .
Again, this peak corresponds to the X-ray reflection on the (002)
planes, and it indicates that the interlayer spacing had expanded
to 6.27 Å by the accommodation of various functional groups on
the graphene.22,23,28,39 However, the FGS has no visible peak for
2θ > 2◦ . This indicates that the distances between the graphene
414
TPUN-5
TPUN-7
-50 0 50 100 150
Temperature (°C)
Figure 2. DSC thermograms of TPU/FGS nanocomposites.
disordered. That is, the long-range order of the GO was destroyed
by sudden thermal expansion.26 – 29
Figure 2 shows the DSC thermograms of the TPU and its
various nanocomposites. The quantitative results are summarized
in Table 1. In the DSC thermogram of TPUN-0, one can see the
glass transition temperature, Tg , and a sharp melting endothermic
peak of the soft segment, Tms , at −45.2 and 41.8 ◦ C, respectively. In
addition, a small endothermic melting peak of the hard segment
(Tmh ) is observed at 103.2 ◦ C. Table 1 shows that, as the amount
of FGS in the nanocomposites is increased, the heat of fusion at
Tms (Hms ) decreases and drops abruptly at higher contents of
FGS. This suggests that the crystallization of the PCL segment is
inhibited by the FGS, more evidently at higher contents of FGS. This
decrease in the crystallinity also seems to cause a decrease in Tg
with increasing FGS content. The heat of fusion at Tmh (Hmh ) does
not vary as much with the FGS content as does Hms (Table 1),
suggesting the possibility that the FGS is dispersed predominantly
in the soft segment domain. However, Tmh of nanocomposites with

layers have been greatly expanded, and the layers are sufficiently high FGS content is higher than Tmh of pristine TPU, indicating

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Properties of a TPU reinforced with FGS www.soci.org

Table 2. Degradation properties of TPU/FGS nanocomposites

Weight loss temperature (◦ C)

TPUN-0
Sample 2% 5% 10% 15% Residue (%)

TPUN-0 273.5 286.8 299.1 307.5 0.3

TPUN-1 277.6 291.4 302.2 309.8 1.5
TPUN-3 TPUN-2 275.2 291.9 301.2 309.4 2.7
Intensity

TPUN-3 277.8 294.6 309.6 319.2 3.6

TPUN-4 268.7 284.1 298.7 307.4 4.2
TPUN-5 271.0 285.8 299.6 308.2 5.3
TPUN-7 258.0 270.7 282.6 297.8 7.3
TPUN-5

concentrations as compared to TPUN-0. However, the degrada-

tion temperature decreases at higher FGS levels. In polymer/clay
TPUN-7 nanocomposites, the thermal degradation is retarded by the pres-
ence of clay, because the thin silicate lamellae with a high aspect
0 5 10 15 20 25 30 35 ratio provides a barrier that hinders the diffusion of the volatile de-
2θ (°) composition products and enhances char formation.41,42 Hence,
the improved resistance to thermal degradation at low levels of
Figure 3. XRD patterns of TPU/FGS nanocomposites.
FGS shown in Table 2 can be similarly explained by the barrier ef-
fect of the thin FGS. However, the fact that this improvement is not
as striking as compared to that of the clay nanocomposites30,43 – 45
120
TPUN-0 and the fact that a high FGS content adversely affects the thermal
TPUN-3 degradation resistance show that the FGS is not as effective, for
100
TPUN-5 thermal decomposition resistance enhancement, as a clay which
TPUN-7 has an inorganic nature.
Weight residue (%)

80

Morphological and physical properties

60
40
20
0 FGSs.
100 200 300 400
Temperature (°C)
Figure 4. TGA thermograms of TPU/FGS nanocomposites.
that the mobility of the hard segment in the melt state is reduced
in the presence of FGS.
The wide-angle XRD patterns of TPU and its nanocomposites
are shown in Fig. 3. The diffractogram of TPUN-0 has two peaks
at 2θ = 21.1◦ and 23.3◦ . These peaks can be attributed to the
reflections on the (110) plane and the (200) plane of the PCL
crystal, respectively.40 The intensity of these peaks decreases as
the content of FGS is increased, supporting the notion proposed
from the DSC results that the crystallinity of the PCL phase is
inhibited by increasing amounts of FGS. Figure 3 also shows that
the dispersed FGS does not give rise to any new wide-angle XRD
peak at 2θ > 2◦ . This suggests that either (1) the distance between
the FGSs is too great to allow for the observation of any signals
in the wide-angle XRD patterns or (2) no long-range order exists
even when the FGS has a stacked structure.
The thermal degradation behaviors of TPU and its nanocom-
posites were examined via TGA. Typical TGA thermograms are
shown in Fig. 4 and quantitative data are summarized in Table 2. It
Figure 5 shows TEM images of TPUN-4, in which one can see a
single FGS or stacks of FGSs whose thickness is less than several
nanometers. These FGSs are finely dispersed throughout the TPU
matrix with a wrinkled or hair-like structure. This morphology
demonstrates that the compatibility between the FGS and the
TPU is good enough to achieve nano-sized fine dispersion of the
500 600
Figure 6 shows the DMA results for TPU and TPU/FGS nanocom-
posites. The storage tensile modulus, E  , of TPUN-0 decreases
slowly upon heating from −150 ◦ C because of thermal expansion.
The rate of reduction of E  increases at Tg , and another sudden
drop of E  occurs at Tms . When the TPU is reinforced with FGS,
the E  values in the temperature regions below Tg and above Tms
are improved in comparison to those of TPUN-0. However, the
E  values between Tg and Tms are reduced compared to those of
TPUN-0. Figure 6 also shows that these variations are more evident
at higher levels of FGS. The E  increase observed in the temperature
regions below Tg and above Tms indicates that the FGS reinforces
the TPU matrix, and this reinforcement becomes more evident as
the matrix polymer weakens from the crystal melting. The E  re-
duction in the presence of FGS in the temperature region between
Tg and Tms indicates that the decrease in modulus caused by the
reduced PCL crystallinity overshadows the reinforcing effect of
the FGS.
In Fig. 6, one can see that tan δ peak temperature at ca −50 ◦ C,
which is Tg measured by DMA, moves to lower temperature as the
FGS content is increased, which shows that Tg is decreased due to
the reduced crystallinity of the soft segment, as found for the DSC
results. Figure 6 also shows that the tan δ value at Tg is increased
as the content of FGS is increased. This suggests that viscous flow
415

is evident that the degradation temperature increases at low FGS rather than elastic deformation of the soft segment by external

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 www.soci.org DA Nguyen et al.

10000
TPUN-0
TPUN-3
1000 TPUN-5
TPUN-7

100

E’ (MPa)
10

0.1
1

TAN δ
0.1

0.01
-150 -100 -50 0 50 100 150
Temperature (°C)

Figure 6. Dynamic mechanical properties of TPU/FGS nanocomposites.

Table 3. Physical properties of TPU/FGS nanocomposites

Tensile properties

Modulus Tensile strength Elongation Conductivity

Figure 5. TEM micrographs of TPUN-4. Sample (MPa) (MPa) at break (%) (S cm−1 )

TPUN-0 458 ± 23 20.0 ± 0.1 814 ± 64 4.58 × 10−11

TPUN-0.5 559 ± 113 18.8 ± 0.1 779 ± 40 8.37 × 10−11
dynamic force is enhanced at Tg in the presence of FGS. This may
TPUN-1 557 ± 85 17.8 ± 0.3 693 ± 34 4.62 × 10−10
be due to the reduced crystallinity of the soft segment.
TPUN-2 639 ± 70 13.4 ± 0.1 686 ± 43 5.41 × 10−4
Table 3 shows that the tensile modulus of the nanocomposites
TPUN-3 657 ± 157 15.5 ± 0.3 693 ± 52 5.88 × 10−4
is improved as compared to TPUN-0 when the reduction of
TPUN-4 636 ± 47 17.0 ± 0.1 517 ± 13 8.54 × 10−4
Hms by the FGS was not very apparent (Table 1). However,
TPUN-5 351 ± 2 18.8 ± 0.9 347 ± 73 9.16 × 10−4
when the reduction of Hms is evident at high FGS levels the
TPUN-7 357 ± 43 18.9 ± 0.2 245 ± 22 4.92 × 10−4
tensile modulus decreases. These results also show that the
FGS can reinforce the TPU matrix. The tensile strength and the
elongation at break generally decreased in the presence of FGS
when compared with those of TPUN-0. This result indicates that about 10−2 S cm−1 with a carbon nanotube loading of 2 vol.%.35
molecular rearrangement and orientation with respect to the Other research groups have reported conductivities lower than
tensile axis during deformation are inhibited in the presence of 10−5 S cm−1 with carbon nanotube loading of 2 wt%.1,33,34 These
the FGS. The reduced soft segment crystallinity can also contribute results suggest that the FGS can be used as an alternative
to these reductions of tensile strength and elongation at break. conductive nanofiller in place of carbon nanotubes.
One can see from Table 3 that a drastic 107 times improvement
in conductivity is observed by the addition of FGS at an amount
of 2 parts of FGS per 100 parts of TPU. This result shows that finely CONCLUSIONS
dispersed FGSs with nano-sized thicknesses and high aspect ratios It was demonstrated that FGS can be finely dispersed on the
(Fig. 5) can create an effective conductive channel. Many research nanoscale in a TPU matrix simply by solution mixing. No further
groups have reported the conductivity of polyurethane/carbon chemical surface modification of the FGS was required. The FGS
nanotube nanocomposites. Cho and co-workers reported a effectively improved the conductivity of the TPU by a factor
conductivity of about 0.3 S cm−1 with a carbon nanotube loading of about 107 as compared to pristine TPU. A conductivity of
416

of 3 wt%,37 and Vaia and co-workers reported a conductivity of 10−4 S cm−1 was achieved in the nanocomposite containing only

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c 2009 Society of Chemical Industry Polym Int 2009; 58: 412–417
Properties of a TPU reinforced with FGS
2 parts of FGS per 100 parts of TPU. The FGS effectively reinforced
the TPU matrix in the temperature region above Tms . However,
because the dispersed FGS hindered the crystallization of the
soft segment, this reinforcing effect was overshadowed by the
softening due to the decreased crystallinity in the temperature
region between Tg and Tms .
ACKNOWLEDGEMENTS
This research was financially supported by the Ministry of
Education, Science Technology (MEST) and the Korean Industrial
Technology Foundation (KOTEF) through the Human Resource
Training Project for Regional Innovation
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