Ionic liquid modified graphene/poly(vinyl alcohol) composite with

enhanced properties
Lei Wang,1,2,3 Wenwen Wang,4 Ping Fan,1 Menglong Zhou,1 Jintao Yang,1 Feng Chen,1
Mingqiang Zhong1
1
College of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou 310014, People’s Republic of China
2
Institute of Biomaterials and Engineering, Wenzhou Medical University, Wenzhou 325027, People’s Republic of China
3
Wenzhou Institute of Biomaterials and Engineering, CNITECH, CAS, Wenzhou 325027, People’s Republic of China
4
Wenzhou Hospital of Integrated Traditional and Western Medicine, Wenzhou 325000, People’s Republic of China
Correspondence to: P. Fan (E - mail: fanping@zjut.edu.cn)

ABSTRACT: How to preserve the structure integrity of graphene while enhance its dispersion and compatibility in matrix attracts the
attention of researchers in graphene/polymer nanocomposite field. In this paper, methacryloxyethyltrimethyl ammonium chloride
(DMC), a kind of ionic liquids, was first used to non-covalently functionalize graphene in the process of graphene oxide (GO) reduc-
tion. The as-modified graphene (DMC-rGO) was further incorporated into poly(vinyl alcohol) (PVA) matrix by solution casting tech-
nique to fabricate DMC-rGO/PVA composites. The structure and properties of the obtained DMC-rGO were investigated by X-ray
diffraction analysis (XRD), X-ray Photoelectron Spectroscopy (XPS), Transmission Electron Microscope (TEM), Atomic force micros-
copy (AFM), and Raman test. The results showed that graphene could be successfully modified by DMC through ionic–p interaction
and the structure integrity of the graphene could be reserved by this non-covalently approach. Furthermore, after co-reduction pro-
cess, some hydroxyl groups were introduced into DMC-rGO. In virtue of these intrinsic properties of DMC-rGO, the fabricated
DMC-rGO/PVA composites exhibit considerable enhancements in mechanical properties and remarkable improvements in thermal
stability, as well as the enhancement in electrical conductivity at low DMC-rGO loading. This simple modification approach gives a
new opportunity to improve the performances of graphene/polymer composites. V C 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017,

134, 45006.

KEYWORDS: graphene; ionic liquid; non-covalently modification; poly(vinyl alcohol)

Received 5 December 2016; accepted 12 February 2017

DOI: 10.1002/app.45006

INTRODUCTION with polymer hosts.8,9 However, due to the aromatic nature of

Poly(vinyl alcohol) (PVA) is a kind of water soluble polymers.
For its environmental friendly, biocompatible character, good
film-forming capacity and possible coupling of charge transport
with the movement of its hydroxyl groups, PVA has been used
in several applications including drug release,1 tissue engineer-
ing,2 and enzyme immobilization,3 and has been combined with
nanoparticles to produce polymer nanocomposites with
improved mechanical and electrical properties.4–7
Among all the various types of nanoparticles, recently, gra-
phene, a single layered two-dimensional atomic carbon sheet,
possesses extraordinarily electronic, thermal and mechanical
properties, which makes it ideal nanofiller for PVA. For polymer
composites, the realization of successful reinforcement not only
depends on the intrinsic property of the nanofiller, but also
depends on optimizing the dispersion and interface interactions
graphene and the chemically stability of carbon atoms on gra-
phene sheets, graphene sheets cannot be effectively wetted by
hydrophilic PVA matrix, and are prone to form irreversible
agglomerates through p–p stacking and van der Waals attractive
interactions. The difficult dispersion of graphene sheets and
their poor interfacial interaction with matrix pose a big obstacle
for its application in the composites.
Therefore, graphene should be modified to increase its miscibili-
ty with the PVA. For example, graphene oxide (GO), which has
various oxygen containing functional groups (e.g., hydroxyl,
epoxy, and carboxyl) either on the basal plane or at the edges,
has been successfully exploited as a nanofiller for effective rein-
forcement of mechanical properties of PVA due to its good dis-
persibility in water and the strong hydrogen bonding
interaction between the two components.10 Another method is
functionalization of graphene with small molecules or polymers

C 2017 Wiley Periodicals, Inc.

V

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Figure 1. Raman spectra of GO, rGO, DMC-rGO.
which can offer good dispersion and strong interactions. Lee
and Jin.11 and Cano et al.12 covalently functionalized GO with
PVA by esterification of GO and PVA to increase compatibility
between GO and PVA; Wang et al.13 functionalized reduced gra-
phene oxide (rGO) with polyethyleneimine, and then incorpo-
rated the polyethyleneimine functionalized rGO into PVA to
improve the strength and toughness of PVA; Hwang et al.14
modified and reduced GO with poly(dopamine), and then
incorporated the poly(dopamine)-treated rGO into PVA to
obtain PVA-based humidity sensor. These literatures clearly
demonstrated that the functionalization of graphene increases
interfacial interaction between graphene nanosheets and the
polymer matrix, improves dispersion, and enhances the perfor-
mance of the end products. However, either these functionalized
graphenes or GO sheets mentioned above involved creating a
covalent bond between functional groups and graphene surface,
thereby producing structural defects on the conjugated graphene
surface and adversely affecting the electrical and mechanical
properties of the composites. Therefore, proper surface func-
tionalization of graphene is needed to produce well dispersed
and high-quality graphene sheets which can form high-
performance PVA composites for diverse applications.
Ionic liquids (IL), which are room temperature molten salt with
high thermal stability, have been used for functionalization of
carbon nanomaterials to improve specific properties such as
ionic and electric conductivity, thermal and mechanical perfor-
mance of carbon nanofillers. IL, containing imidazolium cation,
or ammonium cation, can be adsorbed onto the conjugated p
structure of carbon nanomaterials because of strong cation–p
interactions.15–17 Thus, ionic liquids could provide a facile and
Figure 2. XRD patterns of GO, rGO, DMC-rGO.
WWW.MATERIALSVIEWS.COM 45006 (2 of 10)
promising way for preserving the electronic structure of carbon
nanomaterials and their intrinsic properties. Furthermore, the
chemical structure of an ionic liquid, i.e., the presence of cati-
ons and anions, can have a dramatic effect on its solvent prop-
erties. More specifically, the physical and chemical properties
can be designed and adjusted by modifying the cationic or
anionic properties with functional groups.18 Therefore, it opens
door to new possibilities in the field of nanofabrication and
nanotechnology due to the availability of wide varieties of the
IL. According to the literature19 different ionic liquids has been
used as dispersing agent for CNTs in different thermoplastics,
such as vinylidene fluoride-hexafluoropropylene copolymer,20
polystyrene,21 polycarbonate,22,23 and polyurethane (PU)24 as
well as polymethylmethacrylate (PMMA).25
In this paper, to alleviate the aggregation of graphene and devel-
op strong interfacial interaction between the hydrophilic PVA
and inert graphene, methacryloxyethyltrimethyl ammonium
chloride (DMC), a kind of IL, was employed as a new coupling
and dispersing agent to modify graphene based on cation–p
interactions. Specifically, reduced graphene oxide modified with
DMC (DMC-rGO) was prepared by a one-step reduction and
surface modifying process. Then the DMC-rGO was incorporat-
ed into poly(vinyl alcohol) (PVA) matrix by solution casting
technique to fabricate DMC-rGO/PVA composites. The struc-
ture and morphology of the obtained DMC-rGO, and its role
played in the interaction between graphene and PVA were inves-
tigated. On this basis, the effect of DMC-rGO on conductivity,
mechanical strength and thermal stability of DMC-rGO/PVA
composites were investigated as well. This investigation might
provide a new route for modification of graphene and a new
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45006
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Figure 3. TEM images of (a) GO, (b) DMC-rGO.

approach to improve the comprehensive performances of gra-
phene/polymer composites.
EXPERIMENTAL
Materials
Pristine flake graphite (PG) was purchased from Qingdao
Guangli Graphite Co. Ltd. (China). Concentrated Sulfuric acid
(98%, H2SO4) was purchased from Quzhou Juhua Reagent Co.
Ltd. (China). Sodium Nitrate (NaNO3) was purchased from
Shanghai Zhenxin Reagent Factory (China). Potassium Perman-
ganate (KMnO4) was purchased from Hangzhou Xiaoshan
Chemical Reagent Factory (China). Hydrogen peroxide (H2O2),
Hydrazine hydrate (N2H4
H2O, 85%) and Polyvinyl Alcohol
(PVA, average degree of polymerization1750 6 50) were pur-
chased from Sinopharm Chemical Reagent Co. Ltd. (China).
Methacryloxyethyltrimethyl ammonium chloride (DMC) was
purchased from Wuxi XinYu Chemical Co. Ltd. (China). All
other reagents were of analytical grade and were used without
further purification.
Preparation of DMC-Functionalized Graphene
At first, graphite oxide was prepared from graphite using
Hummers method,26,27 and the preparation process had been
described in detail elsewhere.28 DMC-rGO was synthesized by
in situ reduction of GO in the present of DMC. Briefly, a solu-
tion of GO (10 mL, 0.8 mg/mL) and DMC (100 mg) was sub-
jected to ultrasonication for 30 min to obtain a yellow brown

Figure 4. AFM images of (a) rGO and (b) DMC-rGO. [Color figure can be viewed at wileyonlinelibrary.com]

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Table I. The Electrical Conductivity of GO, rGO, DMC-rGO
Sample GO DMC-rGO rGO
Conductivity(S/m) 0.0012 33.23 231.66
colloidal suspension and then vigorously stirring at 100 8C for
24 h by adding 1 lL N2H4
H2O. The resulting DMC-rGO was
subsequently centrifuged and washed with ethanol and water
for several times.
Fabrication of DMC-rGO/PVA Composite Films
Firstly, the PVA granules (2 g) were dissolved in deionized water
at 90 8C and the as-prepared DMC-rGO was fully ultrasonicated
to form a homogeneous dispersion. DMC-rGO/PVA composites
were fabricated by compounding DMC-rGO solution and the
PVA solution with the aid of ultrasonic. A series of DMC-rGO/
PVA composite films with different DMC-rGO contents were
further received via casting the compound solutions into glass
dishes.
Characterization
Fourier transform infrared (FTIR) spectra of the materials were
recorded with a Nicolet (6700) FTIR spectrophotometer of
American Thermo Nicolet Corporation. X-ray diffraction analy-
sis (XRD) was carried out using an X’ Pert PRO X-ray diffract
meter of Holland PNAlytical company. X-ray Photoelectron
Spectroscopy (XPS) was carried out using Kratos AXIS Ultra
DLD of Shimazu-KRATOS Company (United Kingdom). Trans-
mission Electron Microscope (TEM) mages were obtained using
a JEM-1230 instrument of JEOL Ltd. (Japan). operating at 120
kV. Scanning Electron Microscope (SEM) mages were obtained
using a Hitachi S-4700 instrument of Hitachi Limited (Japan).
Thermogravimetric Analysis (TGA) was carried out under a
nitrogen atmosphere with a SDTQ600 thermal analyzer. Univer-
sal Tensile Test was carried out using Shenzhen Sans CMT5104.
Photos for optical transparency of films and solutions were
recorded with a digital camera (Canon Power Shot A1000IS).
Atomic force microscopy (AFM) images were taken by Veeco
Nanoman VS in tapping mode.
Figure 5. FTIR spectra of rGO, GO, pure DMC and DMC-rGO (inset
shows molecular structure of DMC). [Color figure can be viewed at
wileyonlinelibrary.com]
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Figure 6. XPS wide spectra of the GO, rGO and DMC-rGO. [Color figure
can be viewed at wileyonlinelibrary.com]
RESULTS AND DISCUSSION
Structure and Morphology Characterization of DMC-rGO
Considering that both GO and DMC are well dispersed in
water, a one-step reduction and surface modifying process was
adopted to prepare DMC-rGO. Namely, rGO and DMC were
solution mix first and then co-reduced by Hydrazine hydrate.
Since it is a powerful tool to characterize carbon materials,29
Raman spectra are tested to characterize the as-prepared sam-
ples and the results are shown in Figure 1. it can be seen that
all the Raman spectra of GO, rGO and DMC-rGO display two
prominent peaks of D band at 1348 cm21 and G band at
1590 cm21. It could be found that the D/G intensity ratio
increased from 1.023 (GO) to 1.369 (rGO) and 1.460 (DMC-
rGO). Since the D band represents the disorder of graphene
which results from the conversion of sp2-hybridized carbon into
sp3-hybridized carbon, while the G band relates to the first-
order scattering of the stretching vibration mode E2g derived
from sp2 carbon atoms,30 the higher D/G intensity of rGO can
be attributed to the increase in smaller sp2 domains and a re-
establishment of conjugated graphene networks (re-aromatiza-
tion),31 suggesting a successful transformation of GO to
Rgo.32’33 Furthermore, the intensity ratio of DMC-rGO
increased from 1.369 to 1.460 compared with that of rGO,
Table II. The Mass Ratio of O and C in GO, rGO, DMC-rGO
Sample GO rGO DMC-rGO
mO/mC 0.65 0.15 0.26
Table III. The Elemental Composition of the DMC-rGO
Sample C N O
DMC-rGO 75.11 4.67 20.22
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Figure 7. XPS carbon 1s core-level spectra of (a) GO, (b) rGO, (c) DMC-rGO. [Color figure can be viewed at wileyonlinelibrary.com]
which not only suggests the p-electronic system of sp2-bonded
carbons of the graphene is not damaged by the modification,
but also suggests that DMC have successfully attached onto gra-
phene surface.
The X-ray diffraction (XRD) patterns of GO, rGO and DMC-
rGO are shown in Figure 2. The characteristic diffraction peak
of GO appears at 10.308 (Figure 2) attributed to the (002) plane
of the interplanar distance (d spacing) of 0.84 nm according to
the Bragg’s Law.34 For rGO and DMC-rGO, however, the peak
at 10.308 is entirely disappeared while a weak broad peak at
about 238 is obviously found. Furthermore, the calculated d
spacing of DMC-rGO is increased from 0.37 to 0.38 nm com-
pared with that of rGO. The XRD results also indicate that after
co-reduction process, GO are successfully reduced and at the
same time, DMC are successfully attached onto the surface of
graphene sheets. The enlarged d-spacing of as-produced DMC-
rGO should be attributed to the DMC attached to graphene.
The morphologies of the GO, DMC-rGO are further investigat-
ed. The TEM images of GO are shown in Figure 3(a), respec-
tively. It can be seen that GO are transparent and have both
thin and smooth surface. While for DMC-rGO shown in Figure
3(b), a much rougher surface with many wrinkles is observed.
More details of the surface morphology of graphenes were
observed by Atomic force microscope (AFM) at the nanoscale.
As it is shown in Figure 4, compared with that of GO, the sur-
face of DMC-rGO is much rougher. The thickness of DMC-
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rGO increased from 1.5 nm to approximately 2.6 nm compared
with that of rGO. This increasing thickness might be contribut-
ed by the absorbed DMC monomer. All the results of TEM and
ATM directly confirmed the successfully functionalization of
graphene with the introduction of DMC on its surface.
As confirmed by AFM, XRD, the sp2-bonded carbons of the
graphene was not damaged by the DMC modification. There-
fore DMC-rGO showed good electrical conductivity of 33.23 S/
m (Table I), which is four orders of magnitude greater than
that of GO. The reduction of one order of magnitude compared
with rGO might due to the absorption of DMC on the surface
of graphene, which enlarged the d-spacing of graphenes and
block the electrons transfer among graphene sheets by steric
hindrance.
FTIR results of GO, rGO and DMC-rGO are shown in Figure 5.
In the spectrum of GO, the presence of CAO (mcAo at
1049 cm21), CAOH (mCAOH at 1410 cm21), C@O (mC@O at
1633 cm21 and 1728 cm21) in carboxyl and OAH (mOAH at
3400 cm21) indicates that the surface of GO is decorated by
oxygenic groups. After reduction, these oxygen-containing
absorption peaks significantly reduced in the FTIR spectra of
both rGO and DMC-rGO. Compared with that of rGO, the
spectrum of DMC-rGO not only shows absorption peak at
3450 cm21 (corresponding to OAH stretch), but also shows
CAN stretch absorption peak at 1169 cm21. This result suggests
the present of DMC on DMC-rGO sheets.
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Figure 8. Photo images of GO, rGO, DMC-rGO dispersed in H2O. [Color

figure can be viewed at wileyonlinelibrary.com]

X-ray photoelectron spectra analyses are significant measures to Figure 9. (a) FTIR of DMC-rGO/PVA composite films with different
reveal the inner structure of C for carbon-based materials. The DMC-rGO content. (b) Absorption peak position of the AOH and
XPS survey spectra with the binding energy ranging from 0 to ACAOH stretching bands vs DMC-rGO content.
1400 eV of GO, rGO, DMC-rGO are present in Figure 6 and
the surface elemental compositions determined by XPS are those of GO. The C1s spectrum of DMC-rGO also exhibit these
listed in Tables II and III. It is shown that the surfaces of peaks corresponding to the functional groups with oxygen, but
untreated GO, rGO, DMC-rGO are dominated by carbon and a new peak at the binding energy of 285.9 eV is observed and
oxygen. And traces of nitrogen (4.67%) are also detected on assigned to the CAN species [Figure 7(c)]. The existence of
DMC-rGO samples. The appearance of N peak on DMC-rGO CAN peak suggests the strong interaction between DMC and
spectrum can be attributed to the nitrogen element in the DMC rGO, such as cation–p or p–p interactions.
and thus indicate the adsorption of DMC on DMC-rGO sam-
ples. As shown in Table II, after reduction, the level of oxygen For preparing composites by solution blending method, the dis-
decreased. C/O ratio of rGO is largely decreased from 0.65 to tribution of fillers in matrix is largely determined by its
0.15 compared with that of GO, suggesting most oxygen func-
tional groups are removed during the reduction process. How-
ever, the C/O ratio of DMC-rGO is a little higher than to that
of rGO. Considering the oxygen atom contained in DMC and
combining the result of Raman spectra, we do not think the
higher C/O ratio suggest the oxidation degree difference
between DMC-rGO and rGO, but suggest the attachment of
DMC on DMC-rGO sheets.
The patterns of the fitting peak treatment for the XPS spectra
of C1s in GO, rGO, DMC-rGO are presented in Figure 7. It
shows that the C1s peak of GO and rGO can be divided into
four types of carbon bonds: CAC/CAH, (284.8 eV), CAO
(286.5 eV), C@O (287.7 eV), @COO (289.0 eV) [Figure
7(a,b)].35,36 It is also observed that the relative intensities of Figure 10. Schematic illustration of the interactions between DMC-rGO
oxygen functionalities in rGO are obviously much weaker than and PVA. [Color figure can be viewed at wileyonlinelibrary.com]

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Figure 11. SEM image (a) Pure PVA; (b) the DMC-rGO/PVA composite; TEM image of (c) DMC-rGO/PVA; (d) photo image of DMC-rGO/PVA solu-
tion; (e) photo image of DMC-rGO/PVA film. [Color figure can be viewed at wileyonlinelibrary.com]

suspending state in the solvent. The suspending behavior of
GO, rGO, DMC-rGO in water was investigated and compared.
The results are shown in Figure 8. After reduction, a distinct
color change from yellow–brown to black can be observed,
which also suggests that deoxygenation of the graphene oxide
effectively happened. It is worthwhile mentioning that the
DMC-rGO powder yielded a stable dispersion in water. This
dispersion can be well-stable for several months without the
observation of any floating or precipitate particles. In contrast,
rGO obtained in the absence of DMC forms aggregates more
readily and rapidly than DMC-rGO. This result suggests that
DMC serves as an effective stabilizing agent for rGO. Figure
8 also presents a scheme to illustrate why DMC can be acted as
an amphiphilic molecule to stabilize rGO in water. DMC con-
tains an ammonium cation and polar carbonyl groups which
make it well dissolved in water. During co-reduction process,
the ammonium cation of DMC can bind strongly to graphene
sheets by cation–p interactions between them, and at the same

Figure 12. XRD patterns of PVA and DMC-RGO/PVA composites with

different DMC-rGO content. [Color figure can be viewed at wileyonlineli- Figure 13. Conductivity of DMC-rGO/PVA composites as a function of
brary.com] DMC-rGO content.

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Figure 14. TGA and DTG curves of DMC-rGO/PVA composites with dif-
ferent DMC-rGO loading. [Color figure can be viewed at wileyonlineli-
brary.com]
time, the carbonyl groups on DMC is reduced to hydroxyl groups.
And these in-situ formed AOH groups at DMC-rGO surface then
form hydrogen bonds with the oxygen atoms of water.
Interaction and Structure of the DMC-rGO/PVA Composite
Film
The DMC-rGO was further integrated to PVA matrix by solvent
evaporation approach. The interfacial function between filler and
host polymer is a key factor to obtain satisfied composites.
Strong interfacial adhesion can facilitate the stress transfer and
maximizes the performance of composites. FTIR characterization
was performed to study the interaction between DMC-rGO and
PVA chains. As shown in Figure 9(a), all the spectra of compo-
sites have similar profiles to that of the neat PVA. It is well
known that both the AOH stretching (3000–3600 cm21) and the
ACAOH stretching (1260–1000 cm21) bands are sensitive to the
hydrogen bonding. Figure 9(b) shows relative tOAH and tCAOH
shifts of DMC-rGO/PVA composites with different DMC-rGO
loading. On the whole, both tOAH value and tCAOH value
decrease monotonously with increasing loading of DMC-rGO,
for example. With the increase in DMC-rGO content, the charac-
teristic peak corresponding to AOH gradually shifts from
3313 cm21 for pure PVA to 3266 cm21 for DMC-rGO/PVA com-
posites with 0.2 wt % DMC-rGO, then to 3248 cm21 for DMC-
rGO/PVA composites with 0.3 wt % DMC-rGO. Such prominent
shifts strongly suggest strong intermolecular H-bond interac-
tions37 take place between the hydroxyl groups on PVA and the
polar groups on DMC-rGO, which may improve the compatibili-
ty between the filler and matrix (as shown in Figure 10).
To evaluate the dispersion state of DMC-rGO sheets in PVA
and interfacial interactions between DMC-rGO and PVA matrix,
Table IV. The Decomposition Temperatures of Series DMC-rGO/PVA Composite Films
Content of DMC-rGO (%) 0 0.1
Decomposition temperature(8C) 253.62
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Figure 15. Tensile strength curves of the DMC-rGO/PVA composite with
different DMC-rGO loading.
the fractured surface morphology of DMC-rGO/PVA composites
were characterized by SEM and TEM (Figure 11). The fracture
surfaces were created by tensile test of the specimens. It can be
seen that the fracture surface of pure PVA is relatively smooth
while the morphology of the DMC-rGO/PVA with 2 wt % filler
is entirely different from that of the pure PVA, which are very
rough. Besides, it can be also seen from Figure 11(b) that the
DMC-rGO sheets are wrapped by PVA matrix. Both observa-
tions illustrates that a strong interfacial interaction exists in
DMC-rGO/PVA composite, which can transfer the stress load
from filler to polymer matrix and result in more efficient
absorption of energy by deformation of polymer. The TEM
images [Figure 11(c)] and photographs [Figure 11(d,e)] of
DMC-rGO/PVA composite show that DMC-rGO sheets are
homo-dispersed in PVA matrix from macroscopic angle. No
aggregation of graphene sheets can be observed in DMC-rGO/
PVA composite and the adjacent graphene sheets are connected
to each other and tend to form a network structure.
The degree of crystallinity has a significant impact on the
mechanical properties of the PVA composites since PVA is a
semi-crystalline polymer. To get information about the effect of
DMC-rGO on crystallinity of PVA, XRD of the samples was
performed and the results are shown in Figure 12. Based on
these XRD curves, the degree of crystalline of samples could be
obtained through curve-fitting method and the calculated data
are also shown in Figure 12. It can be seen that compared with
the pure PVA, no obvious differences observed for DMC-rGO/
PVA composites, which suggest that the DMC-rGO nanosheets
do not have a noticeable effect on crystallinity of PVA.
Properties of the DMC-rGO/PVA Composites
The DMC-rGO/PVA composites were expected to exhibit good
electrical conductivity due to the exceptionally high
0.3 0.5 1.0
339 342.44 349.49 353.25
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ARTICLE WILEYONLINELIBRARY.COM/APP
conductivity of DMC-rGO and its large surface area, which pro-
mote the formation of a conductive network in the PVA matrix
at low filler loading. The log of the electrical conductivity
increases as the filler contents increased and is six orders of
magnitude greater than neat PVA in the DMC-rGO/PVA-2 wt
% composites (Figure 13). This attributes to the formation of a
conductive network as evidenced by TEM analysis.
The thermal stability values of pure PVA, DMC-rGO/PVA com-
posites were evaluated by Thermogravimetric analysis (TGA)
and derivative thermogravimetry (DTG) and shown in Figure
14 and Table IV. In pure PVA and its composites, the mass loss
occurs in two steps at 250 to 400 8C and 400 to 500 8C due
to the decomposition of the side chain and main chain of PVA,
respectively. However, the thermal degradation of DMC-rGO/
PVA composites is delayed due to the incorporation of DMC-
rGO. With the increasing mass of DMC-rGO, DMC-rGO/PVA
composites exhibit higher thermal stability. In DTG curve, the
temperature for peak decomposition of DMC-rGO/PVA-0.3 wt
% increases by approximately 88 8C and the DMC-rGO/PVA-1.0
wt % increases by about 100 8C. This improvement of thermal
stability should be ascribed to: (1) more hydrogen bonds are
formed between DMC-rGO and PVA matrix with increasing
DMC-rGO loading; (2) The physical barrier effect of graphene
which slows down the diffusion of pyrolysis products, as has
been reported for other layered materials such as clay and lay-
ered double hydroxides.38–41
Figure15 shows the tensile strength of pure PVA and DMC-
rGO/PVA composites with varies DMC-rGO loading. It could
be seen that the tensile strength of the composites increases
with the increasing of the DMC-rGO fillers and reaches a value
as high as 32.5 MPa at 0.5 wt % DMC-rGO content, which was
85.2% higher than that of pure PVA. As shown in Figure 15,
DMC-rGO nanosheets do not have a noticeable effect on crys-
tallinity of PVA. Therefore, the improvement of DMC-rGO/PVA
composites should attribute to DMC at DMC-rGO surface
which plays “bridge” roles between PVA and fillers via hydrogen
bond. This strong hydrogen bond benefits the effective wetting
of DMC-rGO and improves interfacial adhesion. When an extra
stress is applied to the composites, the hydrogen bonds between
matrix and filler in DMC-rGO/PVA composites make the stress
easier to be transferred between the matrix and fillers and thus
results in improved mechanical properties compared with pure
PVA.
CONCLUSIONS
In conclusion, we successfully modified graphene using ionic
liquid with favorable dispersion. The DMC can be attached
onto graphene sheets through the electrostatic interaction,
which dramatically enhance the dispersion of rGO in water.
Using the aqueous solution of DMC-rGO, DMC-rGO/PVA
composites containing well exfoliated and dispersed graphene
sheets can be prepared by a simple solution casting method.
Owe to the “bridge” role of DMC between PVA matrix and fill-
ers via hydrogen bond, the DMC-rGO/PVA composites obtained
considerable enhancements in mechanical properties and
remarkable improvements in thermal stability. Furthermore, this
WWW.MATERIALSVIEWS.COM 45006 (9 of 10)
non-covalently modification approach reserved the structure
integrity of the graphene. Thus, conductive pathways can be
formed in composite at low DMC-rGO loading. When DMC-
rGO loading was 2 wt %, the electrical conductivity DMC-rGO/
PVA composites was six orders of magnitude greater than that
of pure PVA.
ACKNOWLEDGMENTS
This study was financially supported by the National Natural Sci-
ence Foundation of China (grant numbers 51303158, 21274131,
51273178, and 51203139), Natural Science Foundation of Zhejiang
Province (grant numbers LY17E030006).
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