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Chinese Journal of Physics 55 (2017) 412–422

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Chinese Journal of Physics

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Synthesis and characterization of nanocomposites films with

graphene oxide and reduced graphene oxide nanosheets
Meryem Goumri a, Christophe Poilâne b, Pierre Ruterana b, Bessem Ben Doudou b,
Jany Wéry c, Anass Bakour a,c, Mimouna Baitoul a,∗
University Sidi Mohammed Ben Abdellah, Faculty of Sciences Dhar El Mahraz, Laboratory of Solid state Physics, Group of Polymers and
nanomaterials, PO Box 1796 Atlas Fez 30 000, Morocco
CIMAP, UMR6252 CNRS-CEA-ENSICAEN-Université de Caen Basse Normandie, Caen 14050, France
Institut des Matériaux Jean Rouxel, Université de Nantes, CNRS, UMR 6502, 2 rue de la Houssinière, PO Box 3229 Nantes, Cedex 44322

a r t i c l e i n f o a b s t r a c t

Article history: Graphene oxide (GO) and reduced graphene oxide (CRGO), as a graphene derivatives, pos-
Received 18 July 2016 sess unique properties and a high aspect ratio, indicating great potential in nanocomposite
Revised 11 December 2016
fields. The present work reports the fabrication of the nanocomposite films by a simple and
Accepted 29 December 2016
environmentally friendly process using aqueous solution and optimized time sonication for
Available online 27 February 2017
better exfoliation of the graphene sheets within Poly(Vinyl alcohol) (PVA) as matrix. The
Keywords: films were characterized using high-resolution TEM (HRTEM), X-ray diffraction (XRD), Mi-
Composite materials crotensile testing, Differential scanning calorimetry (DSC) and Thermogravimetric analysis
Graphene (TGA). The TEM images revealed a successfully exfoliation of the GO/CRGO nanosheets.
Poly (vinyl alcohol) XRD combined with TGA and DSC measurements showed an improvement in the ther-
Thermal and mechanical properties mal stability and tunable thermal properties. In addition, the Young’s modulus and tensile
yield strength of the composite films containing 1 wt% GO were obtained to be 4.92 GPa
and 66 MPa respectively. These excellent reinforcement effects were achieved by the strong
interaction between the components.
© 2017 The Physical Society of the Republic of China (Taiwan). Published by Elsevier B.V.
All rights reserved.

1. Introduction

Since its discovery in 2004 [1], graphene as an allotrope carbon form of periodic sp2 bonded carbon atoms that are
densely packed in a honeycomb crystal lattice and nanoscale materials based on graphene have attracted considerable atten-
tion due to their unique electronic, thermal and mechanical properties such as the high intrinsic mobility (20 0,0 0 0 cm2 /Vs)
[2], thermal conductivity (50 0 0 W/mK) [3], Young’s modulus (1.0 TPA), breaking strength (125 GPa) [4], and high theoretical
specific surface area (2630 m2 /g) [5]. Graphene and its derivative such as graphene oxide (GO) and functionalized graphene
have been extensively studied for various applications including power devices, sensors, conductive materials, transistors,
photovoltaic devices and biomedical applications [6,7].
Currently, graphene does not exist naturally, but it can be produced by chemical [8] or thermal reduction of GO pro-
duced by a chemical treatment of graphite by different methods [9]. Graphene has a tendency to agglomerate in a polymer
matrix due to intrinsic Van Der Waals bonds and its high specific surface area. The oxidation followed by a chemical

Corresponding author:.
E-mail addresses: (M. Goumri), (M. Baitoul).
0577-9073/© 2017 The Physical Society of the Republic of China (Taiwan). Published by Elsevier B.V. All rights reserved.
M. Goumri et al. / Chinese Journal of Physics 55 (2017) 412–422 413

functionalization will facilitate the dispersion and stabilization of graphene [10]. The graphene oxide carries various func-
tional oxygen groups and therefore, it is hydrophilic and easily dispersible in water [11]. Furthermore, for polymer/graphene
nanocomposites, the functional groups of graphene oxide enhance interfacial bonding between polymer and graphene
oxide (GO), and ensure a homogeneous dispersion using a compatible solvent. It has been shown that the incorporation
of graphene and its derivatives can remarkably improve the properties of conventional polymers. For example, graphene
showed good thermal stability of Polypropylene [12], the electrical conductivity of polystyrene was increased with a loading
of 0.4 wt% graphene [13], thus the Young’s modulus of poly (vinylidene fluoride) was increased from 1302 to 3173 MPa with
the addition of a weight fraction of 4 wt% graphene [12]. The development of a fluorescent composite based on Poly (vinyl
alcohol) or Porphyrine and graphene oxide was studied [14,15] and an intense UV visible blue to red luminescence was
obtained, in our previous work, from few layered graphene/ Zinc oxide nanorods [16]. The polymer / Graphene nanocompos-
ites can be prepared by different routes such as melt blending, in-situ polymerization and solution mixing [10,17].Thus, the
matrix’s choice is also important to achieve efficient load transfer. Many studies have been focused on hydrophilic polymers
such as poly (vinyl alcohol) (PVA) due to their hydroxyl groups, which makes its high water solubility. PVA is a synthetic
polymer soluble in water, non-toxic and biocompatible. Also, it has excellent adhesive and emulsifying properties [18].This
polymer was used in the preparation of several composites based on carbon, such as multiwall carbon nanotubes [19,20].
In the present study, we report a simple and practical approach to synthesize nanocomposite films based on PVA and
appropriate contents of GO/ chemically reduced GO (CRGO) using distilled water as a solvent and conduct a comparative
study of the morphological, structural, mechanical and thermal properties of the films based on GO/PVA and CRGO/PVA. The
grafting of the PVA onto the GO/CRGO surface and the effect of GO reduction on the PVA-based nanocomposite properties
were investigated. Furthermore, mechanical theoretical study using Cox model [21] was carried out and correlated to the
experimental modulus data.

2. Experimental

2.1. Materials

Graphite was purchased from Sigma–Aldrich. GO was obtained by graphite oxidation according to modified Hummers
method using H2 SO4 , KMnO4 as oxidants [11]. Reduction of GO was performed by chemical method using hydrazine hydrate
(N2 H4 ) as reducing agent and more details were reported in our previous work [11]. Poly (vinyl alcohol) (PVA) with a
molecular weight of 95.0 0 0 g/mol used in this study was purchased from Arkema.

2.2. Sample preparation

Preparation of graphene oxide and reduced graphene oxide solutions, A colloidal aqueous suspension of the GO and
reduced graphene oxide (CRGO) nanosheets were prepared as follows, amounts of graphite oxide powder of 5, 10 and 20 mg
were dispersed in10 ml distilled water. Then, we used ultrasonication method for one hour at a room temperature. The
CRGO was prepared by using a solution of hydrazine hydrate that weighed 10% of the GO dispersed in water for 24 h at
80 °C and sonication was applied for one hour at 80 °C to obtain the exfoliated nanosheets. More details about the quality
of the GO and CRGO using hydrazine hydrate were reported in our previous work [11].
Preparation of GO/PVA and CRGO/PVA nanocomposites, The technique of solution mixing using distilled water was used
for the preparation of nanocomposite films based on PVA and two different types of nanofillers such as GO and CRGO with
loading of 0.5, 1 and 2 wt% with respect to the PVA. GO/PVA nanocomposites containing different amounts of the filler were
prepared as follows: PVA (4g) was dissolved in 40 ml of deionized water using a magnetic stirrer for 3 hours at 80 °C. Then,
10 ml of the PVA solution was added into the solutions of GO and kept for one hour at a room temperature under uniform
stirring. To prepare the CRGO/PVA solutions, 10 ml of the PVA solution was added to solutions of CRGO and agitated for 1 h
at 80 °C. The homogeneous solutions obtained were cast into glass petri dishes and dried at 60 °C for 24 h Pure PVA film
was also prepared in the same conditions and used as a reference.

2.3. Characterization

Transmission electron microscopy (TEM) images were obtained using the JEM-ARM 200F microscopy which has a point
resolution of 0.18 nm at 80 kV in order to minimize damage to the local structure in the phase contrast high-resolution
TEM (HRTEM) imaging mode. The TEM analyses included amplitude-contrast bright field (BF) images, HRTEM images, and
selected area electron diffraction (SAED) patterns. X-ray diffraction (XRD) experiments were conducted using the Bruker
diffractometer with a Cu Kα wavelength λ = 0.154 Å and at room temperature. The mechanical properties of the nanocom-
posites were evaluated using microtensile tests. The composite films were cut into pincushion strips of 5 mm wide in re-
duced section and 40–70 mm length with a razor blade. The displacement fields were calculated by image correlation (DIC)
in the reduced section zone and using SPA handmade software [22]. For loaded PVA films, agglomeration of nanolayers acted
as speckle for white-light DIC method while laser speckle was used in case of pure PVA films for coherent-light DIC method.
The thicknesses of the films were measured utilizing a digital micrometer. Tests were performed with a 500 N load cell. The
number of tested specimens exceeded three or four. Thermogravimetric analysis (TGA) measurements were performed using
414 M. Goumri et al. / Chinese Journal of Physics 55 (2017) 412–422

Fig. 1. Optical images of the dispersion of 1 wt% (a) GO/PVA and (b) CRGO/PVA nanocomposites.

the Setaram TG-ATG 92 from 20 to 600 °C at a linear heating rate of 6 °C/min in nitrogen atmosphere. The thermal behavior
of the nanocomposites was studied by differential scanning calorimetry (DSC) using the Setaram DSC121RS. The samples
were heated from 20 to 300 °C at a linear heating rate of 6 °C/min under nitrogen.

3. Results and discussion

3.1. Morphological Analysis: transmission electron microscopy (TEM)

Stable aqueous dispersion and exfoliation of 1 wt% GO/CRGO nanolayers were shown in Fig. 1. For TEM analysis, a solution
of GO was deposited on a conventional lacey carbon support shown in Fig. 2a. The GO nanosheets are homogeneous and
quite smooth. Fig. 2b exhibits a high resolution imaging (HRTEM) of a single GO nanosheet, illustrating their amorphous
character and disordered structure. Selected area electron diffraction (SAED patterns, inset in Fig. 2b) confirmed the disorder
nature of the GO nanolayers. The SAED pattern of GO shows only diffraction rings and the diffraction dots are unresolved,
confirming that the GO nanosheets are amorphous [23]. Moreover, the SAED pattern shows two sharp rings corresponding to
graphene crystal planes (100) (intralayer d1- spacing of 0.213 nm) and (110) (intralayer d2-spacing of 0.126 nm) [23,24]. The
inner ring is more intense than the outer, which is consistent with exfoliated graphene like sheets rather than AB-stacked
graphitic material.
The morphology and structure of PVA nanocomposites were observed via TEM analysis as shown in Fig. 2(c and d). The
parallel dark lines in Fig. 2c (2 wt% GO/PVA) and Fig. 2d (2 wt% CRGO/PVA) are the side views of GO and CRGO nanosheets,
respectively, which consist of GO/CRGO nanolayers. The thickness of the GO nanosheets is about 7 nm (Fig. 2c), indicating
few GO nanolayers (1–3 layers), the thickness of the graphene nanosheets is about 20 nm (Fig. 1d), and indicating aggrega-
tion of graphene nanolayers. In general, the GO nanosheets are well dispersed in the PVA matrix [25].
As is known, both GO and PVA are hydrophilic, with oxygen-containing groups [11], which are removed in the reduction
process and the CRGO becomes hydrophobic [10]. Therefore, GO can be more easily dispersed in aqueous PVA than CRGO.
The aggregation of CRGO nanolayers is attributed to the restoring of the Van Der Waals interactions between the nanolayers.
Although there are some oxygenated functionalities in CRGO, the hydrogen bond between the CRGO nanolayers and the
PVA matrix is not strong enough to counterbalance the strong Van Der Waals interactions between the CRGO nanolayers.
As against, GO has much more oxygenated functionalities, so the H-bonding between the carboxyl groups of GO nanolayers
and the hydroxyl groups of PVA matrix has led to a better exfoliation and dispersion in the PVA matrix.
M. Goumri et al. / Chinese Journal of Physics 55 (2017) 412–422 415

Fig. 2. (a) Bright field TEM images of GO sheet on a visible lacey carbon support, (b) HRTEM images of single GO layers, illustrating their amorphous
character, the inset shows the corresponding SAED patterns, TEM image of the 2 wt%, (c) GO/PVA and (d) CRGO/PVA nanocomposites.

3.2. Structural analysis: X-ray diffraction (XRD)

The structures of GO, CRGO, the neat PVA and the composite films were studied by X-ray diffraction. The obtained XRD
patterns are shown in Fig. 3(a and b). The XRD diffraction peak of GO appeared at 2θ = 11.62°, corresponding to a (001)
plane [25,26]. The distance between two lattice planes of GO is given by Bragg’s equation with a wavelength λ = 1.5406 nm:

d = λ/2sinθ (1)

The GO characteristic peak at 2θ = 11.62° corresponds to an interlayer d-spacing of 0.76 nm, indicating the presence of
oxygen functional groups, to facilitate exfoliation and hydration of the GO nanosheets in an aqueous solution while an inter-
layer d-spacing of graphite is of 0.33 nm [25,27]. The GO characteristic peak disappeared in the nanocomposites suggesting
that GO was reduced and well dispersed in the PVA matrix without formation of the stacked structures. Thus, GO were
completely covered by the PVA chains [25,28–30].
The PVA spectrum exhibits the diffraction peaks at 11.04°, 19.28°, 22.15° and 40.32° which correspond to the planes (110),
(101), (200) and (020) of the crystalline phase of the neat polymer [31]. However, the peaks at 11.04°, 22.15° and 40.32°
416 M. Goumri et al. / Chinese Journal of Physics 55 (2017) 412–422

Fig. 3. XRD patterns of (a) GO/PVA, (b) CRGO/PVA nanocomposite films with different graphene loading showing a decrease in crystallization with the
incorporation of nanoparticles.

Table 1
FWHM of the main peak of the nanocomposites at 19.36° and crystallite size calculated by
Scherrer’s equation.


0.5wt% 1wt% 2wt% 0.5wt% 1wt% 2wt%

FWHM (°) 2.11 2.56 2.58 2.58 2.48 2.77 2.93

Crystallite size(nm) 37.78 31.14 30.90 30.90 32.17 28.80 27.22

disappeared by incorporation of the GO/CRGO nanofillers and the full width at half maximum (FWHM) of the nanocom-
posites peak at 19.36° increased showing a decrease in the crystallization [32]. To estimate the crystallite size, we used the
Scherrer equation described below:

T = 0.89 × λ/(2θ ) × cos θ (2)

In which λ is the wavelength of the incident wave, θ is half of the wave deflection and the peak width ((2θ )) is
inversely proportional to crystallite size (T).
The XRD analysis was also used to evaluate the reduction of graphene oxide by calculating the distance between the
graphene layers. After chemical reduction, the hydrophilic character of GO decreased. The intensity of GO characteristic
peak decreased and the broad peak located at 2θ = 23.16° indicates a random graphene sheets in the CRGO. This peak is
corresponding to (002) plane of graphite with interlayer spacing of 0.38 nm which is due to the elimination of functional
groups confirming thus the reduction process of GO into graphene sheets [11]. In the nanocomposites patterns, the FWHM
of the main peak increases by increasing the nanofillers fraction, indicating that the crystallization is delayed because of
the reduction of hydrogen bonds in PVA chains after incorporation of the GO/CRGO nanosheets (see Table 1). Thus, GO can
form more hydrogen bonds with PVA matrix than CRGO, that is why a crystallization of the GO/PVA nanocomposites was
improved compared to CRGO/PVA [32,33].

3.3. Mechanical analysis: tensile test

The molecular-level dispersion of the GO nanosheets in the PVA matrix and strong interfacial adhesion due to H-bonding
between graphene oxide and PVA matrix should have a significant effect on the mechanical properties. Typical stress-strain
curves for GO/PVA and CRGO/PVA nanocomposites within the tested range of GO/CRGO weight fractions with varying load-
ings are given in Fig. 3 and the results are summarized in Table 2. In Fig. 4, data are perfectly relevant until maximum value
of stress and above this value the necking disturbs the computation of deformations. Results in Table 2 correspond to the
mean and standard deviation of three or four tensile tests. The mechanical performance of the GO/PVA nanocomposites was
significantly increased as compared to that of the pure PVA matrix.
M. Goumri et al. / Chinese Journal of Physics 55 (2017) 412–422 417

Table 2
Mechanical properties of PVA nanocomposites.

Sample Tensile modulus (GPa) Yield stress (MPa) Yield strain (%)

PVA 4.52 (±0.10) 53.7 (±2.1) 2.03 (±0.33)

0.5% GO/PVA 4.29 (±0.12) 63.8 (±1.1) 2.45 (±0.55)
1% GO/PVA 4.93 (±0.15) 66.8 (±1.0) 2.03 (±0.13)
2% GO/PVA 4.77 (±0.11) 60.3 (±1.0) 2.13 (±0.19)
0.5% CRGO/PVA 2.11 (±0.15) 35.9 (±1.4) 2.59 (±0.22)
1% CRGO/PVA 2.29 (±0.17) 31.3 (±1.4) 3.07 (±0.47)
2% CRGO/PVA 0.56 (±0.11) 18.9 (±1.7) 5.04 (±0.37)

Fig. 4. Stress–strain curves for graphene/PVA nanocomposites with different (a) GO and (b) CRGO weight loadings.

The Young’s modulus (E) and yield stress (σ y ) increased by the incorporation of GO. A GO loading of 1 wt% results in
an increase of the Young’s modulus from 4.52 to 4.93 GPa (Fig. 5a) and of the yield stress from 53.7 to 66.8 MPa (Fig. 5b).
The yield strain (ε y ) of the GO nanocomposites also was slightly increased as compared to pure PVA (Fig. 5c). The enhanced
mechanical properties are believed to arise from the strong interaction between GO and the PVA matrix and homogeneous
dispersion of graphene sheets in the polymer matrix. This material shows a PVA like tensile behavior whatever the nanofiller
content (Fig. 4).When a critical content is reached, between 1 and 2 wt%, the graphene sheets stack together by layers. The
distance between two sheets being so small that they may be apt to stack together easily due to the strong Van Der Waals
force. Therefore, with excess graphene loading, brittle micro-failure can easily occur in the nanocomposites, and as a first
result, the E value decreased. As a second result, one micro-failure can propagate itself causing final failure of specimen
(Fig. 5d).
So for a content between 1 and 2 wt% of GO, the exfoliated graphene sheets could be well dispersed in the polymer
matrix, leading to a significant improvement in the mechanical properties, while further ratio increased the agglomeration
of nanosheets decreasing the efficiency of the mechanical properties improvement [32].
On the other hand, when the loading of CRGO reach 2 wt%, the yield stress and Young’s modulus dramatically decreased
from 53.7 to 18.9 MPa and from 4.52 to 0.56 GPa respectively (Fig. 5 and Table 2). Moreover, the yield strain did not evolve
comparing to pure PVA. In Fig. 4b, the experimental results show that the maximum stress of the polymer composite is
monotonically reduced with the increased CRGO addition. It contradicts with the results shown in Fig. 4a for the case of
GO. It can be attributed to the better dispersion of GO within the PVA matrix due to stronger hydrogen bond between the
contents which results in higher mechanical strength of PVA nanocomposites based to GO compared to CRGO. The poor
dispersion of CRGO in the PVA matrix leads to weak mechanical properties which are not reported in some previous works
2 wt% CRGO nanocomposites principally show a plastic-like behavior with low modulus and without very pronounced
threshold (Fig. 4). We never observe micro-failure as in case of GO material (see Fig. 5d).
These results are explained by poor dispersion of CRGO nanofillers in the PVA matrix on the one hand and weak
CRGO/PVA compatibility on the other hand. The Cox model [21] was used to estimate reinforcement effect of filler in com-
posites, and to predict the modulus of filler-reinforced nanocomposites. The density of the nanofillers and the PVA matrix
418 M. Goumri et al. / Chinese Journal of Physics 55 (2017) 412–422

Fig. 5. Experimental of (a) Young’s modulus (E), (b) Yield stress (σ y ), (c) Yield strain (ε y ) of the graphene/PVA nanocomposite films as a function of
nanofillers content and (d) Optical image of micro-failure of 2 wt% GO/PVA.

was of 1.9 and 1.3 g/cm3 respectively. Originally developed by Cox, this model allows taking into account the aspect ratio of
the fiber (continuity as well as two models of Halpin–Tsai), η is a factor applied to the reinforcement contribution in the
law of conventional mixtures.

Ec = ηEgVg + Em (1 − Vg ) (3)

Eg and Em are the Young’s modulus of the nanofillers and the polymer matrix. Vg is the volume fraction of the nanofillers
in the nanocomposites. The Young’s modulus of the GO sheet was previously measured as around 207 GPa [33] which may
approach to that of the GO and was used here. η takes different values and more particularly to fibers randomly distributed
in the plane η = 1/3 [21]. The Young’s modulus of the nanocomposite was calculated using the above Eq. (3) and are shown
in Fig. 6.
A good agreement was found between the experimental data obtained for graphene/PVA nanocomposites and the theo-
retical simulation results below 1 wt% GO. This result indicates that external tensile loads were successfully transmitted to
the filler across the graphene–PVA interface via strong interfacial interactions [25,26,28]. The graphene sheets prefer to align
parallel to the surface of the films which requires further investigation.
M. Goumri et al. / Chinese Journal of Physics 55 (2017) 412–422 419

Fig. 6. Calculated data derived from Cox model for GO/PVA composite films.

Fig. 7. TGA curves of (a) GO/PVA, (b) CRGO/PVA composite films with different GO/CRGO concentrations indicating their tunable thermal properties.

3.4. Thermal Analysis: thermogravimetric analysis (TGA)

The thermal stability of the composite materials was assessed by thermogravimetric analysis (TGA) in inert atmosphere
(Fig. 7).
There were two steps in the degradation, the first step between 90 °C and 190 °C has been attributed to the elimination
of water present in PVA and between GO/CRGO layers [25,34]. The second step between 254 °C and 480 °C corresponds to
the degradation of the PVA polymer. The degradation temperature for the nanocomposites was increased with respect to the
neat polymer matrix. Improving thermal stability of the nanocomposites by increasing GO/CRGO nanoparticles content can
be attributed to several reasons, (i) high thermal stability of GO/CRGO nanoparticles [29], (ii) mobility of the polymer seg-
ments near the interface has decreased by strong interactions between the two components [26,30,32,34], (iii) suppression
of diffusion of the volatile decomposition produced throughout the nanocomposites and it strongly depends on the hydro-
gen bond interactions between GO/CRGO and the PVA segments [12] and finally degradation from outer surface inward can
be considered as an important factor for increasing thermal stability of the nanocomposites [35].
Graphene-based nanocomposites lose about 5% of mass while GO nanocomposites lose about 10% below 190 °C because
GO has more oxygenated functionalities which can easily hold water. In general, CRGO nanocomposites have much better
420 M. Goumri et al. / Chinese Journal of Physics 55 (2017) 412–422

Fig. 8. DSC thermograms of (a) GO/PVA and (b) CRGO/PVA nanocomposite films with different concentration of graphene used to measure the crystalliza-
tion degree (Xc ), glass-transition temperature (Tg ) and melting temperature (Tf ).

Table 3
Values obtained by DSC and TGA measurements of GO/PVA nanocomposites.

Sample Tg (°C) Tf (°C) Tdi (°C) Tdf (°C) Hf (J/g) Xc (%)

PVA 72 212 254 497 75 54

0.5% GO/PVA 69 210 273 482 69 49
1% GO/PVA 53 213 273.5 482 58.5 42
2% GO/PVA 85 213 273.7 474 54.3 39

Table 4
Values obtained by DSC and TGA measurements of CRGO/PVA nanocomposites.

Sample Tg (°C) Tf (°C) Tdi (°C) Tdf (°C) Hf (J/g) Xc (%)

PVA 72 212 254 497 75 54

0.5% CRGO/PVA 62 210 304 546 70.5 51
1% CRGO/PVA 58 212 308 473 63.4 46
2% CRGO/PVA 73 212 313 473 63.3 45

thermal stability than those of GO, because most of the oxygenated functionalities have been reduced in order to obtain
thermally stable graphene planes [25,29].

3.5. Differential scanning calorimetry (DSC)

Differential scanning calorimetry was used to measure the crystallization and melting temperatures of the samples, and
to determine the crystallinity degree. From Fig. 8, the crystallization and melting parameters of pure PVA and nanocompos-
ites such as the melting temperature and crystallization enthalpies were extracted. In Tables 3 and 4, the values obtained
by TGA and DSC analysis of the PVA matrix and nanocomposites were presented.
By the addition of GO/CRGO in the PVA matrix, the PVA glass transition temperature (Tg ) decreased from 72 °C to 53 °C
and 58 °C for GO/PVA and CRGO/PVA composites respectively and increased again for 2 wt%. It can be attributed to the
presence of significant interactions between the polymer chains and the GO/CRGO surface. The decrease in glass transition
temperature due to the presence of GO/CRGO nanosheets which reduce the hydrogen bonding among the PVA chains and
decrease in PVA molecular weights [25,35]. Thus, the increase in Tg for 2 wt% can be ascribed to the strong hydrogen bond-
ing between the both components, resulting in blocked movement of PVA chains for high graphene loading [28,29,32,36].
The nanocomposite melting temperature exhibited no change by the incorporation of the GO/CRGO nanofillers. These results
suggest that the nanofillers largely affect the amorphous regions in the PVA matrix but no effect on the crystalline regions
M. Goumri et al. / Chinese Journal of Physics 55 (2017) 412–422 421

It is also possible to measure the peak area which represents the latent heat of polymer melting, which can be converted
into melting enthalpy (Hmelt ) by introducing the heating rate (Vheat ).
Hmelt = latent heat/Vheat (cool ) (4)
The degree of crystallinity (XC ) was calculated using the following relationship.
Xc = (Hmelt /H0 ) × 100 (5)
Where Hmelt is the sample melting enthalpy and H0 the theoretical value of the melting enthalpy of a 100% crystalline
PVA at the thermodynamic equilibrium temperature is of 138.6 J/g [28,32]. The melting enthalpy and the degree of crystal-
lization were decreased by increasing the content of GO/CRGO. This result proves that the reduction of hydrogen bonds in
PVA chains by incorporation of GO/CRGO.
Also, the hydrogen bonding between the two components was formed, especially with GO nanosheets, and as a result, the
crystallization of the GO/PVA nanocomposites was enhanced in comparison to CRGO/PVA [32]. This is in a good agreement
with our XRD results.
The GO/PVA nanocomposites have higher Tg than for CRGO/PVA. It can be attributed to the number of hydrogen bonds
built between the PVA matrix and GO/CRGO nanosheets. Therefore, the decrease in PVA crystallinity does not reduce the
mechanical properties of the PVA/graphene nanocomposite films. The increase to some extent of the stress and modulus of
the PVA/graphene nanocomposite films can be ascribed to the homogeneous dispersion of graphene sheets in the polymer
matrix and strong interfacial interactions between both components [28].

4. Conclusion

GO and CRGO were dispersed and functionalized with the PVA. Stable aqueous dispersion and exfoliation of graphene
nanolayers were achieved. By the incorporation of GO and CRGO, the (E) and the (σ y ) increased compared with those of
the pristine PVA film. Furthermore, the agreement between the experimental tensile modulus data and the values pre-
dicted by Cox model indicated that the tensile loads were successfully transferred to the graphene oxide sheets across the
graphene–PVA interface via strong hydrogen bonding. In addition, the strong interfacial interactions are responsible for the
improvement in thermal stability of the nanocomposites based on PVA for a low content of the filler. The hydrogen bonds
between the nanofillers and PVA matrix influence the glass transition temperature and the degree of crystallization of the
PVA. The increase in Tg was observed for composites containing a GO/CRGO loading above 1 wt% indicating their tunable
thermal properties. On the basis of these results, the influence in the mechanical and thermal properties of the nanocom-
posites can be ascribed mainly to the homogeneous dispersion and alignment of graphene in PVA matrix owing to the
efficient interfacial interactions between both components. In conclusion, ecological and simple process used here could be
extended to the development of other nanocomposites based on graphene derivatives and biocompatible polymers and the
excellent results obtained open the way to integrate the graphene derivatives in many practical applications.


We would like to express our sincere thanks to (CIMAP) Laboratory “Centre de Recherche sur les Ions, les Matériaux et
la Photonique” (France) for mechanical measurements.


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