Composites Part B 128 (2017) 155e163

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Noncovalent functionalization of reduced graphene oxide with

pluronic F127 and its nanocomposites with gum arabic
Rama K. Layek a, Md. Elias Uddin b, Nam Hoon Kim c, *, Alan Kin Tak Lau d,
Joong Hee Lee c, e, **
a
Department of Material Science, Tampere University of Technology, P.O. Box 589, 33101 Tampere, Finland
b
Department of Leather Engineering, Khulna University of Engineering & Technology (KUET), Khulna, 9203, Bangladesh
c
Advanced Materials Institute of BIN Convergence Technology (BK Plus Global) & Dept. of BIN Convergence Technology, Chonbuk National University,
Jeonju, Jeonbuk 54896, South Korea
d
Faculty of Science, Engineering and Technology, Swinburne University of Technology, Hawthorn, VIC 3122, Australia
e
Carbon Composite Research Centre, Department of Polymer & Nano Science and Technology, Chonbuk National University, Jeonju, Jeonbuk 54896, South
Korea

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

Article history: Nanocomposites of pluronic F127 modied reduced graphene oxide (PF127-rGO) with polyethylene
Received 14 February 2017 glycol plasticize gum arabic (PGA) was prepared by evaporating an aqueous solution mixture of PF127-
Received in revised form rGO and PGA. PF127-rGO was synthesized by the in-situ reduction of graphene oxide using hydrazine in
11 June 2017
presence of pluronic F127 and characterized by the UveVis spectroscopy, transmission electron micro-
Accepted 3 July 2017
Available online 4 July 2017
scopy (TEM), wide angle x-ray scattering (WAXS), Fourier transforms infrared spectroscopy (FTIR),
thermogravimetric analysis (TGA) and Raman spectroscopy. The UveVis and Raman spectroscopy results
indicate that pluronic F127 functionalization does not hamper the structure of rGO, and TEM image
Keywords:
Polymer-matrix composites (PMCs)
indicates, the pluronic F127 anchored rGO sheets remain exfoliated in diluted aqueous solution of PF127-
Nano-structures rGO. WAXS, FTIR and TGA studies conrms the functionalization of rGO with pluronic F127. PF127-rGO
Mechanical properties 2.5, PF127-rGO 5 and PF127-rGO 7.5 nanocomposites were fabricated, where the numbers represent the
Electron microscopy weight percentage of PF127-rGO with respect to PGA. The composite lms were characterized by eld
Thermal analysis emission scanning electron microscopy (FESEM), FTIR, WAXS and mechanical property study. FESEM and
WAXS studies show good dispersion of PF127-rGO sheets in the PGA matrix. The FTIR results indicate a
signicant interaction between functional groups of PF127-rGO and functional groups of PGA. PF127-rGO
7.5 shows a 124% increase of stress at break and 185% increase of Young's modulus compared to pure
PGA.
2017 Elsevier Ltd. All rights reserved.

1. Introduction [12e15]. One of the simplest routes to utilize the properties of

During the last few years, research on graphene based carbon
nanomaterial has been gaining widespread attention due to its
promising physical, mechanical, electrical, electronic and barrier
properties [1e11]. By taking, advantages of these properties, gra-
phene is now being used in various elds such as nanoelectronic,
supercapacitors, lithium ion batteries, and packaging materials
* Corresponding author.
** Corresponding author. Carbon Composite Research Centre, Dept. of BIN
Convergence Technology, Chonbuk National University, Jeonju, Jeonbuk 54896,
South Korea.
E-mail addresses: nhk@chonbuk.ac.kr (N.H. Kim), jhl@chonbuk.ac.kr (J.H. Lee).
graphene is the incorporation of graphene with uniform dispersion
in different polymer matrixes by utilizing interfacial interaction
between graphene sheets and polymer matrix [16]. Graphene oxide
(GO) is highly dispersible in aqueous medium and can form a high
performance nanocomposite with hydrophilic polymers due to its
hydrophilic character. However, GO possesses many defects and
holes [17] which diminish of its various physical properties. While
graphene produced by chemical vapor deposition and micro-
mechanical cleavage methods has fewer defects, its production
yield is very low which limits its applications in the eld of gra-
phene based polymer nanocomposites. Reduced graphene oxide
(rGO) possesses better properties than GO due to the presence of
fewer defect. In addition, rGO can be produced on a large scale,

http://dx.doi.org/10.1016/j.compositesb.2017.07.010
1359-8368/ 2017 Elsevier Ltd. All rights reserved.
156 R.K. Layek et al. / Composites Part B 128 (2017) 155e163
which meets the demand of nanollers for graphene based poly-
mer nanocomposite preparation. Therefore, rGO is better than GO
for fabricating high performance graphene based polymer
nanocomposites.
However, one of the most signicant problems with using rGO
as a nanoller is associated with its processability. The rGO acquires
precipitate from most of the common solvents due to the high
cohesive van der Waals (VDW) energy between the rGO sheets in
solutions [18]. Hence, rGO is incompatible with both hydrophilic
and hydrophobic polymers. Therefore, functionalization of rGO
sheet with suitable functional groups is necessary to make rGO
sheet compatible with various polymer matrixes. To fabricate a
highly compatible graphene based polymer nanocomposite, the
rGO should be functionalized with suitable functional groups to
ensure an interfacial interaction occurs between the graphene
sheets and the polymer matrixes. In recent times, two different
strategies i.e (1) covalent [19,20] and (2) non covalent [20e22]
strategies were used to functionalize graphene for the enhance-
ment of dispersibility in solution and in polymer matrix. Covalent
functionalization produces more defects on graphene ring and it
decreases the properties of graphene [23]. The noncovalent func-
tionalization of graphene produces fewer defects than covalent
functionalization, as the graphene sheets are functionalized
without hampering the properties of graphene [24]. The dispersion
and compatibility of graphene with polymer matrix depends on the
physical interaction between the functional groups of modied
graphene and functional groups of matrix polymer [16,25,26].
Hence, the dispersion and compatibility of the rGO sheets can be
tailored by altering the nature of the functional groups. For
example, PMMA modied rGO [27] shows good dispersion in
chloroform and by utilizing the compatibilizing property of PMMA,
it can be used to prepare composite with polymethyl methacrylate.
Isocyanate modied graphene [28] shows good dispersion in DMF
and by utilizing the compatibilizing property of the isocyanate
group, it has been used to fabricate composite with polystyrene.
Sulfonic acid modied graphene [29] is highly soluble in water and
by utilizing the compatibilizing property of the sulfonic acid group,
it has been used to prepare composites with chitosan. Thus, the
incorporation of functional groups on graphene surfaces via non-
covalent functionalization has been attracting considerable atten-
tion for fabricating graphene based polymer composites with
uniform dispersion and improved interfacial interaction.
Here, we report the facial synthesis of noncovalent functional-
ization of rGO with pluronic F127 (PF127-rGO) using the in-situ
reduction of GO with hydrazine in the presence of pluronic F127
and its integration in polyethylene glycol (PEG) plasticize gum
arabic (GA) matrix (PGA) to produce PF127-rGO/PGA composite.
PF127-rGO has many oxygen containing ether and ehydroxyl
groups, which interact with the hydroxyl functional groups of GA.
PF127-rGO is therefore expected to produce high performance
nanocomposites with GA. Signicant interest has been paid to GA
as it is highly biocompatible [30] and can be produced from the
seria tree, which is naturally available. It is widely used in food
processing, cosmetics, and biomedical applications [31e33]. The
PF127-rGO/PGA nanocomposite lms obtained in this study show
signicantly enhanced mechanical properties that may have po-
tential applications in the area of environmental friendly plastic
materials.
2. Experiments
Graphite ake (Sigma Aldrich, Germany) and potassium per-
manganate (Junsei Chemical Co. Ltd., Japan) were used as received.
Sulfuric acid, hydrogen peroxide and hydrazine hydrate, were
purchased from Samchun Pure Chemical Co. Ltd. (Korea) and were
used as received. Pluronic F127 was purchased from Sigma Aldrich
and used as received. GA (weight average molecular
weight 250,000) and PEG (weight average molecular
weight 200) were purchased from Sigma Aldrich and used as
received. The water used for the experiment was collected from
Milli-Q system.
2.1. Preparation and purication of GO
Graphene oxide was synthesized by the oxidation of graphite
using modied Hummers method [34]. Briey, 46 mL sulfuric (95%)
was poured into a conical ux and stirred using a bar magnet on an
ice bath. Subsequently, 0.1 g sodium nitrate and 2 g graphite ake
were added at constant stirring. Then, 6 g potassium permanganate
was added gradually to the reaction mixture. During the addition,
the temperature of the reaction mixture was kept at 0e5  C using
an ice bath. At the end of the KMnO4 addition, the ice bath was
removed and placed in an oil bath for 30 min to maintain a tem-
perature of 35  C. The reaction mixture forms a thick paste by
stirring. Next, 100 mL Milli-Q water was poured into the reaction
mixture, which causes a sudden increase in the of temperature of
the reaction mixture ~90  C. Then, an additional 300 mL of water
was added to the reaction mixture followed by the addition of
20 ml of 30% H2O2. The color of the reaction mixture changed from
dark brown to yellow. Then, the reaction mixture was centrifuged
and repeatedly washed until the pH of the supernatant solution
was neutral. Finally, the GO was collected by drying the bottom part
after centrifugation and drying at 60  C at vacuum.
2.2. Synthesis of PF127-rGO
PF127-rGO was synthesized by treating the aqueous dispersion
of GO with hydrazine [35] in the presence of pluronic F127. In this
typical procedure, 100 mg GO was dispersed in 100 mL water via
ultrasonication (Sonosmasher ULH 700S, 20 kHz) in a round bottom
ask. 2 gm Pluronic F127 was dissolved in another round bottom
ask in 100 ml water. Then, pluronic F127 solution was mixed with
the GO dispersion with constant stirring. The reaction mixture was
then sonicated again for half an hour to create a homogeneous
solution. Then, the reaction mixture was reuxed at 100  C for 6 h
with the addition of 0.1 mL hydrazine hydrate [35]. Finally, the
reaction mixture obtained was vacuum ltered and washed with
water through a 0.2 mm pore size cellulose acetate membrane to
remove the unfunctionalized pluronic F127.
2.3. Fabrication of PF127-rGO/GA nanocomposite
The solvent evaporation technique was used to prepare PF127-
rGO reinforced GA nanocomposite lms. Typically, in a culture
tube, the required amount PF127-rGO was dispersed in 10 ml of
water by ultra-sonication. In another culture tube, 1 g of GA and
20 wt% plasticizer PEG with respect to GA were dissolved in 10 ml
water. The, solutions were then mixed together and sonicated for
another 10 min to produce homogeneous dispersion. The com-
posite lms were then prepared by evaporating the solution in petri
dishes at room temperature. 2.5, 5 and 7.5% (w/w) PF127-rGO/PGA
nanocomposites were prepared and designated as PF127-rGO 2.5,
PF127-rGO 5, and PF127-rGO 7.5 respectively. Pure PGA lm was
prepared in the same manner without using any PF127-rGO.
Finally, the lms were collected by eliminating the trap water via
drying in a vacuum at 50  C for three days. The preparation of
PF127-rGO and PF127-rGO/PGA composite has illustrated in
Scheme 1.
 R.K. Layek et al. / Composites Part B 128 (2017) 155e163
Scheme 1. Schematic representation of the preparation of PF127-rGO and PF127-rGO/PGA composites.
2.4. Characterization
A sample was prepared for transmission electron microscopy
(TEM) by spreading a drop of 0.05% w/v aqueous dispersion of
PF127-rGO on a lacey carbon coated cupper grid and allowing to
dry at room temperature. Then, a TEM study of the dried sample
was conducted using JEOL JSM-2200 FS, Japan. The cross-sectional
Field emission scanning electron microscopy (FESEM) (JSM-6701
Jeol, Japan) of the pure composite lms were performed by frac-
turing the lms using liquid nitrogen and sputtering the osmium
prior to the study. The UVeVis spectroscopy measurements of GO,
rGO and PF127-rGO were carried out by passing UVeVis light
through the aqueous dispersion of the samples using a UVS-2100
SCINCO spectrometer. For the Fourier transforms infrared spec-
troscopy (FTIR) measurement of the GO, rGO and PF127-rGO a
small quantity of the sample was mixed with KBr to prepare a
pellet. Then, the FTIR of the sample was measured using a Necolet
6700 spectrometer using the KBr pellet as reference. Attenuated
total reection (ATR) FTIR of the gum arabic and the composites
was also recorded by a Necolet 6700 spectrometer. Wide angle x-
ray scattering (WAXS) studies were performed using D/Max 2500V/
PC (Rigaku Corporation, Japan) with a scan rate (2q) of 2 /min. A
thermogravimetric analysis (TGA) experiment was carried out un-
der nitrogen atmosphere with a scan rate of 10 /min (TA In-
struments, Q20). Raman spectra of the samples were recorded
using the Nanonder 30 instrument (Tokyo Instruments Co., Osaka
Japan). The solvent cast lms of uniform thickness were cut into a
dumbbell shaped with a dimension of 40 mm  5 mm X 0.05 mm to
measure the mechanical property. The mechanical test of the
samples were performed at 25  C using a universal testing machine
(LR5K, Lloyd Co., England) at a strain rate of 5 mm/min. The elec-
trical resistivity of the composites was measured by Keithley 2000
(Keithley Instruments Inc., Cleveland, Ohio, USA) instrument.
157
3. Results and discussion
3.1. Functionalization of rGO with pluronic F127
GO develops a stable brown colored homogeneous aqueous
dispersion by ultra sonication. The resulting brown colored GO
solution was treated with hydrazine hydrate at 100  C to form a
black colored precipitate of rGO from the aqueous solution. This
rGO cannot re-disperse in any polar or non-polar solvent in the
presence of surfactant pluronic F127. But when reduction was
performed in presence of pluronic F127, a stable homogeneous
black colored solution was obtained. This solution was vacuum
ltered and washes with water to obtain PF127-rGO. Pluronic F127
is a block copolymer of (polyethylene oxide)x-b- (polypropylene
oxide)y- (polyethylene oxide)z (Scheme 1). Its hydrophobic poly-
propylene oxide segment interact noncovalently with hydrophobic
rGO surface and hydrophilic polyethylene oxide segment remain
spread over the rGO surface that causes noncovalent functionali-
zation of rGO with pluronic F127 [36,37]. The obtained PF127-rGO
shows high dispersion in aqueous medium (inset of Fig. 1) and was
characterized by UVeVis spectroscopy, TEM, XRD, FTIR, TGA and
Raman spectroscopy measurements.
To elucidate the formation of PF127-rGO, the UVeVis spectra of
GO, rGO, pluronic F127 and PF127-rGO were carried out and rep-
resented in Fig. 1. The aqueous dispersion of GO exhibits a char-
acteristic broad absorption peak at 230 nm for the p-p * transition
of CC [38]. In addition, a hump like peak appears at 308 nm for the
n- p * transition of the CO bond [38]. In rGO, the peak at 308 nm
disappears and the peak of GO at 230 nm is red shifted to 269 nm,
indicating that p-conjugation is signicantly enhanced in rGO
compared to GO [38,39]. The PF127-rGO shows the existence of a
peak at 270 nm, indicating that the presence of pluronic F127 does
not hamper the reduction process of GO.
158 R.K. Layek et al. / Composites Part B 128 (2017) 155e163

Fig. 1. Uvevis spectra of GO, rGO and PF127-rGO and their aqueous dispersion picture
(inset).

The TEM image, HR-TEM and selected area electron diffraction

(SAED) pattern of PF127-rGO is presented in Fig. 2(aec). The TEM
image of PF127-rGO shows pluronic F127 anchored large rGO
sheets spread on the carbon coated Cu-grid, indicates that PF127-
rGO sheets remain exfoliated in aqueous medium (Fig. 2(a)) [40].
The image also indicates that PF127-rGO sheets are exible and
become folded on the Cu grid. Therefore, it is possible to capture an
HR-TEM image of the cross-section (view at edge) of the PF127-rGO
sheets. The HR-TEM image of the edge of PF127-rGO shows 2e3
dark line; that indicates the existence of 2e3 layers of graphene in
PF127-rGO (Fig. 2(b)) [41]. The SAED pattern of PF127-rGO pre-
sented in Fig. 2(c) shows a hexagonal diffraction pattern, which is
the characteristic diffraction pattern of graphene [42].
To investigate the structure of the PF127-rGO, WAXS studies of
GO, rGO and PF127-rGO were carried out and are presented in
Fig. 3. It is clear from the gure that the GO shows characteristic
diffraction peaks at 2q 10.6 , indicating that the interlayer
spacing in GO is 0.83 nm [43]. In rGO, the peak at 2q 10.6 dis-
appears and shows a characteristic diffraction peak at 2q 24.5
[44]. This indicates that after reduction due to the removal of most
of the oxygen containing functional groups the interlayer spacing in
rGO is reduced to 0.36 nm. The pluronic F127 shows characteristic
diffraction peaks at 18 and 23 [45]. The PF127-rGO shows char-
acteristic diffraction peaks at 2q 18 and 23 for pluronic F127
and a hump like diffraction peak for rGO which is merged with the
pluronic F127 peak. In PF127-rGO, the diffraction peak of rGO is
shifted to lower angle, indicating that pluronic F127 is incorporated
into the rGO galleries, and increase the distance between the rGO
galleries.
To explain the formation of PF127-rGO, the FTIR spectra of GO,
rGO and PF127-rGO were acquired and presented in Fig. 4. The GO
shows characteristic CO stretching vibration at ~1728 cm1 for the
eCOOH group, C-OH stretching vibration at ~1240 cm1 & O-H
stretching vibration at ~3426 cm1, C-O stretching vibration at
~1050 cm1 for the epoxy group, and skeletal vibration of unoxi-
dized sp2 cluster at ~1620 cm1 [46,47]. In addition, the tetrahedral
C-H stretching peak at ~2925/2855 cm1 indicates the presence of
some CH2 or CH groups in GO [46,47]. In the FTIR spectra of rGO, the
peak of the epoxide group vanishes and the hydroxyl & carboxylic
group peak intensity decreases, although it remains present. The
FTIR spectra of rGO shows a sp3-CH peak at ~2925/2855, which
indicates that hydrazine hydrate treatment, cannot restore all sp2-
CH [48]. The FTIR spectra of pluronic F127 shows characteristic C e
OeC stretching band at 1107 cm1, C-H stretching band at 2880/
2940 cm1, OeH stretching band at 3540 cm1 [49]. The FTIR Fig. 2. (a) TEM image, (b) HRTEM image of the cross-section and (c) SAED pattern of
PF127-rGO.
spectra of PF127-rGO exhibits all characteristic peaks for pluronic
F127 along with characteristic peak of rGO (graphitic skeleton
 R.K. Layek et al. / Composites Part B 128 (2017) 155e163
Fig. 3. WAXS patterns of GO, rGO and PF127-rGO.
1576 cm1 and O-H stretching at 3450 cm1) that conforms the
functionalization of pluronic F127 with rGO [49]. The C-H peak
intensity increases in PF127-rGO compared to rGO due to the
presence of pluronic F127 in PF127-rGO.
To examine the thermal stability and calculate the amount of
pluronic F127 functionalization with rGO in PF127-rGO; TGA
studies of GO, rGO and PF127-rGO were performed and the TGA
thermogram is presented in Fig. 5. The gure clearly shows that GO
is thermally unstable and starts to degrade below 100  C. This may
be due to the removal of intercalated water molecules present in
GO [41,50]. In addition, GO shows a rapid weight loss in the tem-
perature region of 100e250  C. The weight loss in this region is
attributed to the removal of labile oxygen containing functional
groups of GO [50,51]. rGO shows no weight loss below 100  C due to
the absence of water molecules and very signicantly reduced
amount of weight loss in the region of 100e250  C compared to GO
due to the existence of considerably fewer oxygen containing
function groups in rGO [52]. PF127-rGO shows 3% loss of weight in
the temperature range of 100e250  C, due to the removal of the
oxygen moiety present in PF127-rGO. In addition, PF127-rGO
shows a 61% weight loss in the temperature region of
Fig. 4. FTIR spectra of GO, rGO, pluronic F127 and PF127-rGO.
159
Fig. 5. TGA thermograms of GO, rGO and PF127-rGO.
~300e400  C due to the degradation of pluronic F127 which in-
dicates that 61% pluronic F127 has present in PF127-rGO.
Raman spectroscopy is a key tool used to examine electronic
structure of the carbon-based materials. To acquire information
about the defect on graphene based materials, the Raman studies of
graphite, GO, rGO and PF127-rGO were performed and are pre-
sented in Fig. 6. The Raman spectrum of graphite exhibits two
characteristic peaks at ~1575 cm1 and ~1340 cm1, for the
graphitic (D) band (breathing mode of A1g symmetry) and dia-
monded (G) band (E2g symmetry of sp2 carbon atoms) respectively
[53,54]. In GO, these two band positions shifted to 1584 cm1 and
1347 cm1 respectively which may be due to the destruction of
conjugated network of aromatic ring and creation of defects in GO.
The intensity ratio of these two bands (ID/IG) was found to be 0.89 in
GO [55]. In rGO, the peak position of the G and D bands shifted to
1580 cm1 and 1343 cm1 respectively. The ID/IG intensity ratio
increased to 1.07 in rGO indicating the generation of enhanced sp2
Fig. 6. Raman spectra of graphite, GO, rGO and PF127-rGO.
160 R.K. Layek et al. / Composites Part B 128 (2017) 155e163

character in rGO via the removal of oxygen functionality of GO [56]. sheets into the PGA matrix.
PF127-rGO shows almost similar ID/IG intensity ratios that indicates To understand the dispersion of PF127-rGO sheets within the
that pluronic F127 has no effect on the restoration sp2 character in PGA matrix, the WAXS of PGA and its various composite lms was
GO. carried out (Fig. 8). Due to amorphous nature of GA, WAXS pattern
of PGA shows broad diffraction peak, with a maximum intensity at
3.2. Nanocomposites with gum arabic 2q 20.6 and the corresponding d spacing 4.4064 A , de-
termines the average grain length of PGA [58]. PEG component
2.5, 5 and 7.5 wt % PF127-rGO/PGA nanocomposite solutions peak is not appear in the PGA and this may be due low molecular
were prepared by solvent evaporation technique. The dispersibility weight PEG taken for the study or the presence of low concentra-
of PF127-rGO is signicantly increases in the presence of gum tion of PEG compared to GA. The nanocomposite lms of PGA with
arabic solution due to the polymer solvent synergy effect. The PF127-rGO also showed similar diffraction peaks to those of PGA,
composite lms are obtained by drying the solutions at room while no any characteristic peak were observed for rGO. This may
temperature for 2 days and nally drying in a vacuum oven for 3 be due to the exfoliation of rGO sheets in the PGA matrix or pres-
days. The composite lms are designated as PF127-rGO 2.5, PF127- ence of very less amount PF127-rGO compared to GA.
rGO 5 and PF127-rGO 7.5. PF127-rGO produces a homogenous The FTIR study of PGA and its nanocomposites was carried out to
dispersion in aqueous solution upon sonication. Pluronic F127 of investigate the interaction of PF127-rGO with PGA and the results
PF127-rGO is highly compatible with gum arabic, which can help are presented in Fig. 9(a). The FTIR spectra of PGA [59,60] shows
the homogeneous integration of rGO into the GA matrix. GA lms characteristic broad band at 3320 cm1 for the O-H stretching vi-
are very brittle due to the strong intermolecular H-bonding ef- bration of the hydroxyl group, at 1605 cm1 for C-O stretching
ciency among the GA. There is a study of GA/PVA blends, where
ethylene glycol and polyethylene ethylene glycol are used as a
plasticizer to fabricate polymer blend [57]. PEG decrease the
intramolecular H-bonding efciency by making intermolecular H-
bond and hence, a exible lm of GA is produced with the plasti-
cizer PEG. The composite lms were characterized by morphology,
FTIR, WAXS, mechanical property and electrical resistivity mea-
surements. The cross-sectional FESEM images of the PF127-rGO 5
and PF127-rGO 7.5 samples were studied to investigate the
dispersion of the rGO sheets into the PGA matrix (Fig. 7). The gure,
clearly demonstrations that, both the PF127-rGO 5 and PF127-rGO
7.5 show dispersion of the few layers of exfoliated rGO sheets
throughout the composite matrix. Dispersion plays a signicant
role to fabricate high performance graphene/polymer composites.
However, it is very difcult to disperse rGO sheets in the polymer
matrix due to the presence of large Van der waal interaction among
the rGO sheets. Functionalization of rGO with suitable functional
groups produce a good dispersion in the polymer matrix and form
high-performance rGO/polymer composites. In our study, poly-
propylene oxide segment of pluronic F127 interacts with rGO by
hydrophobic interaction and polyethylene oxide segment will
interact with oxygen containing functional groups of PGA that will
help to disperse rGO sheets in the PGA matrix. This indicates that
pluronic F127 can act as a good compatibilizer to disperse the rGO Fig. 8. WAXS patterns of PGA and its nanocomposites.

Fig. 7. FESEM images of (a) PF127-rGO 5 and (b) PF127-rGO 7.5.

 R.K. Layek et al. / Composites Part B 128 (2017) 155e163 161

Fig. 9. (a) FTIR spectra of PGA and its nanocomposites and (b) enlarged O-H stretching band.

vibration and at 1022 cm1 for the pyranose units. The character-
istic peak of PF127-rGO does not appear in the composites due to
the presence of a small amount of PF127-rGO with respect to the
gum arabic in the composite lms. However, in PF127-rGO 7.5, the
O-H stretching band appears at 3308 cm1 indicating a slight shift
of O-H stretching band in the composite lm to the lower fre-
quency. The enlarge FTIR spectra of hydroxyl peak of the pure PGA
and the composites lms is also presented to show the shift of the
maximum intense peak position. There are few studies on polymer
composites, which also shows similar shift of eOH stretching peak
to give an evidence of H-bonding interaction between the ller and
polymer matrix [61,62]. Furthermore, the peak in PGA at 1605 cm1
attributed for C-O stretching vibrations is shifted to 1598 cm1 in
PF127-rGO 7.5 and it indicates that the presence of the H-bonding
interaction between the PF127-rGO and PGA.
To investigate the mechanical performance of PGA and its
nanocomposites mechanical property measurements were per-
formed and the characteristic stress-strain curves are presented in
Fig. 10 and Table 1. Five samples for each test condition were tested Fig. 10. Stress - strain curves of PGA and its nanocomposites.
repeatedly in order to get the reliable data and the average values of
measured mechanical parameters, such as stress at break, strain%
and Young's modulus of the samples were presented in Table 1 with Table 1
the errors. The strong interfacial interaction within the GA chain Summary of the mechanical property of PF127-rGO/PGA composites.
produces a brittle lm and mechanical property measurement is Sample Strain % at Stress at Young's
not possible with such type of lm since the sample breaks when break break (MPa) modulus (GPa)
gripped. PEG can interact with GA via H-bonding interaction, which PGA 25.1 0.4 3.3 0.12 0.27 0.05
decreases the interfacial interaction among the GA chain and pro- PF127-rGO 2.5 21.1 0.5 4.9 0.4 0.42 0.04
duces a exible lm that can be easily gripped for mechanical PF127-rGO 5 17.2 0.8 6.4 0.3 0.55 0.04
property measurements. This lm shows the stress at break of PF127-rGO 7.5 10.6 1.1 7.4 0.15 0.77 0.06

3.3 0.12 MPa and strain% at the break of ~25.1%. The gure clearly
shows that, with addition of PF127-rGO, stress at break increases
with the decrease of strain % at break. PF127-rGO 7.5 shows the
stress of 7.4 0.15 MPa at break (increases ~124% compared to
PGA). PGA exhibits a Young's is modulus of 0.27 0.05 GPa and in
the composites this gradually increased with the increase of PF127-
rGO concentration. PF127-rGO 7.5 shows, ~185% improvement the
in Young's modulus compared to pure PGA. Hence, it is clear that
the mechanical property of the PF127-rGO/PGA nanocomposite is
signicantly enhanced compared to PGA. The mechanical property
of the graphene/polymer composites depend on the dispersion and
interaction of graphene sheet with the polymer matrix. Hence,
dispersion & interfacial interaction of PF127-rGO with PGA plays a
signicant role for the enhancement of mechanical property of
162 R.K. Layek et al. / Composites Part B 128 (2017) 155e163
PF127-rGO/PGA composites. There are several reports of polymer
composites regarding the interfacial interaction of ller with
polymer matrix that transfer exterior load effectively to the ller
from polymer matrix & it causes enhancement of mechanical
property of polymer composites [63,64]. A recent study of GO/
polyvinyl alcohol composite shows interfacial H-bonding interac-
tion between GO & PVA chain, causes enhancement of mechanical
property of GO/PVA composites and its occurs via transferring load
to GO from PVA matrix [65]. The sensible dispersion of few layers
exfoliated PF127-rGO sheets in the PGA matrix and H-bonding
interaction between functional groups of PF127-rGO (e.g., hy-
droxyls, carboxyls and ethereal oxygen) and oxygen containing
functional groups of PGA can transfer stress from PGA matrix to rGO
sheets. It causes signicant enhancement of the mechanical prop-
erty of the PF127-rGO/PGA nanocomposites like other graphene
based polymer composite system [65,66].
PGA has high electrical resistivity (~0.7  10 13 U cm). The
electrical resistivity decreases to 2.6  10 10 U cm, 1.8  107 U cm
and 4.5  10 5 U cm in PF127-rGO 2.5, PF127-rGO 5 & PF127-rGO 7.5
respectively due to incorporation of PF127-rGO in PGA matrix. The
resistivity of graphene/polymer composites depend on dispersion
and loading of graphene sheets in the polymer matrix [67,68]. The
resistivity of PF127-rGO/PGA composite is not decreased signi-
cantly with PF127-rGO loading and this may due to the wrapping of
nonconducting pluronic F127 on rGO surface.
4. Conclusions
In summary, we developed a valuable method for the prepara-
tion of functionalized reduced graphene oxide sheets by wrapping
pluronic F127 using a non-covalent functionalization technique.
The PF127-rGO obtained shows good dispersion in aqueous me-
dium due to the presence of the hydrophilic polyethylene oxide
segment in pluronic F127. The PF127-rGO obtained was character-
ized by UVeVis spectroscopy, TEM, WAXS, FTIR, TGA and Raman
spectroscopy measurements. Because pluronic F127 is an amphi-
philic material, it is expected that PF127-rGO may have extensive
research scope for the production of a wide variety of high-
performance graphene based polymer composite materials and
for the nanoparticles stabilization on graphene surface. Since
pluronic F127 is a biocompatible polymer, the obtained PF127-rGO
could have potential application in biotechnology. The PF127-rGO/
PGA nanocomposite lms were successfully prepared via drying in
an aqueous solution of PF127-rGO/PGA at room temperature.
Pluronic F127 acts as a compatibilizer and PEG acts as a plasticizer
for the successful fabrication of graphene-based GA nano-
composites. The nanocomposites obtained were characterized by
FESEM, FTIR, WAXS mechanical property and electrical resistivity
measurements. The mechanical property measurements show a
124% increase of stress at break and 185% increase of Young's
modulus in PF127-rGO 7.5 compared to PGA. Since GA is a bioplastic
material, the newly designed PF127-rGO/PGA nanocomposite lms
could have prospective applications in the development of envi-
ronmental plastic materials.
Acknowledgments
The authors acknowledge support from the Basic Research
Laboratory Program (2014R1A4A1008140) and Nano-Material
Technology Development Program (2016M3A7B4900117) through
the National Research Foundation of Korea (NRF) funded by the
Ministry of Science, ICT and Future Planning of Republic of Korea.
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