Polymer Testing 31 (2012) 31–38

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Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Material properties

Effect of functionalized graphene on the physical properties of linear low

density polyethylene nanocomposites
Tapas Kuila a, Saswata Bose a, Ananta Kumar Mishra b, Partha Khanra a, Nam Hoon Kim c,
Joong Hee Lee a, b, c, *
a
Department of BIN Fusion Technology, Chonbuk National University, Jeonju, Jeonbuk 561-756, Republic of Korea
b
BIN Fusion Research Team, Department of Polymer & Nano Engineering, Chonbuk National University, Jeonju, Jeonbuk 561-756, Republic of Korea
c
Department of Hydrogen and Fuel Cell Engineering, Chonbuk National University, Jeonju, Jeonbuk 561-756, Republic of Korea

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

Article history: Dodecyl amine-modified graphene (DA-G)/linear low density polyethylene (LLDPE)
Received 6 August 2011 nanocomposites were prepared through solution mixing. Field emission scanning electron
Accepted 19 September 2011 microscopy analysis revealed homogeneous dispersions of graphene layers in the
nanocomposites. X-ray diffraction analysis showed that the average crystallite size of the
Keywords: nanocomposites was increased. However, the % crystallinity was found to decrease due to
Graphene
the formation of a random interface. Dynamic mechanical analysis showed that the storage
Nanocomposites
moduli of the nanocomposites were much higher than that of neat LLDPE. The
Dynamic mechanical analysis (DMA)
Thermomechanical analysis nanocomposites were also more thermally stable than neat LLDPE. Isothermal thermog-
Gas barrier property ravimetry showed that homogeneously distributed graphene could act as a good inhibitor
during thermal degradation of the nanocomposites. Differential scanning calorimetry
showed that the crystallization temperature of the nanocomposites increased with
increasing DA-G content. Thermomechanical analysis showed that the dimensional
stability of the nanocomposites was significantly increased by the addition of the DA-G.
The coefficients of thermal expansion decreased with increasing DA-G content. The
oxygen and nitrogen permeability of the nanocomposites was lower than that of neat
LLDPE.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction carbon nanotubes (CNTs) and carbon nanofibers (CNFs)

Polymer nanocomposites have attracted considerable
attention due to their wide range of applications such as
automobiles, aerospace, packaging materials, coatings and
pigments and construction engineering [1–5]. Nanofiller
distributed in the polymer matrix can improve mechanical,
thermal, gas barrier, flame retardant and electrical prop-
erties of the nanocomposite materials [1–5]. Carbon-based
nanofillers such as carbon black, exfoliated graphite (EG),
* Corresponding author. Department of BIN Fusion Technology,
Chonbuk National University, Duckjin-dong 1Ga 664-14, Jeonju, Jeonbuk
561-756, Republic of Korea. Tel.: þ82 63 270 2342; fax: þ82 63 270 2341.
E-mail address: jhl@chonbuk.ac.kr (J.H. Lee).
have been widely used to prepare polymer nanocomposites
[6–10]. Among these, CNTs have been reported to be very
effective conductive fillers [10,11] in terms of mechanical,
electrical and thermal properties. However, the high
production cost of CNT limits their application as nano-
fillers for the preparation of polymer nanocomposites. The
discovery of graphene in 2004 has largely circumvented
this problem [12,13].
Graphene, a monolayer of carbon atoms arranged in
honeycomb networks, has extraordinary electrical,
thermal, and mechanical properties arising from its unique
structure [14–16]. Its unique properties make it suitable for
use as inorganic filler to improve the electrical, thermal and
mechanical properties of polymer composites [10,13–20].
However, pristine graphene is not compatible with organic

0142-9418/$ – see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymertesting.2011.09.007
32 T. Kuila et al. / Polymer Testing 31 (2012) 31–38
polymers and does not form homogeneous composites: it
requires surface modification prior to nanocomposite
preparation [13]. Graphene has been surface modified by
a range of techniques employing various organo modifying
agents [10]. Among these reported techniques, the nucle-
ophilic addition of organic molecules to the surface of
graphene is an effective way to the bulk production of
surface-modified graphene [13,17]. This work reports the
use of dodecyl amine (DA) for the surface modification of
graphite oxide to obtain-DA modified graphene (DA-G).
Linear low density polyethylene (LLDPE) was selected as
the polymer matrix due to its excellent flexibility,
mechanical strength and durability. In addition, it is
chemically inert to acids and alkali and can easily elongate
while applying a tensile stress. The preparation of DA-G/
LLDPE nanocomposites by solution mixing techniques (for
better dispersion of DA-G in LLDPE) is discussed herein and
the dynamic mechanical analysis, thermomechanical
analysis and gas barrier properties of the resulting nano-
composites are evaluated.
2. Experimental
2.1. Materials
Graphite flake was purchased from Sigma Aldrich,
Steinheim, Germany. Sulfuric acid, hydrochloric acid, ethanol
and hydrogen peroxide were obtained from Samchun Pure
Chemical Co. Ltd. (Pyeongtaek-si, Korea). Potassium
permanganate (Junsei Chemical Co. Ltd., Tokyo, Japan) was
used as oxidizing agent. The organic modifier, dodecyl amine
(DA), and the reducing agent, hydrazine monohydrate, were
procured from TCI, Tokyo, Japan and used without further
purification. LLDPE (density, 944 kg/m3 at 23  C) was
supplied by Hanwha Chemical, Korea. Xylene (Duksan
reagent and chemicals, Youngdeungpo-Gu, Korea) was used
as the solvent to prepare the DA-G/LLDPEcomposite.
2.2. Preparation of dodecyl amine modified graphene (DA-G)
Graphite oxide was prepared by a modified Hummers
method [21]. For surface modification, graphite oxide was
dispersed in 200 ml of distilled water (2 mg/ml) by
ultrasonication for 30 min using a ULH 700S bath-type
sonicator. Then, the dispersion of graphite oxide was
centrifuged (Beckman Coulter, AllegraÔ X-22R) for
15 min at 3000 rpm to remove the unexfoliated graphite
oxide. The stable brown coloured dispersion was trans-
ferred to a 500 ml round bottom flask. 500 mg of dodecyl
amine (DA) was dissolved in ethanol and the solution was
added to the graphite oxide dispersion followed by stir-
ring at room temperature for 24 h. The nucleophilic
substitution occurred through the amine functionality of
DA to the epoxy functionality of the graphite oxide. The
reduction of DA functionalized graphite oxide was carried
out using hydrazine monohydrate. The final product was
washed with water-ethanol mixture to remove the excess
DA adsorbed on the surface of the modified graphene
(DA-G). The black powder was dried under vacuum at
60  C for 72 h.
2.3. Preparation of DA-G/LLDPE nanocomposites
For nanocomposite preparation, a calculated amount of
DA-G (0.075, 0.15, 0.45, 0.75, and 1.20 g, respectively) was
dispersed in 40 ml xylene by ultrasonication for 30 min. In
a 250 ml Wit’s apparatus, 15 g LLDPE was dissolved in
100 ml xylene at 140  C to obtain a viscous solution. The
dispersion of DA-G was then added to the polymer solution
and stirred for ca. 20 h at 140  C. Finally, the composite
solution was cast onto a glass Petri dish and dried at
reduced pressure inside a vacuum oven at 75  C to remove
the solvent. The samples were then compression molded to
obtain sheets of DA-G/LLDPE nanocomposites. DA-G/LLDPE
nanocomposites containing 0.5, 1.0, 3.0, 5.0, and 8.0 wt.% of
DA-G have been designated as LDG-0.5, LDG-1, LDG-3, LDG-
5, and LDG-8, respectively.
2.4. Characterization
X-ray diffraction (XRD) study of all the samples was
carried out at room temperature on a D/Max 2500V/PC
(Rigaku Corporation, Tokyo, Japan). The crystallite size of
pure LLDPE and DA-G/LLDPE nanocomposites was carried
out by using the Scherrer formula [22]
Dp ¼ 0:89l=bcos q
where b is the half height width (in radian) of the crystal-
line peak, q is the Bragg’s angle and l is the wave length
(0.154 nm for Cu). The degree of crystallinity of the samples
was calculated from the ratios of integrated intensities of
the crystalline and amorphous regions. The percentage of
crystallinity, cc was obtained using the following relation-
ship [23]:
Ic
cc ¼  100
Ia þ Ic
where, Ic and Ia are integrated intensity of the crystalline
and amorphous region.
Fourier transform infrared spectroscopy (FTIR) was
performed using a Nicolet 6700 spectrometer (Thermo-
scientific, USA) over the wave number range, 4000 -
400 cm1. The powdered sample of DA-G was mixed with
KBr and pressed into a thin pellet for FTIR study. Pure LLDPE
and its nanocomposites were compression molded to
prepare a thin film (w 40–50 mm).
Field emission scanning electron microscopy (FESEM)
was carried out using a JSM-6701F (JEOL, Japan). Pure
LLPDE and the nanocomposite samples were coated with
a thin layer of platinum under argon (Ar) atmosphere at
a vacuum pressure of w 102 Torr prior to being scanned in
a high resolution scanning electron microscope. The
thickness of the platinum coating was approximately
20 nm.
Thermogravimetric analysis (TGA) of neat LLDPE and
the nanocomposites (z5.5 mg) was carried out on a Q50
TGA (TA instruments, USA) with a heating rate of 5  C/min
from 60 to 600  C in air. Isothermal TGA was performed
with the same instrument at constant temperature (300  C)
in the presence of air.
 T. Kuila et al. / Polymer Testing 31 (2012) 31–38 33

Differential scanning calorimetry (DSC) analysis of the Table 1

nanocomposites was performed with a TA instruments Q- Crystallite size and crystallinity of pure LLDPE and DA-G/LLDPE nano-
composites determined by XRD analysis.
20 from room temperature to 180  C. First, the sample was
heated from room temperature to þ200  C (5  C/min) and Sample Peak Peak Crystallite Crystallite % crystallinity
held for 10 min at this temperature to eliminate the angle angle size (nm) size (nm) (cc)
(2q1) (2q2) at 2q1 at 2q2
thermal history. Then, the samples were cooled to room
LLDPE 21.37 23.68 13.41 16.31 53.8
temperature at a rate of 5  C/min followed by reheating up
LDG-0.5 21.33 23.58 16.50 20.19 50.5
to þ200  C at the same rate. LDG-1 21.38 23.64 20.12 20.20 50.1
Dynamic mechanical analysis (DMA) of neat LLDPE and LDG-3 21.28 23.64 16.25 16.00 48.1
its nanocomposites were carried out with a Q 800 DMA (TA LDG-5 21.89 24.21 16.25 16.32 47.2
instruments, USA) in tension mode at a frequency and LDG-8 21.55 23.87 13.64 13.48 44.8

heating rate of 1 Hz and 2  C/min, respectively.

In order to measure the dimensional stability of neat
LLDPE and its composites, thermomechanical analysis
(TMA) was carried out with a TMA Q 400 (TA instruments,
USA) at a heating rate of 3  C/min.
Oxygen and nitrogen barrier properties were measured
on a Toyoseiki (Japan) gas permeability machine at 1 atm
pressure. The sample was cut from the compression mol-
ded sheet and used directly for gas barrier property
analysis.
3. Results and discussion
Fig. 1 shows the XRD pattern of pure DA-G, pure LLDPE
and their nanocomposites with 0.5, 1, 3, 5, and 8 wt.% of DA-
G. The XRD pattern of pure GO is shown in the inset of Fig. 1.
The 002 reflection peak of graphite oxide appeared at 2q w
11.2 corresponding to the d spacing values of 0.79 nm.
Upon surface modification and reduction of graphite oxide,
the 002 reflection peak fully disappeared due to the
extensive intercalation and exfoliation of graphite oxide by
dodecyl amine. The spectrum of pure LLDPE showed two
amorphous peaks at 2q ¼ 21.42 and 23.73 . It was found
that the XRD pattern of DA-G/LLDPE consisted of the
characteristic peaks of pure LLDPE. Table 1 show the crys-
tallite size and % crystallinity of pure LLDPE and DA-G/
LLDPE nanocomposites. The crystallite size of the DA-G/
LLDPE nanocomposites was increased compared to the
pure LLDPE. The increase in apparent crystallite size is
considered to be due to both an increase in the true mean
size and improvements in local lattice order [24]. On the
contrary, the % crystallinity of the nanocomposites was
gradually decreased with the addition of DA-G. This is
probably due to the formation of a random interface. The
presence of homogeneously distributed DA-G layers in the
LLDPE matrix inhibited the ordered crystalline structure of
the polymer chains causing a significant decrease in %
crystallinity of the DA-G/LLDPE nanocomposites [25].
Fig. 2 shows the FTIR spectra of pure graphite oxide, DA-
G, LLDPE and DA-G/LLDPE nanocomposite with 3 wt.% DA-
G loading. A broad peak at 3437 cm1, assigned to O–H
stretching, appeared in the spectra of pure graphite oxide
and DA-G, indicating the incomplete reduction of graphite
oxide to graphene. The peaks at 1721 cm1 and 1066 cm1
were due to carboxyl and epoxy groups of graphite oxide
and were not observed in the spectrum of DA-G [26,27].
The peak at 1628 cm1 in the spectrum of graphite oxide
indicates the presence of remaining graphitic sp2. The
emergence of peaks at 2950, 2928 and 2857 cm1, corre-
sponding to C–H stretching vibrations of CH3, CH2 and CH
groups in DA-G, indicates the successful modification of the
graphite oxide. The band at 1644 cm1 was assigned to
carbonyl stretching vibration, indicating the formation of
an amide-carbonyl (NHCO) bond between the graphene

Fig. 1. XRD pattern of pure DA-G, LLDPE and their nanocomposites with 0.5,
1, 3, 5, and 8 wt.% of DA-G. Fig. 2. FTIR spectra of (a) graphite oxide, (b) DA-G, (c) LLDPE and (d) LDG-3.
34 T. Kuila et al. / Polymer Testing 31 (2012) 31–38

sheets and DA molecules [28]. The peak at 1560 cm1
further confirms the formation of amide linkage. LLDPE and
its nanocomposites showed bands at 2950, 2928 and
2857 cm1, attributable to the C–H stretching vibrations of
CH3, CH2 and CH groups. The spectrum of the DA-G/LLDPE
composite had the peaks at 1470 and 1375 cm1 (defor-
mation of CH2 and CH3 groups) shift slightly to 1466 and
1370 cm1, possibly due to interactions between the
modified graphene and LLDPE polymer.
The FE-SEM images of DA-G and DA-G/LLDPE nano-
composites show a flake-like morphology of DA-G (Fig. 3).
The morphology of DA-G consisted of randomly aggre-
gated, thin, crumpled sheets closely associated with each
other [29]. Their lateral dimension varied between 1–5 mm.
The thickness is undeterminable from the FE-SEM images.
In solid powder form, the DA-G exists as aggregates. Fig. 3
(c,d) show the surface morphology of the nanocomposites
with a DA-G content of 3 wt.% (LDG-3). This reveals that the
graphene sheets were dispersed in the LLDPE matrix. The
dispersion of graphene layers in the LLDPE matrix indicates
the formation of DA-G/LLDPE nanocomposites. The fracture
surface morphology of neat LLDPE and LDG-3 are shown in
Fig. 3 (e,f). The fracture surface of neat LLDPE was smooth
while the nanocomposites had a comparatively rough
surface. The appearance of rougher surface morphology
and the presence of interfacial interaction between filler

Fig. 3. FE-SEM photomicrographs of (a,b) DA-G, (c,d) surface morphology of LDG-3, (e,f) fracture surface morphology of neat LLDPE LDG-3.
 T. Kuila et al. / Polymer Testing 31 (2012) 31–38 35

and polymer is an indication of stronger mechanical Table 2

properties. Therefore, the SEM images of the fracture DMA values of pure LLDPE and DA-G/LLDPE nanocomposites.

surfaces are in good agreement with the observed Sample E0 (MPa) E0 (MPa) E0 (MPa) E0 (MPa) tan da-max
mechanical properties of the nanocomposites. at 75  C at Tg ¼ 28  1  C at 25  C at 50  C at 80  C
The storage moduli (E0 ) of DA-G/LLDPE nanocomposites LLDPE 1821 1046 289 134 0.2389
with different amounts of DA-G were greater than that of LDG-0.5 2167 1310 425 214 0.2271
LDG-1 2272 1387 446 195 0.2356
neat LLDPE (Fig. 4(a)). At 50  C, the modulus of the nano-
LDG-3 2199 1326 447 207 0.2256
composites with 8 wt.% DA-G (LDG-8) was 293 MPa, which LDG-5 2272 1436 496 244 0.2189
is 118% higher than that of neat LLDPE. This is because LDG-8 2528 1582 569 293 0.2134
graphene acts as a reinforcing filler, significantly decreasing
the chain mobility of the LLDPE polymer. The effect of DA-G
content on the tan d of the nanocomposites is shown in
the nanocomposites with DA-G. Similar results were also
Fig. 3(b), and the related values are listed in Table 2. The
observed from plotting loss modulus (E00 ) against temper-
neat LLDPE and the nanocomposites exhibited two relax-
ature. This may be because of the homogeneous distribu-
ations, one at 29  C (b-relaxation) and another in the
tion of graphene in the nanocomposites. Fig. 4(b) also
range of 79–90  C (a-relaxation) [30–32]. The loss factor,
shows that the height of the tan dmax (a-relaxation) peak of
tan d, is the ratio of the loss modulus to the storage
the nanocomposites at 80  C decreases with increasing DA-
modulus and is very sensitive to structural transformations.
G content. This is indicative of the reinforcing effect of DA-G
The tan d peak (b-relaxation) can also be used to identify
in the LLDPE matrix and the decrease in damping behavior
the glass transition temperature (Tg). However, it can be
with increasing DA-G content.
difficult to determine Tg from the tan d peak, as evident
As evident from the DMA results, no significant changes
from Fig. 4(b). It shows a marginal change in both
in Tg was observable with the addition of DA-G to the LLDPE
b-relaxation (Tg) and a-relaxation for both neat LLDPE and matrix. Hence, DSC measurements were carried out to
quantify any changes of melting endotherm and crystalli-
zation temperature in the nanocomposites. The melting
endotherms of the nanocomposites were slightly higher
(w1  C) than that of neat LLDPE (Fig. 5), falling within the
error limit of the instrument. The crystallization tempera-
tures (Tc) of the nanocomposites were comparatively
higher than that of neat LLDPE, ascribable to the nucleation
(seeding) effect of DA-G on the LLDPE matrix [31,33]. Tc
increased with increasing DA-G content, except at 8 wt.%
loading, possibly because the number of nucleation sites
increased with increasing DA-G content. However, the
value of Tc for LDG-8 remained higher than neat LLDPE.
Fig. 6 shows TGA thermograms of neat LLDPE and its
nanocomposites with varying DA-G contents. The onset
degradation temperature of the nanocomposites was
significantly faster than that of neat LLDPE. This is

Fig. 4. Variation of storage modulus (a) and tan d (b) value of the DA-G/ Fig. 5. Cooling and second heating DSC cycle of neat LLDPE and DA-G/LLDPE
LLDPE nanocomposites at different amount of DA-G content. nanocomposites with 0.5, 1, 3, 5 and 8 wt.% of DA-G contents.
36 T. Kuila et al. / Polymer Testing 31 (2012) 31–38

Fig. 6. TGA curves of neat LLDPE and the nanocomposites of DA-G/LLDPE Fig. 7. Isothermal TGA curves of neat LLDPE and the nanocomposites 0.5, 1,
with various amounts of DA-G contents. 3, 5 and 8 wt% DA-G contents.

attributable to the early degradation of dodecyl amine of

functionalized graphene. The final degradation tempera-
ture of the nanocomposites (LDG-3, LDG-5, and LDG-8) was
much higher than that of neat LLDPE. The 50% weight loss
temperatures of LLDPE, LDG-1, LDG-3, LDG-5 and LDG-8
were 407, 408, 413, 442 and 454  C, respectively. Table 3
also lists the degradation temperature for 80% weight loss
as being much higher for the nanocomposites than that for
neat LLDPE. The enhanced thermal stability of the nano-
composites was attributed to the very high aspect ratio of
graphene which prevented the emission of small gaseous
molecules during thermal degradation. The homoge-
neously dispersed graphene also disrupted the oxygen
supply by forming charred layers on the surfaces of the
nanocomposites [6]. This indicates that graphene can act as
a good barrier to prevent the thermal degradation of LLDPE.
This was corroborated by studying the isothermal TGA of
neat LLDPE and the nanocomposites (Fig. 7). The rate
constants for neat LLDPE and the nanocomposites were
calculated considering first order kinetics (W ¼ W0ekt,
where W0 is the initial weight, W is the remaining weight
at time t and K is the first order rate constant). The rate
constant for neat LLDPE was much higher than those of the
nanocomposites (Table 3). The rate of thermal degradation
of the nanocomposites was slower than that of neat LLDPE,
with increasing DA-G content further slowing the degra-
dation (Fig. 7). This can be ascribed to increased char
formation with increased DA-G content.

Table 3
TGA and isothermal TGA data for pure LLDPE and DA-G/LLDPE
nanocomposites.

Sample Onset degradation Temperature Temperature Rate constant

temperature ( C) ( C) at 50% ( C) at 80% (s1)
weight loss weight loss
LLDPE 317 407 443 9.57  104
LDG-1 299 408 443 1.95  104
LDG-3 300 413 448 1.65  104 Fig. 8. (a) Variation of dimensional stability of pure LLDPE and its
LDG-5 300 442 462 6.02  105 composites with the change in temperature and DA-G content, (b) The
LDG-8 302 454 464 4.22  105 coefficient of thermal expansion (CTE) of DA-G/LLDPE nanocomposites in
the range of 40–70  C and 80–110  C.
 T. Kuila et al. / Polymer Testing 31 (2012) 31–38
The variation of dimensional stability of pure LLDPE and
its nanocomposites with the change in DA-G content and
temperature are shown in Fig. 8a. The change in dimen-
sional stability of pure LLDPE is almost linear at higher
temperatures (70–110  C). On the contrary, the slopes were
much lower for the nanocomposites as compared to that of
the pure LLDPE. This is attributed to the increased hardness
proportional to the content of DA-G in the nanocomposites
[34]. The TMA results showed that the dimensional change
of the nanocomposites was significantly decreased by the
addition of the DA-G.
Coefficients of thermal expansion (CTE) were calculated
over two different temperature ranges (40–70  C and 80–
110  C) from the TMA curves and are shown in Fig. 8b. It was
determined individually from the linear portions of each
thermogram below 70  C and above 80  C. The CTE of neat
LLDPE was 575.63  106/ C below 70  C and 977.25  106/

C above 80  C. A significant change of CTE was observed
upon addition of only 0.5 wt.% DA-G. This was attributed to
the very large surface area and low CTE of graphene [35]. A
similar observation was found by Kim et al. for exfoliated
graphite nanoplatelets/LLDPE nanocomposites prepared by
Fig. 9. (a) Oxygen and nitrogen permeability of DA-G/LLDPE nano-
composites at room temperature and 1 atm pressure, (b) “Tortuous path”
model for DA-G/LLDPE nanocomposites.
37
solution and melt mixing [36]. Therefore, the CTE of the
nanocomposites decreased regularly with increasing DA-G
content, with no sharp change observed between 0.5 wt.%
and 8 wt.% DA-G loading. It is also interesting to note that
CTE did not change greatly between the two temperature
ranges (40–70  C and 80–110  C).
Oxygen and nitrogen permeability of the LLDPE nano-
composites are shown in Fig. 9a. The oxygen permeability
was decreased from 36.8 to 19.5 fm/Pa.S with the addition of
only 1 wt.% DA-G. At the same amount of DA-G loading,
nitrogen permeability was decreased to 5.7 from 11.9 for pure
LLDPE. This is attributed to the very high aspect ratio of
graphene which prevents the permeation of gaseous mole-
cules through the nanocomposites by creating multiple
layers which forces gaseous molecules to flow through the
nanocomposites materials in a “tortuous path”, forming
complex barriers to gases, as shown in Fig. 9b. The gas
permeation properties are also largely dependent on the
thermal stability of the nanocomposites and the interfacial
interaction between the filler and the matrix polymer [37,38].
The improved gas barrier properties were in good agreement
with the morphological characterization and thermal prop-
erties of the nanocomposites. It is interesting to note that no
significant change in permeability (both for O2 and N2) was
observed as DA-G content increased from 1 to 5 wt.%.
4. Conclusions
High performance novel polymer nanocomposites were
prepared by solution mixing of LLDPE with DA-G. FTIR
showed that DA-G was doped onto the LLDPE polymer. FE-
SEM showed the homogeneous dispersion of graphene in
the LLDPE matrix. XRD analysis showed the formation of
DA-G/LLDPE nanocomposites. It was also noted that the
percent crystallinity was decreased in the nanocomposites
due to the formation of random interfaces. The storage
moduli of the nanocomposites were much higher than that
of neat LLDPE. The high surface area and aspect ratio of DA-
G reduced the chain mobility of the nanocomposites. The
nanocomposites were more thermally stable in air than
neat LLDPE. The gas barrier properties of the nano-
composites in terms of oxygen and nitrogen permeability
were also improved compared with the neat LLDPE.
Isothermal TG results of the nanocomposites were in good
agreement with their observed barrier properties. DSC
analysis showed that the crystallization temperature of the
nanocomposites was affected by the presence of DA-G due
to the nucleation effects of DA-G. TMA showed that the
addition of DA-G in the nanocomposites increased its
dimensional stability due to the increased material hard-
ness. The CTE values of the nanocomposites was decreased
significantly with the addition of only 0.5 wt.% of DA-G.
Acknowledgement
This study was supported by the Converging Research
Center Program (2011K000776), the Human Resource
Training Project for Regional Innovation, and the World
Class University (WCU) program (R31-20029) funded by
the Ministry of Education, Science and Technology (MEST)
and National Research Foundation (NRF) of Korea.
38 T. Kuila et al. / Polymer Testing 31 (2012) 31–38
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