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Fabrication of functionalized graphene filled

carboxylated nitrile rubber nanocomposites as
Cite this: DOI: 10.1039/c6qm00025h
flexible dielectric materials†
Rakesh Manna and Suneel Kumar Srivastava*
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Hexadecylamine (HDA) was used to covalently functionalize graphite oxide followed by its reduction to
form functionalized graphene nanosheets (GNS–HDA). Subsequently, GNS–HDA has been used as filler in
fabricating carboxylated nitrile rubber (XNBR) nanocomposites via solution mixing. Mechanical measure-
ments of XNBR/GNS–HDA-2 nanocomposites compared to neat XNBR exhibited 60% improvement in
tensile strength (TS), 62% improvement in elongation at break (EB) and 13% reduction in Young’s modulus
(YM). Thermogravimetric studies demonstrate that incorporation of GNS–HDA into a XNBR polymer matrix
Received 21st April 2016, increases the thermal stability of composites with GNS–HDA loading. Further investigations show signifi-
Accepted 17th October 2016 cant enhancement in the dielectric constant of XNBR/GNS–HDA-2 (127.6) compared to neat XNBR (8.9)
DOI: 10.1039/c6qm00025h at 100 Hz. The corresponding value of the dielectric loss of the composite was enhanced only B2 times.
Such enhanced TS, EB, reduced YM and dielectric constants while retaining low dielectric loss enables the
rsc.li/frontiers-materials possible application of XNBR/GNS–HDA as flexible dielectric materials in electronic devices.

1. Introduction Dielectric elastomers (DEs) are electroactive-polymers (EAPs),

which have the ability to convert electrical energy to mechanical
Graphene is a two-dimensional material which is composed of energy over a broad frequency range.7,8 The lightweight, low
several atomic sheets of sp2 carbon atoms arranged in a hexa- modulus, large strain, fast response, high energy density and high
gonal lattice. It remains one of the thinnest material compared electromechanical coupling efficiency9,10 of DEs account for their
to other allotropes of carbon (graphite, CNTs, CF, fullerenes etc.). application in artificial muscles, sensors, micro-air vehicles, flat-
The high specific surface area, high aspect ratio, superior high panel speakers, micro-robotics and responsive prosthetics.11–14 In
Young’s modulus, fracture strength, and thermal conductivity order to obtain DEs in the application of high actuated strain and
of graphene make it an attractive material for many important at a low electric field, a high value of electromechanical sensitivity,
applications.1–3 Graphene has successfully been used as a b (b = dielectric constant, k)/(elastic modulus, Y) is required.
reinforcing filler in polymers, exhibiting its outstanding struc- Accordingly, a high dielectric constant and low elastic modulus
tural, electrical, and mechanical properties. The low price and are the solution for this problem. When a conducting filler is
availability of pristine graphite, followed by a simple method- incorporated into polymer matrices, k as well as Y values usually
ology applied in the formation of graphene make it one of the increase simultaneously.
potential conductive fillers in polymers. However, poor dispersion The dielectric constant of the polymer can be enhanced by
of graphene in a polymer matrix remains a major barrier and can incorporating high dielectric constant ceramic materials such
be overcome by covalent and noncovalent functionalization.4–6 as BaTiO3 and TiO2. But a high amount of ceramic material
Furthermore, the low dielectric constants (less than 10) of most of (50 vol%) is required to enhance the desired dielectric constant,
the polymers restricts their direct application in many electrical resulting in an enhancement of the elastic modulus, lowering
fields. Therefore, it is desirable to find out ways to enhance the of flexibility and poor processability, which narrow down the
dielectric constant of polymers, while retaining a low dielectric applications of DEs. Alternatively, DEs can also be fabricated
loss and good flexibility. through percolative composites by incorporating conducting
fillers such as graphene sheets and carbon nanotubes.15–18 The
choice of graphene in such work is also guided by its easy
Inorganic Materials and Nanocomposites Laboratory, Department of Chemistry,
synthesis from natural graphite compared to carbon nanotubes.
Indian Institute of Technology, Kharagpur-721302, India.
E-mail: [email protected]
The dispersion of covalent19–23 and non-covalent modified24–29
† Electronic supplementary information (ESI) available: Stress–strain plots and graphene and filler–polymer interfacial interactions account for
comparative table of Young’s modulus. See DOI: 10.1039/c6qm00025h its reinforcing ability, especially at low filler loading. Interestingly,

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the dielectric constant of such polymer composites increases (GONS) on XNBR latex particles and the in situ thermal reduction
abruptly near the percolation threshold.18 When the percolation in GONS at a moderate temperature.39 The corresponding nano-
threshold is reached, an undesirable enhancement in the dielectric composites exhibited high dielectric constant, low dielectric
loss of composites is also inevitable.4 The existing literature loss and low percolation threshold. The available literature also
also highlights the inferior extensibility of these polymer suggests that a high aspect ratio and low content of graphene37–39
nanocomposites.30,31 In view of this, several rubbers filled with are enough to enhance the k value compared to ceramic dielectric
graphene oxide or graphene have been investigated as DE fillers,7,8 and retains a low elastic modulus and better process-
materials. Poly(isobutylene-co-isoprene)/reduced graphene oxide ability. It is to be noted that carboxylation of the butadiene-
nanocomposites were prepared by a solution blending method acrylonitrile latex confers colloidal stability.40 In addition, XNBR
at 5 wt% loading. It introduces the dielectric properties over a latex is also stabilised with at least one external surface-active
broad frequency range and at different temperatures. The result agent.40 However, the drawbacks of latex stabilization during
shows that the dielectric constant at room temperature for storage, mixing, and processing are determined by time, tem-
reduced graphene oxide nanocomposites increases 10 times perature, phase separation, pH drift, shear in mixing etc.41
(29 at 10 2 Hz) when compared with that of expanded graphite Therefore, it would be interesting to use raw rubbers as alter-
composites (2.9).32 Al-Hartomy et al.33 studied the dielectric and
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natives in order to overcome all these undesirable hurdles in the

microwave properties of graphene nanoplatelets (1 to 5 phr)/ fabrication of flexible dielectric elastomeric nanocomposites.
carbon black (50 phr) filled natural rubber composites in the However, no significant advances have been made in fabricating
1–12 GHz frequency range. Graphene oxide-based dielectric mechanically improved and thermally enhanced XNBR/graphene
elastomer composite materials exhibited high dielectric con- dielectric materials directly from XNBR rubber and overcoming
stants and electric breakdown strength and low dielectric undesirable hurdles in fabrication imposed by the corres-
loss.4,34–39 Potts et al.34 fabricated NR/2 wt% reduced graphene ponding latex.
oxide (RGO) nanocomposites by co-coagulating latex compo- Motivated by this, we focused our work on the functionaliza-
sites followed by mixing in two roll mill. Subsequently, they tion of graphene nanosheet (GNS) surfaces using hexadecylamine
observed reduction in the elongation at break by 50% in the (HDA). It is anticipated that such a modification of graphene
corresponding XNBR nanocomposite. It is reported that increased could also reduce the dielectric loss by preventing the direct
dispersion level and interactions between the rubber chain and current conductance and enhance the compatibility of function-
filler materials render the dissipation of external stress through- alized reduced graphene oxide with the polymer matrix. Further-
out the polymer matrix. Liu et al.35 reported that dissipation of more, the low elastic modulus of the composite could overall
external stress can occur through alignment and slippage of lead to its application as a flexible dielectric material. The choice
rubber chains adsorbed on the surface of nanofiller. Poly(dimethyl) of carboxylated nitrile rubber (XNBR) in our work is mainly
siloxane embedded with 2 wt% thermally expanded graphene guided by the presence of strong polar carboxyl and cyano
sheets showed an increment in k from 2.7 to 23 at frequency groups, which could form a strong adhesion between GNS–HDA
of 10 Hz.4 The low increment in the dielectric constant than and XNBR. Finally, these XNBR/GNS–HDA nanocomposites have
expected could be ascribed to the poor dispersion and restacking been studied for their thermal stability, mechanical and dielectric
of graphene sheets. In another interesting work, Jiang et al.14 properties.
prepared 5 wt% loaded hyper branched aromatic polyamide
functionalized graphene sheets (GS–HBA) into a TPU matrix
and achieved an enhancement in the k value to 850 at 1000 Hz. 2. Experimental
However, the low dielectric loss is retained (o1.5) due to the 2.1 Materials
suppression of leakage current by hyperbranched aromatic
polyamide functional groups. Noncovalent-modified graphene XNBR (Krynacs X 740, LANXESS) and graphite Micro-850 were
(3%) polyurethane nanocomposite showed a dielectric constant procured from Germany and Asbury Graphite Mills, Inc.,
of 350, a dielectric loss of 0.20 and a loss modulus of 200 MPa Asbury, NJ, respectively. HDA (98%), ethanol, dicumyl peroxide
at room temperature in 1 kHz.36 According to Ning et al.,37 (DCP), and sodium nitrate (NaNO3) were supplied by SRL (Mumbai),
poly(dopamine) (PDA) coated GO (GO-PDA) assembled around a Hercules (USA) and S. D. Fine Chemicals (India) respectively.
carboxylated nitrile rubber (XNBR) latex showed that dielectric Potassium permanganate (KMnO4), concentrated sulfuric acid
loss and elastic modulus decrease, and breakdown strength (H2SO4), hydrogen peroxide (H2O2), and hydrazine hydrate
increases upon increasing the thickness of the PDA shells. Tian (N2H4) were purchased from Merck, India. Tetrahydrofuran (THF)
et al.38 reported carboxylated nitrile rubber (XNBR)/graphene was obtained from RFCL Limited, New Delhi.
oxide nanosheet encapsulated carbon sphere (GON–CNS) nano-
composites by latex. The compounding dielectric composites 2.2 Preparation of graphene oxide
exhibited a low dielectric loss and improved breakdown strength GO was prepared by the modified Hummers’ method reported
and actuated strain at a low electric field facilitating the wide earlier.42 According to this method, graphite (500 mg) along
application of dielectric elastomers. Another work involved the with sodium nitrate (250 mg) were taken in a beaker, containing
formation of dielectric composites prepared by using the com- 30 ml concentrated H2SO4, followed by addition of 1.5 g KMnO4
bined strategy of encapsulating graphene oxide nanosheets under stirring for 30 min. The resulting mixture was diluted with

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deionized water and then 10 ml of H2O2 was added to this. tensile fractured surface of the samples was studied using a
As a result, the color of the solution turned to brilliant yellow, Novanano SEM 430 scanning electron microscope (Germany).
indicating the formation of fully exfoliated graphene oxide. Atomic force microscopy (AFM) measurement was carried out on
Finally, the product free from metal ions was obtained by a Veeco Multimode V scanning probe microscope in the tapping
washing it several times with dilute HCl followed by deionized mode. Samples for AFM images of GNS–HDA and GNS were
water to remove the free acid. prepared by spin coating on a mica surface using 0.1 mg ml 1
dispersion in THF. The thermal stability of the samples was
2.3 Preparation of hexadecylamine functionalized graphene determined on a TGA Q5000 instrument in the temperature
Graphene oxide (200 mg) nanosheets prepared earlier by Hummers’ range of 60–600 1C at a heating rate of 10 1C min 1 in nitrogen
method were dispersed in 30 ml of water by sonication for 30 min. gas purging. Differential scanning calorimetry (DSC) measure-
Subsequently, HDA modified graphene was prepared based on ment of the samples was recorded on a TA instruments Q-20
an idea from earlier work.43,44 Accordingly, HDA (300 mg) was from 50 1C to room temperature. Dielectric properties were
dissolved in ethanol (60 ml) followed by heating and cooling. obtained using a QuadTech 7600 precision LCR meter in the
This cooled solution of HDA was added to the dispersion of frequency range of 10 Hz to 1 MHz.
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graphite oxide in water prepared earlier with sonication continuing

for 30 min. The resultant mixture was subsequently refluxed at
100 1C in the presence of hydroquinone (400 mg) for 24 hours. The 3. Results and discussion
formed solid product (GNS–HDA) was centrifuged followed by 3.1 Structure and morphology of GNS–HDA
washing with ethanol and drying at 65 1C in a vacuum for 24 h.
Fourier transform infrared (FTIR) spectra of HDA and GNS–HDA
The prepared GNS–HDA is indicated by its dispersion in organic
are displayed in Fig. 1. It is clearly evident that two asymmetric
nonpolar solvents (tetrahydrofuran, cyclohexane, toluene, and
bands appeared at about 2849 cm 1 and 2917 cm 1 in HDA as
ethanol etc.).
well as the presence of an amine group (–NH2) in GNS–HDA,
2.4 Preparation of GNS–HDA/XNBR composites clearly signifying the functionalization of graphene nanosheets
by HDA. Furthermore, the appearance of the carbonyl stretching
XNBR/GNS–HDA nanocomposites were prepared by a solution
vibration at 1644 cm 1 established the formation of a linkage
mixing method. Initially, GNS–HDA nanofillers (0, 0.5, 1, 1.5,
between the reduced graphite nanosheets and HDA. It is known
2 phr) were dispersed in THF with the assistance of an ultra-
that graphene oxide (GO) consists of hydroxyl (–OH) and epoxy
sonicator for 5 min. Accordingly, 5 g of XNBR was dissolved in
groups lying above and below the basal planes and the carboxyl
50 ml THF in a 100 cc beaker. In another beaker, the required
groups (–COOH) bound to the edges.37 Therefore, it is anti-
amount of GNS–HDA nanofiller was dispersed in THF under
cipated that functionalization of GO takes place via covalent
ultrasonic treatment for 5 min. Following this, it was added to
bonding between the –NH2 (HDA) and –COOH (GO) groups as
XNBR solution at room temperature and magnetically stirred
proposed in Scheme 1.
for half an hour, followed by the addition of 2 phr DCP. The
Fig. 2 shows XRD patterns of GNS and GNS–HDA. It is noted
stirring was continued for another 6 h. Finally, the solution was
that a (002) diffraction peak appeared for GNS at B241, corres-
cast in a glass petri dish to evaporate the solvent, THF, at room
ponding to a d-spacing of 0.34 nm. However, a (002) diffraction
temperature. Finally, the cast films were cured at 160 1C for
peak of GNS–HDA appeared at 21.51 (d002 = 0.41 nm). These
10 min, according to the cure time obtained from oscillating
findings further strengthened our contention based on FTIR
disc rheometer analysis (ODR). In a similar manner, XNBR
about the attachment of an amine group (HDA) on the graphene
composites filled with 0.5, 1.0, 1.5 and 2 phr of GNS–HDA were
nanosheets. In order to achieve further validation, AFM analysis
also fabricated. The obtained sheets were taken for further
characterization and application.

2.5 Characterization
The structure of GNS–HDA was analyzed by Fourier transform
infrared spectroscopy (FTIR) on a PerkinElmer RXI FTIR spectro-
meter, USA, in the frequency range of 400–4000 cm 1. The
crystalline/amorphous nature of GNS–HDA was obtained by
carrying out X-ray diffraction analysis on a Bruker D8, Advance
X-ray diffractometer with Cu Ka (l = 0.1542 nm) radiation in the
2y range of 51 to 801 and at a scan rate of 101 min 1. The
morphology of the samples was analyzed by TEM using a
JEOL2100 microscope at a voltage of 200 keV. The sample
preparation for TEM observation was carried out by cutting
the composite film with an ultramicrotome into thin sections
of 100 nm thickness with a diamond knife and the sample was
collected on 200-mesh copper grids. The morphology of the Fig. 1 FTIR spectra of (a) GNS–HDA and (b) HDA.

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Scheme 1 Chemical functionalization of HDA on graphene sheets.

Fig. 2 XRD patterns of (a) GNS and (b) GNS–HDA. Fig. 3 AFM image of (a) GNS, (b) height profile of GNS, (c) AFM image of
GNS–HDA, and (d) height profile of GNS–HDA.

of GNS and GNS–HDA was performed in the tapping mode and

is displayed in Fig. 3. The multilayers with broad distribution in
thickness and size are clearly evident from this. The height of
the GNS layers was found to be B1 nm and less than that of
graphite oxide due to the expulsion of different oxygen func-
tionalities (4CQO, –COOH, –OH, –O–).
However, HDA functionalized graphene sheets exhibited
relatively higher thickness (B2 nm).5 Our findings are also in
agreement with AFM studies reported on individually dispersed
graphene and rhodamine B noncovalently modified graphene
exhibiting a thickness of about 1 and 1.6 nm respectively.45
The morphology of GNS and GNS–HDA has been studied by Fig. 4 (a) FESEM and (b) TEM images of GNS–HDA.
FESEM and TEM analysis and the corresponding findings are
displayed in Fig. 4. It is clearly evident that GNS–HDA exists as
aggregated, thin crumpled nanosheets which are largely asso- dispersed GNS–HDA thin layers, while darker regions indicated
ciated with each other. The TEM image of GNS–HDA showed the stacking of the GNS–HDA layers.
the appearance of a flat and rippled morphology. The presence The thermal stability behavior of GO, GNS, and GNS–HDA
of light gray color in this image corresponds to the formation of has been investigated in the temperature range of 60–600 1C

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Fig. 6 Digital picture of the dispersion stability of (a) GNS–HDA and (b) GNS.
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Fig. 5 TGA of (a) GO, (b) GNS, and (c) GNS–HDA.

under a nitrogen atmosphere and the corresponding findings

are displayed in Fig. 5. The initial weight loss (B12%) in GO
between 60 1C and 130 1C can be ascribed to the adsorbed
water. At further higher temperatures, TG shows a weight loss
of 56% in the range of 130–325 1C due to pyrolysis of hydroxyl,
carbonyl, epoxy, and carboxylic acid groups in GO. After 325 1C
no significant weight loss is noticed due to the expulsion of
oxygen functionalities in GO. It is also noted that GNS and
GNS–HDA are both thermally stable up to 195 1C. This suggested
that neither GNS nor GNS–HDA is sensitive towards moisture Fig. 7 XRD spectra of (a) GNS–HDA, (b) neat XNBR, (c) 0.5 phr, (d) 1 phr,
adsorption. This could be ascribed to the enhanced hydrophobic (e) 1.5 phr, (f) 2 phr GNS–HDA filled XNBR composites.
nature of GNS–HDA achieved by effective functionalization of
HDA on the graphene surface. At higher temperatures, GNS
undergoes a significantly low weight loss of B5% due to incom-
plete reduction of the remaining oxygen functionalities in GO. In
contrast, degradation of GNS–HDA takes place much faster and
achieves a weight loss of B80% (495 1C). This is attributed to the
complete degradation of hexadecylamine due to the function-
alization of GNS. However, the possibility of a fraction of HDA
adsorbed on the surface of graphene also cannot be ruled out.35
The room temperature dispersion stability of GNS–HDA and GNS
has been investigated for THF (10 mg ml 1) for about 1-month
duration by recording its digitized image. Fig. 6 shows that Fig. 8 HRTEM of (a) 1 phr and (b) 1.5 phr GNS–HDA filled XNBR composites.
chemically functionalized GNS–HDA has significantly higher
dispersion stability in THF compared to GNS.
and accounts for the significantly enhanced properties of
3.2 Structure and morphology of GNS–HDA/XNBR composites XNBR/GNS–HDA nanocomposites.
Fig. 7 shows XRD patterns of XNBR and its 0.5, 1, 1.5 and 2 phr
GNS–HDA loaded nanocomposites. It is noted that the crystal- 3.3 TGA of XNBR composites
line and broad diffraction peak of GNS–HDA (2y = 21.50) There are various studies which demonstrate that the incorpora-
completely disappeared for all nanocomposites. Such observa- tion of graphene sheets into the polymer matrix enhances the
tions demonstrated the possible exfoliation of GNS–HDA in thermal stability of the composites under nitrogen atmospheric
the XNBR matrix.39,46 In order to further validate this, HRTEM conditions.47 Fig. 9 shows the thermal stability behavior of neat
analysis of XNBR/GNS–HDA composites has also been carried XNBR, 0.5, 1, 1.5, and 2 phr GNS–HDA filled XNBR under a
out and the findings are displayed in Fig. 8. It clearly shows that nitrogen atmosphere and the corresponding thermal data
the wrinkled and folded sheets of GNS–HDA exhibit good referring to thermal degradation temperature at 10 wt% loss
dispersion in the XNBR matrix. This is in all probability due (T10) are 388, 392, 393, 393, and 394 1C for 0, 0.5, 1, 1.5, and
to the compatibility between GNS–HDA and the XNBR matrix 2 phr GNS–HDA loadings respectively. These findings clearly

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Fig. 10 DSC curve of XNBR and various GNS–HDA/XNBR composites.

Fig. 9 TGA curve of XNBR and various GNS–HDA/XNBR composites.

demonstrate that incorporation of GNS–HDA into the XNBR

polymer matrix increases the thermal stability of composites
with GNS–HDA loading. However, XNBR/GNS–HDA (0.5 wt%)
shows significant improvement in thermal stability compared
to neat XNBR. Such an enhancement in the thermal stability of
XNBR/GNS–HDA nanocomposites is ascribed to the high aspect
ratio of graphene and complete exfoliation of GNS–HDA in the
XNBR polymer matrix. As a result, emission of volatile decom-
posed gaseous products and supply of oxygen from the surface
to the bulk are hindered due to an effective barrier effect of
GNS–HDA.47

3.4 DSC
Chemically modified graphene loaded polymers usually show
an enhancement in glass transition temperature (Tg).48,49 This
is attributed to the close proximity of embedded nanoparticles in
the polymer macromolecules, which restricts the chain mobility
of polymer chains at the interface.48–50 In contrast, DSC analysis
of neat XNBR and its GNS–HDA filled nanocomposites in Fig. 10
showed that Tg of XNBR decreased from 18 1C in all XNBR/
GNS–HDA nanocomposites. The maximum decrease in Tg of
20 1C is attained in 2 phr GNS–HDA loaded XNBR. This could
be ascribed to the enhanced chain mobility due to the presence of
Fig. 11 (a) Tensile strength and (b) elongation at break of neat XNBR and
free surfaces and repulsive interfaces in XNBR/GNS–HDA nano- various GNS–HDA/XNBR composites.
composites.51,52 Alternatively, lowering of Tg in XNBR/GNS–HDA
nanocomposites could be attributed to the plasticization effect53
or free volume existing at the polymer surface interface.54 improvement in 1, 1.5 and 2 phr filled GNS–HDA in XNBR
compared to neat XNBR. It is also noted that EB of neat XNBR
3.5 Mechanical properties (227%) increased substantially to 365% in 2 phr loaded GNS–HDA
The reinforcing effect of GNS–HDA on the mechanical properties in XNBR. The toughness of the GNS–HDA/XNBR composites also
of neat XNBR has also been investigated. Tensile strength (TS), increases significantly with filler loading. It is well anticipated that
elongation at break (EB), toughness (W), and Young’s modulus higher dispersion of nanomaterials in the polymer matrix
(YM) data have been generated from a stress–strain plot (ESI†) renders better performance of its nanocomposites. Such an
and are displayed in Fig. 11–13, respectively. It is noted that TS of enhancement in the mechanical properties of XNBR/GNS–HDA
neat XNBR (2.9 MPa) increases with the incorporation of filler nanocomposites could be attributed to the interfacial interaction
loading and attained maximum improvements (4.63 MPa) in between GNS–HDA and the XNBR matrix and effective load
2 phr GNS–HDA loaded XNBR. The variation in EB also shows transfer from the filler to the polymer matrix.46,50 Alternatively,

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Fig. 12 Young’s modulus of neat XNBR and various GNS–HDA/XNBR

composites.
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Fig. 14 FESEM images of the tensile fracture surface of (a) neat XNBR,
(b) 1 phr, (c) 1.5 phr and (d) 2 phr GNS–HDA loading.

single sheet adopting a wrinkled morphology imparts a measure

of entropic and rubber like elasticity itself.51 Furthermore, the
low modulus of wrinkled GNS–HDA single sheets and the high
compatibility between XNBR and GNS–HDA can also account for
the lowering of the modulus in its XNBR nanocomposites.

3.6 Dielectric properties

Fig. 15 and 16 show variation in dielectric permittivity (k) and
dielectric loss of neat XNBR and its GNS–HDA composites as a
function of frequency (log f ). It is inevitable that dielectric per-
mittivity decreases with increasing frequency for XNBR and its
Fig. 13 Toughness of neat XNBR and various GNS–HDA/XNBR composites. GNS–HDA composites. Such strong frequency dependence of
dielectric permittivity can be attributed to the interfacial polariza-
tion effect between the GNS–HDA and XNBR (Maxwell–Wagner–
the role of molecular level dispersion of GNS–HDA and its wrinkled
Sillars effect).39 The findings based on dielectric constants and
shape leading to mechanical interlocking and transmitting the
dielectric loss data of XNBR and its GNS–HDA composites at
applied stress to XNBR also cannot be ruled out.51 In addition,
100 Hz along with the values reported on other elastomers are
crumpled GNS–HDA adds some extra reinforcement at high
presented in Table 1. HDA filled XNBR nanocomposites increase
elongation when it is stretched, which is attributed to the
nearly 15 fold, whereas dielectric loss increases only 2 fold com-
enhancement in toughness and elongation at break.51 Fig. 14
pared to neat XNBR. It is also evident from Fig. 15 that the
shows FESEM images of the tensile fracture surface of XNBR
dielectric permittivity of GNS–HDA/XNBR composites is relatively
and its GNS–HDA filled nanocomposites. It demonstrates that
higher in the low frequency range (log f: 1–3) followed by a
XNBR exhibits a smooth surface in contrast to the corresponding
GNS–HDA composites, exhibiting divergence on the surface. The
extent of divergence increases with an increase in GNS–HDA
loading in the XNBR matrix. The YM defines the slope of the
curve in the elastic region. It is inferred from Fig. 13 that the YM
of the composites is reduced remarkably in GNS–HDA incorpo-
rated XNBR. This clearly indicates the reduced stiffness and
enhanced flexibility of fabricated XNBR/GNS–HDA nanocom-
posites. It is also noted that 2 phr of GNS–HDA loaded XNBR
showed a maximum decrease of about 13% in YM compared to
neat XNBR. Such findings are found to be considerably superior
compared to those reported for TRG/XNBR nanocomposites
earlier.39 In most of the graphene polymer composites, the
modulus enhances with the incorporation of filler loading,38,39
which is contrary to our study (ESI†). The increase in toughness Fig. 15 Dielectric constant vs. log(frequency) for neat XNBR and various
and decrease in YM suggest that GNS–HDA existing as almost a GNS–HDA/XNBR composites.

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be noted that GNS–HDA/XNBR achieved dielectric permittivity

(127 at 100 Hz) compared to that reported in TRG/XNBR (2211 at
100 Hz),39 PDA-GO/XNBR (250 at 100 Hz),37 PEDOT:PSS-RGO@PU
(350 at 1000 Hz)36 and GO@CNS/XNBR (650).38 However, the
dielectric loss values of GNS–HDA/XNBR (0.8 at 100 Hz) were
found to be comparable with the TRG/XNBR (0.6 at 100 Hz),39
PDA-GO/XNBR (1.2 at 100 Hz),37 PEDOT:PSS-RGO@PU (B0.2 at
1 kHz)45 and GO@CNS/XNBR (1.7 at 100 Hz)46 systems.

4. Conclusion
A simple facile solution mixing method has successfully been
Fig. 16 Dielectric loss vs. log(frequency) for neat XNBR and various GNS–
used in developing highly dispersed HDA functionalized graphene
HDA/XNBR composites.
nanocomposites of XNBR and their characterization. The mecha-
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nical properties at various loadings of HDA functionalized graphene

showed efficient load transfer. As a consequence, XNBR/GNS–
Table 1 Dielectric properties of XNBR and composites
HDA-2 exhibited a significant improvement in tensile strength
Dielectric permittivity Dielectric loss (60%) and elongation at break (62%). Furthermore, measurements
GNS–HDA (phr) @ 100 Hz @ 100 Hz
of the dielectric properties indicated a maximum enhancement in
0 8.9 0.38 the dielectric constant by 15 times (100 Hz), whereas the dielectric
0.5 17.8 0.46 loss was increased only 2 fold. The thermal study showed that
1 28 0.54
1.5 46.3 0.60 reduction in the glass transition temperature (Tg) of XNBR/GNS–
2 127.6 0.73 HDA-2 is responsible for the reduction in elastic modulus. This is
in all probability due to the lower elastic modulus of the wrinkled
and single sheet graphene produced by hexadecylamine function-
significant decrease at the higher frequency region. In all alization compared to XNBR. Such reduction in elastic modulus
probability, accumulation of charge between GNS–HDA and including enhanced tensile strength/dielectric permittivity and
XNBR at the interfaces in the low frequency region accounts very low dielectric loss makes these composites useful for applica-
for the higher dielectric permittivity values of the composites. tions as flexible dielectric materials in various electronic devices.
At a higher frequency, interfacial polarization lags behind
the frequency of electrical field. The dielectric permittivity of
the composites increases with the increase in filler loading. Acknowledgements
Furthermore, it may be interesting to mention that the presence
of conductive GNS–HDA fillers (electrodes) in XNBR (insulating) S. K. Srivastava and Rakesh Manna gratefully acknowledge DRDO,
allows forming the microcapacitor network.14 However, success- India, and IIT Kharagpur for grants to R. Manna for perusing this
ful functionalization also plays a crucial role in the enhancement research.
of its dielectric permittivity. Alternatively, there is a possibility
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