Superlattices and Microstructures 82 (2015) 287292

Contents lists available at ScienceDirect

Superlattices and Microstructures

journal homepage: www.elsevier.com/locate/superlattices

Preparation and characterization of graphene

nano-platelets integrated polyaniline based
conducting nanocomposites
Mamata Reddy Tokala a, Balaji Padya b, P.K. Jain b, C.H. Shilpa Chakra a,
a
Centre for Nanoscience and Technology (CNST), Institute of Science and Technology, Jawaharlal Nehru Technological
University, Hyderabad 500085, India
b
International Advanced Research Centre for Powder Metallurgy and New Materials, Hyderabad 500005, India

a r t i c l e

i n f o

Article history:
Received 21 November 2014
Received in revised form 31 December 2014
Accepted 7 January 2015
Available online 25 February 2015
Keywords:
Graphene nanoplatelets
Polyaniline
Conducting nanocomposites
Thermally expanded graphite

a b s t r a c t
Natural graphite akes were intercalated with strong oxidizing
agents and were converted into thermally expanded graphite
(TEG) through thermal exfoliation. Thermally expanded graphite
was delaminated and transformed into graphene nanoplatelets
(GNP) by using ultrasonic irradiation. GNP integrated polyaniline
(PANi) nanocomposites were synthesized via in-situ polymerization of aniline monomers in the presence of GNP. The structure
and morphology of composite was evidenced by scanning electron
microscopy, Transmission electron microscopy (TEM), X-ray
diffraction and Raman spectroscopy. TEM micrographs revealed
that GNP consists of 2025 graphene layers and PANi was uniformly coated on GNP. From Raman analysis it was showed signicant
interactions between GNP and polyaniline. Electrical conductivity
was measured by using 4-point probe device, enhanced conductivity was obtained for composite.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
Graphene nanoplatelets (GNP) are nanoparticles comprised of short stacks of platelet shaped graphene sheets that are identical to those found in carbon nanotube walls, but in a planar form.
Corresponding author at: Centre for Nanoscience and Nanotechnology, Institute of Science and Technology, Jawaharlal
Nehru Technological University, Hyderabad 500085, Telangana State, India.
E-mail address: shilpachakra.nano@gmail.com (C.H. Shilpa Chakra).
http://dx.doi.org/10.1016/j.spmi.2015.01.001
0749-6036/ 2015 Elsevier Ltd. All rights reserved.

288

M.R. Tokala et al. / Superlattices and Microstructures 82 (2015) 287292

Enhancement in thermal conductivity, chemical and thermal stability, electrical conductivity and
mechanical properties of nanocomposites can be obtained with inclusion of GNP into the matrix
due to their unique nanoscale structure, morphology and material composition. And GNP can be used
to improve the properties of wide range of polymeric materials, including thermoplastic and thermoset composites, natural or synthetic rubber, thermoplastic elastomers, paints and coatings.
Conducting polymers have attracted more attention in recent years due to their potential applications
in various elds like electrochemical displays, sensors, catalysis, lithium ion batteries [1]. Among all
conducting polymers, polyaniline (PANi) rapidly become the subject of interest because of its easy
chemical synthesis and its high stability toward environment [2,3]. Polyaniline can exist in many
oxidation forms so that it can be very easy to tailor its properties. However, only one form called emeraldine salt is electrically conducting and it can be easily synthesized by electrochemical or chemical
oxidation of aniline [4,5].
Conducting polymer composites are attractive for various applications due to their unique futures
like low cost, corrosion resistance and ease of processing and shaping [6,7]. Amongst carbon/conducting polymer composites, multi walled carbon nanotubes (MWCNT)/polyaniline (PANi) composite has
been studied more because MWCNT/PANi composite shows increased electrical conductivity than
individual components. The increased electrical conductivity is due to effective sit selective interaction between MWCNT and quinoid rings of PANi which leads to easy charge transfer between them
[8]. Poor dispersibility of nanoparticles is major obstacle to prepare the composites with improved
properties. In same way, dispersion of carbon nanotubes is major problem due to the rigidity and
strong pp interactions. GNP can be easily dispersed into the matrix and composites can be made
therefrom.
In the present work, graphene nano platelets/polyaniline composites were prepared by in-situ chemical oxidative polymerization reaction to obtain the synergistic effect of PANi and GNP.
2. Experimental
2.1. Synthesis of GNP and PANi
All the chemicals used in this work were of analytical grade and were used without further purication. For GNP synthesis, initially natural graphite akes (99% pure) were intercalated with nitration
mixture and then subjected to a thermal shock at 900 C for 10 s. Finally the obtained thermally exfoliated graphite was sonicated for 24 h by using ultra probe sonicator to obtain GNP [18]. For PANi synthesis, 250 ml of aqueous hydrochloric acid was taken in the beaker and 20 ml of aniline was added to
it. The solution was maintained at 05 C by using ice bath. By taking ammonium persulfate solution
(APS) in burette, APS is added drop by drop to the aniline solution for 1 h under continuous mechanical stirring (at 05 C). PANi was obtained by vacuum ltration, followed by neutralization by adding
copious amount of distilled water and methanol. Finally PANi was obtained drying at 90 C under
vacuum for 48 h.
2.2. Synthesis of GNP/PANi nanocomposite
GNP/PANi was synthesized by in-situ polymerization reaction which lines similar as PANi synthesis. Here, 1 wt% of GNP was added to as prepared aniline solution and sonicated to obtain homogenous
mixture. On the addition of APS by drop wise, the polymerization reaction starts and it was allowed for
2 h with continuous stirring. GNPPANi nanocomposite was obtained by ltration followed subsequent neutralization and drying in vacuum at 90 C for 48 h. It was crushed and characterized using
various characterization techniques.
2.3. Characterization
Field emission scanning electron microscope (FESEM) (Model Hitachi S-4300SE/N) was used to
study surface morphology of synthesized materials. Microstructure of GNP, PANi and GNP PANi

M.R. Tokala et al. / Superlattices and Microstructures 82 (2015) 287292

289

composite was studied using transmission electron microscope (TEM, Model FEI Technai G2 S-Twin).
Micro Raman spectroscopic study was carried out using LabRam HR800 Raman spectrometer;
514.5 nm green line of argon + ion laser was used as the excitation source. X-ray diffraction (XRD)
(Brukers AXS Model D8 Advance system) patterns were recorded using Cu Ka as the X-ray source.
3. Results and discussion
Fig. 1a and b shows the electron micrograph of randomly aggregated, thin and at GNP structures.
It can also be observed that some of the regions with micro folding and scrolled structures. Each GNP
was consists of 2025 graphene layers. Fig. 1c depicts the morphology and structure of PANi in emeraldine salt form. PANi was in the form of particular existence of highly agglomerated tubular and granular morphology, the diameters of nanotubes are in sub-micron range with length in the order of few
microns. This due to the large proportion of solution polymerized of PANi existing in the agglomerated
form. According to the chemical theory of nucleation [9], the polymerization of aniline in the absence

Fig. 1. FESEM and TEM plane view images of GNP (a, b), PANi (c, d) and GNP/PANi structures (e, f).

290

M.R. Tokala et al. / Superlattices and Microstructures 82 (2015) 287292

of any additional structures gets initiated with the formation of PANi nuclei which are homogeneously
distributed in the acidic solution. In the subsequent stage, heterogeneous growth of PANi takes place
on the already formed nuclei. As synthesized PANi was granule nature as illustrated in Fig. 1d.
FESEM and TEM plane view images of GNP/PANi composite structures are shown in Fig. 1e and f. As
anticipated, it is evident from the electro micrographs that PANi is uniformly coated on the GNP structures in turn resulting in the formation of uniform networks of composites structures. It is observed
that the original shape of the starting material i.e., GNP is maintained even after the in-situ polymerization. The unchanged shape of GNP structures in the composites indicates that the polymerization of
aniline monomers has taken place predominantly on the GNP surface. If the polymerization had taken
place predominantly in the space between the graphite multilayers of individual GNP structures, the
layer would have delaminated and denite shape change would have taken place [14,17,20]. Fig. 1f
depicts that the GNP is acted as a site for PANi nucleation and PANi was coated uniformly over
GNP surface.
Fig. 2 shows the XRD patterns of GNP, pure PANi and GNP/PANi composite. For GNP, the diffraction
peaks at 2h = 26.5 and 45.8 can be attributed to the graphite like structures (0 0 2) and (1 0 0), respectively. For pure PANi, the crystalline peaks appear at 2h = 15.3, 20.7 and 25.2, corresponding to
(0 1 1), (0 2 0) and (2 0 0) crystal planes of PANi in its emeraldine salt form, respectively
[10,15,16,19,20]. The XRD of GNP/PANi composites presents crystalline peaks similar to those
obtained for pure PANi, revealing that no additional crystalline order has been introduced into the
composite.
Fig. 3 depicted the Raman spectroscopy of GNP, PANi and GNP/PANi composite. Broad D bands
approximately at 1340 cm 1and G bands approximately 1582 cm 1 were observed in the Raman
spectrum. In the Raman spectrum, the G band represents the in-planebond-stretching motion of
the pairs of C sp2 atoms (the E2g phonons), while the D band corresponds to breathing modes of rings
or K-point phonons of A1g symmetry [11]. In addition, the intensity of the G band is higher than the D
band for GNP due to the ordered crystal structure of GNP, suggesting that the GNP has less
defects.[12].
For GNP/PANi composite, CAH bending of quinoid ring at 1164 cm 1, CAN+, Stretching at
1340 cm 1 and C@N stretching vibration at 1542 cm 1 are observed, revealing the presence of
PANi structures. Compared with PANi, the GNP/PANi composite presents a shift of the CAN+, stretching peak toward low wavenumbers resulting from the pp electron interaction between GNP and
aniline monomer. The comparison of the ratios of D and G band peaks intensities (ID/IG) gives a measure of quality of the sample [13]. Thus, as the ratio approaches zero (as minimum as possible) the
carbon will have a more orders structures. ID/IG is 0.85 for GNP structures, these ratio shows that
GNP structures are more graphitic with fewer defects. In the GNP/PANi composites, due to the PANi

Fig. 2. Typical XRD patterns of (a) GNP and (b) PANi, GNP/PANi nanocomposite.

M.R. Tokala et al. / Superlattices and Microstructures 82 (2015) 287292

291

Fig. 3. Raman spectroscopy of (a) GNP and (b) PANi, GNP/PANi nanocomposite.

coating, the disorders increased for GNP structure. The ID/IG ratio in the case of GNP/PANi composites
is 0.86.
4. Electrical conductivity
The electrical conductivity of the GNP/PANi composite was measured using 4-point probe device.
Two probes are for voltage and other two are for current. The resistances offered by the voltage sensing probes can be neglected because the reading from the voltmeter is approximately equal to drop
across specimen. The correction factors need to be applied to compensate for the sample dimensions
and probe distances from the sample edges. From the measured current, voltage and correction factors
values the electrical conductivity will be derived. Due to the addition of PANi to GNP, the conductivity
of composite was increased from 2.54  10 4 S/cm to 16.93 S/cm [13,21].
5. Conclusions
GNP/PANi nanocomposite with uniformly PANi coated on GNP was synthesized using in-situ polymerization. In-situ polymerization process is a effective method to synthesize GNP/PANi composites.
From FESEM and XRD, it was found the PANi was coated uniformly on to the GNP resulting in the network of uniform composite structures. Raman analysis showed signicant interactions between GNP
and PANi. The electrical conductivity of GNP/PANi composite was signicantly enhanced.
Acknowledgements
I want to thank ARCI for giving me opportunity do my project. I want to thank Mr. Venkat Reddy
and Mr. Suba Rao, Lab Technicians ARCI for their support during my work.
References
[1] A. Malinauskas, Chemical deposition of conducting polymers, Polymer 42 (2001) 39593972.
[2] Q. Wu, Z. Xue, Z. Qi, F. Wang, Synthesis and characterization of Pan/clay nanocomposite with extended chain conformation
of polyaniline, Polymer 41 (6) (2000) 20292032.
[3] J. Unsworth, B.A. Lunn, P.C. Innis, Z. Jin, Technical review: conducting polymer electronics, J. Intel. Mater. Syst. Struct. 3
(1992) 380395.
[4] H. Letheby, XXIX On the production of a blue substance by the electrolysis of sulphate of aniline, J. Chem. Soc. 15 (1862)
161.
[5] A.G. Green, A.E. Woodhead, Aniline black and allied compounds, J. Chem. Soc. 97 (1910) 2388.
[6] X. Lu, W. Zhang, C. Wang, T. Wen, Y. Wei, Prog. Polym. Sci. 36 (5) (2011) 671712.

292

M.R. Tokala et al. / Superlattices and Microstructures 82 (2015) 287292

[7] D.W. Hatchett, M. Josowicz, Composites of intrinsically conducting polymers as sensing nanomaterials, Chem. Rev. 108 (2)
(2008) 746769.
[8] T.M. Wu, Y.W. Lin, Synthesis and characterization of externally doped sulfonated polyaniline/muti walled carbon nanotube
composites, Comput. Sci. Technol. (2009) 25592565.
[9] W.F. Smith, Principles of Material Science and Engineering, third ed., McGrew Hill Inc, New York, 1996.
[10] H.K. Chandhari, D.S. Kelkar, Investigation of structure and electrical conductivity in doped polyaniline, Polym. Int. 42 (4)
(1997) 380384.
[11] A.C. Ferrari, J. Robertson, Interpretation of Raman spectra of disordered and amorphous carbon, Phys. Rev. B 61 (20) (2000)
1409514107.
[12] X.L. Li, X.R. Wang, L. Zhang, S.W. Lee, H.J. Dai, Chemically derived, ultrasmooth graphene nanoribbon semiconductors,
Science 319 (5867) (2008) 12291232.
[13] G. VenkataRamana, Balaji Padya, Electrically conductive carbon nanopipegraphite nanosheet/polyaniline composites,
Carbon 49 (2011) 52395245.
[14] Jun Yan, Tong Wei, Bo shao, Preparation of a graphene nanosheet/polyniline composite with high specic capacitance,
Carbon 48 (2010) 487493.
[15] V. Gupta, N. Miura, Inuence of microstructure on the supercapacitive behavior of polyaniline/single walled carbon
nanotubes, J. Power Sources 157 (1) (2006) 616620.
[16] Du. Xs, M. Xiao, Facile synthesis of highly conductive polyniline/graphite nanocomposites, Eur. Polym. J. 40 (7) (2004)
14891493.
[17] J. Jang, J. Bae, M. Choi, Fabrication and characterization polyaniline coated carbon nanober for supercapacitor, Carbon 42
(13) (2005) 27302736.
[18] S. Stankocich, D.A. Dikin, R.D. Piner, Synthesis of graphene based nanosheets via chemical reduction of exfoliated graphite
oxide, Carbon 45 (7) (2007) 15581565.
[19] C.H. Ashok, K. Venkateshwara Rao, ZnO/TiO2 nanocomposite rods synthesized by microwave assisted method for humidity
sensor application, Superlattices Microstruct. 76 (2014) 4654.
[20] V. Rajender, T. Dayakar, K. Venkateshwara Rao, Systematic approach on the fabrication of Codoped ZnO semiconducting
nanoparticles by mixture of fuel approach for antibacterial applications, Superlattices Microstruct. 75 (2014) 551563.
[21] M. Neelgund Gururaj, Aderemi Oki, A facile method for the synthesis of polyaniline nanospheres and the effect of doping
on their electrical conductivity, Soc. Chem. Ind.: Polym. Int. 60 (2011) 12911295.