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Composites B 2015
Composites B 2015
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Anoop Anand
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P S Alegaonkar
Suwarna Datar
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Composites: Part B
journal homepage: www.elsevier.com/locate/compositesb
Department of Applied Physics, Defence Institute of Advanced Technology, Deemed University, Girinagar, Pune 411 025, India
Research & Development Establishment, DRDO, Pioneer Lines Dighi, Pune 411 015, India
a r t i c l e
i n f o
Article history:
Received 3 July 2014
Received in revised form 1 September 2014
Accepted 21 September 2014
Available online 28 September 2014
Keywords:
A. Nano-structures
A. Polymer-matrix composites (PMCs)
B. Mechanical properties
EMI shielding
a b s t r a c t
The advent of graphene heralded by the recent studies on carbon based conducting polymer composites
has been a motivation for the use of graphene as an electromagnetic interference (EMI) shielding material. One of the variants of graphene, graphene nanoribbon (GNR) shows remarkably different properties
from graphene. The EMI shielding effectiveness of the composite material mainly depends on llers
intrinsic conductivity, dielectric constant and aspect ratio. We have synthesized graphene nanoribbon
(GNR) Polyaniline (PANI) epoxy composite lm for effective shielding material in the X-band frequency range of 8.212.4 (GHz). We have performed detailed studies of the EMI shielding effect and
the performance of the composite and found that the composite shows 40 dB shielding which is sufcient to shield more than 95% of the EM waves in X Band. We checked the shielding effectiveness of the
composite lm by varying the GNR percentage and the thickness of the lm. The strength properties of
the synthesized composited were also studied with a aim to have a material having both high strength
and EMI shielding properties.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
Electromagnetic interference (EMI) has become a serious problem whose impact can be seen from day to day life like the interference of mobile signals with laptop, television or speakers
causing ickering of picture or disturbance in sound to the space
exploration, military applications and so on [14]. The impact of
EMI is not limited to the malfunctioning of electronic gadgets but
it also affects human health, for example, continuous exposure of
electromagnetic radiation increases the risk of cancer, asthma,
heart problems, migraine and even leads to miscarriage [5]. To provide solutions to these problems there is a very active quest for
making materials which are light weight, resistant to corrosion,
exible, as well as have effective and practical shielding applications. Carbon nanobers [6], carbon nanotubes [712], graphene
[13,14], carbon foam [15,16], etc. have proved to be useful nanofillers in polymer composites. Increase in the concentration of such
llers increases the cost of the material and degrades the strength
of the composite [17]. An EMI shielding material may not turn out
to be a high strength material. Therefore, for an application such as
aerospace industry which requires a high strength material as well
Corresponding author.
E-mail address: suwarna.datar@gmail.com (S. Datar).
http://dx.doi.org/10.1016/j.compositesb.2014.09.014
1359-8368/ 2014 Elsevier Ltd. All rights reserved.
as EMI shielding capabilities, a very special polymer ller combination is needed to provide both the capabilities reasonably well.
Epoxy resins are thermosetting polymers and hence offer a
wide range of applications owing to their excellent mechanical
properties like high stiffness, specic strength, dimensional stability, low cost, good adhesion to many substrates, chemical resistance and so on [18]. Many groups have worked on the use of
epoxy based carbon composites to enhance its properties.
Nanocomposite with carbon ller in polymer, faces issues related
to interfacial interaction between the ller and the polymer for
high strength applications. Cooper et al. have investigated the
detachment of MWCNT from the epoxy matrix. They observed that
the shear strength depended on the size of the interface. Good
mechanical properties require homogeneous dispersion of carbon
nanoller in epoxy matrix and strong interfacial interaction
between the two [19]. Sufcient stress transfer from polymer
matrix to carbon nanostructure is required for this. This can be
achieved by chemical modication of the carbon nanostructures.
Several groups have reported enhancement in mechanical properties using epoxy/carbon nanostructure composite. Liao and his
co-workers have studied the thermo mechanical property of epoxy
based nanocomposite of SWCNT [20]. Allaouis group has investigated the inuence of MWCNTs in rubber epoxy [21]. Gallego
and co-worker used cationic photo polymerization technique to
473
SET dB 10log10
PT
ET
HT
20log10
20log10
PI
EI
HI
2
ET
jS21 j2 jS12 j2
EI
2
ER
jS11 j2 jS22 j2
EI
Aeff
1 R T
1 R
SER and SEA are also expressed in terms of reectance, transmittance and effective absorbance as
T
1R
2. Experimental
2.1. Materials
Potassium permanganate (KMnO4), sulfuric acid (H2SO4), aniline, (1S)-(+)-Camphor-10-Sulfonic acid (CSA), ammonium peroxydisulfate, Epoxy LY 1564, Hardener XB 3486 were of analytical
grade. Aqueous solution was prepared using doubledistilled water.
474
Fig. 2. SEM image of (a) pure Epoxy and (b) 0.1 wt% GNR/PANI composite in the epoxy matrix.
Fig. 3. (a) Raman spectra of GNR/PANI epoxy and only GNR. Inset show the Raman spectra of epoxy (b) FTIR spectra of GNR/PANI epoxy composite.
Table 1
Assignment of functional group to various peaks of Fig. 3(b).
Peak number
Wavenumber (cm1)
Group
1
2
3
4
5
6
7
8
9
10
11
12
3358
3000, 2860
2182
1735
1608, 1506
1454
1371
1300
1089
1020
820
540
COOAH/OH
c CAH epoxy stretching
AN@C@NA
C@O stretch
C@C in ring
CAH bending
NAO symmetric stretch
CAN stretch aromatic amine
c CAO epoxy
CAN med
CH and @CH2 out of plane bending
Alkyl halide
Fig. 4. TGA trace PANI/GNR, Plain epoxy and epoxy PANI/GNR composite.
ples were ltered and washed with ethanol and vacuum dried
for 24 h at 80 C.
2.3. Synthesis of PANI functionalized GNR/epoxy solution blend
Fig. 1 shows the schematic for the synthesis of composite.
0.1 wt% of PANI/GNR loaded epoxy composite was prepared by
solution blend technique by separately dispersing PANI/GNR in
chloroform and then probe sonicating the mixture for 30 min with
Mechanical Probe Sonicator (13 mm Vibra Cell Processor VCX 750)
operating at 40% of the max power 750 W. Thereafter the solution
475
was added to the Epoxy LY 1564 and stirred for 10 min and the
solution was heated at approx 70 C to evaporate the chloroform.
Subsequently, XB 3486 hardener was added to the above solution
in the known ratio and stirred for 5 min followed by degassing
for 10 min. The solution was then poured in the molds for preparing the desired dog bone shape of 1.7 mm and 3.4 mm thickness.
The molds were made as per ASTM D 638 Type-I standard. The
sample took 24 h to cure after which post curing of the sample
was done for 8 h at 80 C.
Table 2
Comparison of the Tensile strength and Youngs modulus of
different samples.
Sample
Tensile strength
(MPa)
Youngs modulus
(GPa)
Epoxy
C1
C2
C3
63.72
59.63
56.20
44.18
3.089
2.609
2.363
2.136
2.4. Characterizations
The morphological details of the PANI/GNR samples were characterized using scanning electron microscope (SEM). Raman spectroscopy was performed using unpolarized Raman spectroscopic
technique. The spectra was recorded at wavelength k = 633 nm
using Horiba HR800 Raman spectrometer. The molecular structure
of the synthesized sample was obtained by Fourier transform infrared (FTIR) spectroscopy using Brucker Tensor 37 spectroscope. The
thermal decomposition behavior of the PANI/GNR composite as
well as epoxy blended PANI/GNR composite was studied using
thermogravimetric analysis (TGA) under a nitrogen atmosphere
from room temperature to 650 C operated at a heating rate of
20 C min1. The tensile test and the Youngs modulus of elasticity
were measured using the Servo Hydraulic Universal Testing
Machine (BISS India) with total cell 10 kN capacity. The EMI shielding effectiveness of the composite lms was measured using Rhode
& Schwarz ZVA-40 1040 MHz vector network analyser. The calibration was performed using OSL (Open-Short-Load) technique.
Electromagnetic waves were injected directly into the lm using
354B X-band wave guide of standard dimension of the window
0.900 0.400 . The frequency was scanned from 8.2 to 12.4 GHz. The
EMI shielding effectiveness was measured using Rohde & Schwarz
Vector Network analyser in the range of 8.212.4 GHz.
difference Fig. 2(a) and (b). There is very little contrast in case of
only epoxy lm (Fig. 2(a)) whereas the image becomes clear once
the ller is added (Fig. 2(b)). The small percentage of GNRPANI
in epoxy is completely changing the microstructure of the epoxy
as observed from these images. A good interaction between epoxy
and GNR/PANI is the key in getting good dispersion which can
be achieved by ultrasonic dispersion and controlled solvent
evaporation.
476
Fig. 7. (a) SE of GNR/PANI composite of 2.5 wt% and (b) 5 wt% in epoxy matrix of different thickness i.e. 1.7 mm and 3.4 mm.
477
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