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Materials Today: Proceedings 5 (2018) 15348–15353 www.materialstoday.com/proceedings

ISCAS 2017

To study the effect of MWCNT incorporated into PVDF-Graphite

composites for EMI shielding applications
Krishna Kamal Halder1, Monika Tomar2, V. K. Sachdev1, Vinay Gupta1*
1
Department of Physics and Astrophysics, University of Delhi, Delhi, India
2
Department of Physics, Miranda House, University of Delhi, Delhi, India

Abstract

Present work reports the fabrication of EMI shielding composites consisting of multi-walled carbon nanotubes (MWNTs) and
graphite uniformly dispersed in an insulating polymer matrix i.e. polyvinylidene fluoride (PVDF). The EMI shielding is
measured in the X-band frequency range (8–12 GHz) for all the composites. Absorption and reflection radiations are seen to be
increasing with increasing the graphite and MWCNT level in the composite and a high EMI shielding effectiveness (SE) value of
14.64 dB has been achieved. The results are promising for the development of a novel, low cost, light weight, and flexible EMI
shielding material.

© 2018 Elsevier Ltd. All rights reserved.

Selection and Peer-review under responsibility of 10th NATIONAL CONFERENCE ON SOLID STATE CHEMISTRY AND ALLIED
AREAS (ISCAS - 2017 ).

Keywords: Electromagnetic Interference Shielding, shielding efficiency, composite materials, skin depth, filler.

*Email address: drguptavinay@gmail.com

2214-7853 © 2018 Elsevier Ltd. All rights reserved.

Selection and Peer-review under responsibility of 10th NATIONAL CONFERENCE ON SOLID STATE CHEMISTRY AND
ALLIED AREAS (ISCAS - 2017).
 K.K.Halder et al. / Materials Today: Proceedings 5 (2018) 15348–15353 15349

1 Introduction

Most of the modern gadgets and equipment are associated with the electronic surveillance and various types of
wireless communication systems where radiofrequency (RF) waves are used for exchanging the information. This
creates EM pollution and health concerns due to RF exposure. A study on ill effect on health due to long term
exposure to RF radiation has been investigated in mobile telephone users and associated workers and they are found
to be suffering from cancer and neurological disorder [1]. It is also proved that long-term exposer of radiofrequency
electromagnetic radiation may affect the cardiovascular system [2]. EM radiation not only affects the human health
and living cells but also affect the appropriate functioning of a large variety of electrical and RF devices [3]. So, it is
important that these radiations are observed from the radiating instruments so that the human being and other
instruments could be protected from the ill effects in this regard, EMI shielding plays a crucial role and absorbs most
of these harmful EM radiations. Weatherproof, low cost and high link availability make x-band frequency a
popular band for numerous defence and commercial systems. Hence EMI shielding materials development for X
band are of great importance and are in high demand [4]. Incredible efforts have been made by the researchers for
making several kinds of shielding materials and a number of strategies have been adopted over the past three
decades to reduce EMI pollution [5]. Different type of materials are explored such as metals, carbon composites,
conducting polymer, polymer with conducting filler and magnetic materials for EMI shielding [5-8]. Among them
conducting polymer composites are becoming more popular because of their lightweight, flexible, corrosion
resistive, cost effective properties. A conductive polymer composite is prepared by adding electrically conducting
filler to an electrically insulating polymer matrix. Recently carbon-based composites viz., carbon nanotubes (CNTs),
graphite, carbon black, carbon fibers and graphene have become the most popular fillers due to their good electrical
properties [5, 9-14]. In this paper, efforts have been made to develop EMI shielding material with high shielding
performance. Composites of multi-walled carbon nanotubes (MWNTs) and graphite have been prepared within
polyvinylidene fluoride (PVDF). PVDF is used due to its unique properties, like, high-temperature sustainability,
highest chemical resistance, good adhesive nature, environment-friendly and a wide variety of applications [15].
Multi-walled carbon nanotubes (MWCNTs) offer significant performance over that of conventional fillers by
enhancing the electrical conductivity and strengthen the mechanical performances of the polymer composites.

2 Experimental

Dry powders of PVDF, graphite, and MWCNTs were mixed together for two hours using the mortar-pestle method.
The resulting mixture is heated at 165 oC for 15 minutes in the X-band waveguide shape dye and brought back to 90
o
C. A constant pressure of 75 Mpa is applied and finally cooled to room temperature. For each composition at least
two samples were prepared. For electrical measurements, the resistance of pellets is measured using Keithley 4200
SCS setup. For EMI shielding measurements, Agilent’s vector network analyzer (VNA): N5230C PNA-L 10 MHz-
40 GHz is used. VNA measures the complex transmission and reflection characteristics in terms of S (scattering)
parameters.

3 Results and discussion

The dc conductivity (σ) of the composites not only depend on the filler concentration but also on the polymer
properties, the type of network formation and uniform dispersion of filler within the composites. The conductivity
(σ) of composites for different wt.% of MWCNT and graphite is illustrated in Fig.1a & 1b. PVDF is an insulator
having σ ~ 10-14 S cm-1. On addition of 10 wt% of conducting graphite only its σ increases by ~4 orders indicating a
nearby percolation threshold. On addition of only 0.5% MWCNT, conductivity increases by ~7 order for 0.5%
MWCNT. Around this graphite (10%) and MWCNT (0.5%) content, an interconnecting chain of MWCNT and
conducting graphite particles is formed in the composite. Increasing the MWCNT and graphite concentration,
increases the number of chains and conducting paths, which develop a mesh-like structure within the composites.
These structures allow the electrons to hop or tunnel across the gaps or the thin layers of PVDF matrix between
them increasing the conductivity.
15350 K.K.Halder et al. / Materials Today: Proceedings 5 (2018) 15348–15353

0
10
-1
10
-2
10
-3
10

Conductivity (S/cm)
-4
10
-5
10
-6
10
Graph for 1% MWCNT
-7
10
-8
10 0 1.28319E-10
5 1.84701E-10
-9
10 10 0.03169
20 0.27824
-10
10
-11
10
0 5 10 15 20
Graphite wt.%

Fig. 1a Conductivity as a function of graphite wt.% for 1wt.% MWCNT

In fig.1a conductivity of the composite is seen to be increasing with the graphite wt.% up to 10 wt.% and saturates
thereafter with further increasing the graphite wt.% for a fixed MWCNT concentration of 1 wt.%. The percolation
limit of 10 wt.% of graphite is identified from these studies. Further, keeping the graphite wt.% to 10% the
conductivities are increasing with increasing MWCNT wt.% as shown in fig 1b. For SE calculations, S-parameters
are measured in the frequency range of 8.2-12.4 GHz.

0
10
-1
10
-2
10
-3
10
Conductivity (S/cm)

-4
10
-5
10
-6
10 Graph for 10%graphite
-7
10 0.1 2.7497E-9
-8 0.5 7.4581E-7
10
0.7 0.003
-9 1 0.03169
10
2 0.98123
-10
10

0.0 0.5 1.0 1.5 2.0

MWCNT wt.%

Fig. 1b Conductivity as a function of graphite wt.% for 1wt.% MWCNT

Fig.2a &2b illustrates the frequency dependency of SE over the X-band frequency range for PVDF composites with
different wt.% of graphite and MWCNT respectively. SE rises with increasing graphite as well as MWCNT contents
in composites. The composite shows maximum value of SE ~ 14.64 dB for 10 wt % of graphite with 2wt.% of
MWCNT at a frequency of 8.2 GHz.
 K.K.Halder et al. / Materials Today: Proceedings 5 (2018) 15348–15353 15351

14 20% graphite
13 10% graphite
12 5% graphite
0% graphite
11
10
9
SE (dB)

8
7
6
5
4
3
2
1
8 9 10 11 12
Frequency (GHz)

Fig. 2a EMI shielding as a function frequency varying wt.% of graphite and 1 wt.% of MWCNT

18
0% MWCNT
0.1% MWCNT
16
0.5% MWCNT
0.7% MWCNT
14 1.0% MWCNT
2.0% MWCNT
12
SE (dB)

10

4
8 9 10 11 12
Frequency (GHz)

Fig. 2b EMI shielding as a function frequency 10wt.% of graphite and varying wt.% of MWCNT

The graphite particles come nearer to each other with its increasing content in the composite at high pressure of
compression and a mesh-like structure is formed with the MWCNT. When more and more graphite and MWCNT
particles are dispersed uniformly in the PVDF matrix, a high value of σ is expected as observed and progressively
large values of SE is witnessed. The EM waves are likely to interact with the added graphite and MWCNT particles
in the PVDF matrix in higher concentration and these particles attenuate the EM radiations, resulting in an increase
in SE. The SE for all compositions shows a marginal decrease with frequency. Shielding have three mechanisms,
namely, absorption, reflection and multiple-reflection. If the sample thickness is greater than ‘δ’, SE due to multiple
reflection (SEM) can be neglected [16] . Fig. 3 shows the skin depth variation for the composites having 1wt.%
MWCNT and varying graphite concentration. It may be seen that the skin depth is decreasing with filler
15352 K.K.Halder et al. / Materials Today: Proceedings 5 (2018) 15348–15353

concentration and become almost constant after 10wt.% of graphite. It is important to note that the present case, all
the sample thickness are greater than skin depth so absorption and reflection are the only mechanism responsible for
shielding.

1.0

0.9 Graph for 1wt.% MWCNT

0.8
Skin depth (µm)

0.7

0.6

0.5

0.4

0.3

0.2
0 5 10 15 20
Graphite (wt.%)

Fig. 3 Skin depth as a function of different wt% of graphite for 1% MWCNT

26
24 2.0 Wt% MWCNT

22
20
Dielectric constant

18
1.0 Wt% MWCNT
16
14
0.7 Wt% MWCNT
12 0.5 Wt% MWCNT

10 0.1 Wt% MWCNT

8
6 00 Wt% MWCNT

4
8 9 10 11 12
Frequency (GHz)

Fig. 4 Dielectric constant as a function of frequency for 10wt.% graphite and different wt% of MWCNT

Fig.4 represents the variation of dielectric constant with frequency for fixed graphite concentration of 10 wt.% and
different MWCNT wt.%. Dielectric constant rises with filler contration and remains constant with frequency in the x
band. On tne basis of percolation theory, near percolation threshold abrupt change in dielectric constant is observed
[17]. In fig.4 it can be observe that dielectric constant rises abruptly at 10% graphite and 2% MWCNT, which shows
the percolation threshold for the composite.
 K.K.Halder et al. / Materials Today: Proceedings 5 (2018) 15348–15353 15353

4 Conclusion

In conclusion, the EMI shielding characteristic of PVDF, graphite and MWCNT composite are studied. The
composite possesses a low percolation threshold of 10wt.% of graphite and 2wt.% of MWCNT, which can be
accredited to the high skinniness ratio of the PVDF. The conductivity and dielectric constant increase fast when the
content of fillers is at the percolation threshold i.e., 10 wt.% graphite and 2 wt.% MWCNT. The results indicate the
application of the prepared composite material for EMI shielding.

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