Accepted Manuscript

Enhanced Thermomechanical and Electrical Properties of Multiwalled Carbon

Nanotube Paper Reinforced Epoxy Laminar Composites

Sushant Sharma, Bhanu Pratap Singh, Sampat Singh Chauhan, Jeevan Jyoti,
Abhishek Kr. Arya, S.R.Dhakate, Vipin Kumar, Tomohiro Yokozeki

PII: S1359-835X(17)30382-2
DOI: https://doi.org/10.1016/j.compositesa.2017.10.023
Reference: JCOMA 4812

To appear in: Composites: Part A

Received Date: 21 June 2017

Revised Date: 6 October 2017
Accepted Date: 22 October 2017

Please cite this article as: Sharma, S., Singh, B.P., Chauhan, S.S., Jyoti, J., Arya, A.K., S.R.Dhakate, Kumar, V.,
Yokozeki, T., Enhanced Thermomechanical and Electrical Properties of Multiwalled Carbon Nanotube Paper
Reinforced Epoxy Laminar Composites, Composites: Part A (2017), doi: https://doi.org/10.1016/j.compositesa.
2017.10.023

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 Enhanced Thermomechanical and Electrical Properties of Multiwalled
Carbon Nanotube Paper Reinforced Epoxy Laminar Composites
Sushant Sharma1, 2, Bhanu Pratap Singh1, 2*, Sampat Singh Chauhan3, Jeevan Jyoti1, 2, Abhishek
Kr. Arya1, S.R.Dhakate1, Vipin Kumar4, Tomohiro Yokozeki4
1
Advanced Carbon Products, CSIR-National Physical Laboratory,
Dr. K.S. Krishnan Marg, New Delhi-110012, India
2
Academy of Scientific & Innovative Research (AcSIR)
3
Centre for Polymer Science & Engineering, Indian Institute of Technology,

New Delhi-110016, India

4
Department of Aeronautics and Astronautics, The University of Tokyo, 7-3-1 Hongo, Bunkyo-
ku, Tokyo, 113-8656 Japan

Abstract
Thermomechanical and electrical properties of multiwalled carbon nanotubes (MWCNTs)
bucky paper reinforced epoxy laminar composites have been studied. Incorporation of bucky
paper in epoxy matrix led to improvement in thermomechanical properties but it reduced
through-plane electrical conductivity. Therefore, 0.05 wt.% of MWCNTs is incorporated as
secondary network in epoxy matrix to improve the electrical conductivity. The storage modulus
for a 0.05 wt.% dispersed MWCNTs in epoxy resin impregnated 20 plies of bucky paper based
composites (20Ply.05) was 4.84 GPa as compared to 2.24 GPa of pure epoxy. The glass
transition temperature of 20Ply.05 laminar composite reaches to 191.6°C as compared to pure
epoxy 168.5°C. The increment in electrical conductivity (792%) is reflected in improved
electromagnetic shielding effectiveness (SE) over a wide frequency range of X & Ku band. The
SE of more than ~ -50 dB for 20Ply.05 laminar composite in both the bands was obtained.

Keywords: Multiwalled carbon nanotubes (MWCNTs), Bucky paper, Dynamic mechanical

analysis, Storage modulus (E´), Glass transition temperature (Tg , EMI shielding.
1. Introduction

The electromagnetic interference (EMI) of radio frequency radiation has become a

serious concern in modern society due to the fast growth of electronic and communication
system in terms of the development of advanced technology and products. Increased
communication system along with sophisticated electronic equipment has increased the threat of
harmful radiations, which are used to exchange information. Electromagnetic radiation could
interfere electronic devices, which may lead to anomalous operation. Therefore, it has become
essential to shield these electromagnetic emissions not only to protect the electronic devices but
also to get rid of their harmful effect on living beings. The material with good EMI shielding
properties tends to be electrically conducting therefore in recent past many studies are
previously reported on metal based shielding material like metallic fillers, metallic coating,
metal oxides, and metallic fibers due to their excellent conductivity, permeability and shallow
skin depth [1-5]. However, heavy weights, prone to corrosion, processing difficulties are few
limitations in using metal-based EMI shields.

Today’s electronic evolution has led to the emergent need of light weight, corrosion
resistant, high strength and high machinability material for replacing heavy metallic based
shielding materials. The most prominent examples are aerospace, power generation and
automobile applications, where these kinds of materials are used as fuel efficient structures such
as tubular struts, engine covering, and circuit box casing, etc.[6-9].

Epoxy is a well-known thermosetting polymer, which is widely used in advanced

composite for many structural applications [10-13]. Due to its insulating properties, it cannot be
used directly for EMI shielding applications. The incorporation of conductive filler material,
such as carbon nanotubes (CNTs), graphene, carbon black into the matrix, give high-
performance shielding materials by forming a conductive network in the matrix [14-19].
Nowadays, CNTs and their composites with different polymers are often used as a shielding
material due to their exceptional inherited properties [20-24]. However, if this nanoscale filler is
to be used as reinforcement to enhance the mechanical and electrical properties of the composite
material, uniform dispersion and excellent interfacial adhesion are required [25, 26]. By
increasing reinforcement, the intra CNT interaction increases due to its inherited structure and
high aspect ratio [27]. CNTs come out from its uniformly dispersed state and start
agglomerating to form a clustered state, which reduces the critical loading value (also called
percolation threshold) and affects the overall electrical and mechanical performance of the
composites [28-30]. For full utilization of the inherited mechanical and physical properties of
CNTs, it is essential to assemble them into a macroscopic structure. Therefore, the free standing
films of CNTs (Bucky paper) are reinforced in the polymer composite by few researchers.
Bucky paper is the randomly distributed network of CNTs, in which CNTs are interconnected
by Van der Waals forces. It is made up of CNTs, incorporation of bucky paper helps in
transferring the superior mechanical properties of the CNTs in bulk composite without any
dispersion problem.

Although lot of studies are reported on CNT/polymer composites for realising them as
EMI shielding materials, only few reports are available on electromagnetic shielding properties
of bucky paper reinforced composite materials. Most recently, Pourzahedi et al. [6] replaced the
aluminium by CNT/polymer composite for shielding application in spacecraft. They developed
CNT M55J/CE (combination of CNT sheet, carbon fiber, polymer, cyanate ester (CE), etc.)
laminate, which is used for tubular struts and engine covering components of Juno spacecraft.
The study reveals that the use of CNT composite reduces the mass by 50% without hampering
the (SE). This in turn increases the fuel efficiency of the spacecraft. Rawal et al. [31] prepared
three different types of composite samples by using spray-depositing, co-cured CNT membrane
and CNT sheet/CE prepreg. The electrical resistivities of these samples were determined before
making the actual panel. It was observed that the minimum surface resistance offered by carbon
nano-onion (CNO)/ multiwalled carbon nanotubes (MWCNTs) sheet and graphene nano-
platelets (GnP)/ MWCNTs sheet was 2.5 Ohm/Sq and 1.5-2 Ohm/Sq, respectively. The SE was
measured over 200 MHz to 18GHz and it was observed that CNT M55J/CE panel exhibited SE
equivalent to the typical spacecraft panel with aluminium foil-based M55J/CE composite or
solid aluminium panel. CNT sheet was thin having the low density over aluminium, therefore it
provides >50% mass saving. Park et al. [32] took bucky paper of different concentration of
single walled and multi walled carbon nanotube and studied the SE of a single individual layer
of bucky paper in the frequency range of 2-18 GHz. The SE of 20-60 dB for different bucky
papers was observed. The effect of stacking was also examined by making the stacking of two
and three layers of SWCNTs bucky paper. The laminar composite of mixed CNT bucky
paper/polyethylene and long CNT bucky paper/ polyethylene were fabricated, and the effect of
incorporating MWCNTs in epoxy matrix was also analysed. The SE of long CNT bucky paper
composite is higher than any other bucky paper and doping also improved the effectiveness
tremendously. Apart from these structural EMI shielding materials, several researchers have
already studied the EMI shielding properties of bucky paper and their composite including our
group [16, 33, 34]. In one of our previous studies, high loading CNT epoxy composites were
prepared in which at first CNT dispersed epoxy was filtered from the filtration unit followed by
compression moulding of filtered CNT epoxy prepreg. These stacked prepreg were cured. But,
there was a difficulty to control the amount of CNTs in polymer. The dynamic mechanical
properties of these composites have also not been studied in previous work [11].

To predict the material behaviour in the actual application, the relationship between
molecular interactions and processing conditions must be examined. Dynamic mechanical
analysis (DMA) helps in predicting the material behaviour in the composite and hence the
product properties as a function of temperature, frequency, and load. The properties of the
polymer composite system like its glass transition temperature (Tg), storage modulus (E'), loss
modulus (E″), damping behaviour (Tanδ), segmental relaxation, etc. can be determined. Wang
et al. [35] successfully increased the loading of SWCNTs in the form of bucky paper and
correlate the increased dynamic mechanical properties with increased wt. %. Bucky paper
reinforced composite contain SWCNTs (up to 39 wt. %) in three layers. Gou et al. [36]
increased the load transfer capability by increasing the SWCNTs loading (up to 31%) in the
form of bucky paper. Xiong et al. [37] prepared the nanocomposites by using high-performance
poly (phthalazinone ether sulfone ketone) (PPESK) as matrix and MWCNT bucky paper
(MWCNT-BP) as reinforcement by hot pressing and studied the static and dynamic behaviour
of the composite. Wan Dalina et al. [38] studied the properties of fiberglass and bucky paper
hybrid laminar composite and found that both modulus and strength were increased by 70 %
and 30% respectively, after reinforcing with bucky paper.

It is observed that, many past studies have utilised the bucky paper as conductive filler
for making a high performance versatile composite and due to their high flexibility and limited
strength, it can be used in devices like sensors, batteries, and capacitors, etc. which have a light
duty cycle. For structural application, it is imperative to have both excellent electrical and
mechanical properties. Researchers usually use conductive filler incorporated resin and carbon
fiber to provide an electrically conductive composite for structural application. But still, they
are not able to achieve desirable electrical conductivity which can reduce its shielding
performance. Hence, in the present study, we have fabricated the laminar composite by
reinforcing different layers of bucky papers and studied the electrical and EMI shielding
behaviour. For further improving the EMI SE by interlayer absorption, a secondary network of
CNTs is provided by incorporating CNTs into the epoxy resign. Finally, the mechanism of
outstanding EMI shielding properties is elucidated by using high performance one-dimensional
conductive filler paper.

2. Experimental Section

2.1 Material

In the present study, Epoxy Araldite LY 556 Diglycidyl ether of Bisphenol- A having
specific gravity 1.15-1.17, viscosity at 25ºC 9000-12000 mPa-s and epoxy content 5.25-5.45
eq/Kg when stored at 2-40ºC was used as the thermosetting polymer. The hardener was an
aromatic diamine, Aradur HY 5200 having specific gravity 1-1.1 and viscosity 140-200mPa-s.
The MWCNTs were synthesised by chemical vapour deposition technique using toluene as a
carbon precursor and ferrocene as a catalyst injected into a quartz tube reactor in the ratio of 8:1
by wt. The reaction time was optimised for 4 h. Further details about MWCNTs synthesis are
given elsewhere [23, 39]. In order to prepare bucky paper, suspension of MWCNTs, and alkali
soluble emulsifier (ASE) of pH 3.4 was used [40]. The role of surfactant was to improve the
dispersion of MWCNTs in the suspension.

2.2 Preparation of bucky papers

As synthesised MWCNTs were air oxidised at 375°C for 4 hrs in a quartz tube. The
air oxidised MWCNTs were refluxed in surfactant medium (1.3 ml ASE surfactant per gram of
MWCNTs) for 4 hrs at 80°C. CNTs were filtered after cooling and dried for 8 h in a vacuum
oven to remove the moisture completely. Thereafter oxidised refluxed MWCNTs were
dispersed in double distilled water at 0.15 wt. % concentrations, with 1 wt. % ASE surfactant
and homogenised at 40000 rpm by using MICRA laboratory homogenizer to form a uniform
suspension of the MWCNTs. Then the suspension was ultrasonicated for 2 h to further break the
MWCNTs bundles. The 0.15 mm thick, 35 cm X 35 cm bucky paper was prepared by vacuum
filtration of a suspension of MWCNTs through a nylon mesh. The bucky paper was then dried
in the atmosphere as shown in Figure 1. Further, this large square shaped bucky paper was
bifurcated into 10 cm X 10 cm square shaped pieces (plies) to prepare laminar composites.
 a b
)

Figure 1 (a) Filtration unit along with nylon mesh (b) flexible 35 cm X 35 cm bucky paper after
drying

2.3 Preparation of bucky paper reinforced laminar composites

To overcome the problem of entrapment of voids and proper impregnation, composites

were prepared by the vacuum-assisted method (vacuum impregnation). From this technique, the
epoxy resin replaced the air present in the pores of bucky paper and simultaneously removed the
air present in between the layers. The desired numbers of plies of bucky paper were coated with
the mixture of epoxy: hardener in 4:1 ratio by wt. on both sides. These laminated bucky papers
were stacked one by one and put into a desiccator for vacuum impregnation. To avoid unwanted
adhesion, a releasing paper was used before stacking the plies together. A pressure measuring
needle gauge and the mini vacuum pump was connected to the desiccators and 30 mm Hg
vacuum was maintained for 24 h which turned epoxy resin to be gel like. After this the stacking
was hot pressed at 2000 kg/cm2 and simultaneously cured at 120°C for 2 h and at 160°C for 4 h
as shown in Figure 2.
 Homogenizer Ultrasonication Vacuum infiltration
for 2 h
MWCNTs

Aqueous suspension
of MWCNTs
Rotary vacuum pump
Vacuum impregnation Epoxy coating
Bucky Bucky paper of 35cm X 35cm
paper Glass rod
Bucky paper coated
with epoxy stacking

Mini rotary Rolling and pressing

Desiccator vacuum pump Bifurcation 9X100cm2
Bucky paper reinforced
Hydraulic pressing laminar composite

Bucky paper reinforced

epoxy stacking

FESEM micrograph of laminar

composite at low magnification
3 mm spacer

Figure 2 Schematic of process flow diagram for bucky paper reinforced epoxy laminar
composite preparation method

2.4 Characterizations

The structural and morphological detail of oxidised refluxed bucky paper was studied by
field emission scanning electron microscopy (FESEM, ZEISS Supra 40VP) and high resolution
transmission electron microscopy (HRTEM, Technai G20-stwin operated at 300kV with 0.2 nm
point resolution and 0.14 nm lattice resolution). X-ray diffraction of bucky paper was carried
out by Rigaku X-ray diffractometer using a CuKα source (λ=1.5418Å) at the scanning rate of 5°
per min. The data is well compared with the joint committee on powder diffraction standards
(JCPDS). Raman analysis of bucky paper was done by Renishaw in-Via Raman Spectrometer,
UK with a monochromatic excitation source of 514 nm. Fractured surface of laminar composite
is studied by SEM (model EVO-MA10 ZEISS).
 Dynamic mechanical properties of composites (size 30 mm X 6 mm X 3 mm) were
analysed by using Perkin Elmer DMA 8000 instrument in dual cantilever mode. The
temperature scanned up to 250ºC at a constant frequency of 1 Hz with a strain of 0.05 mm. The
temperature scan rate was 2ºC/min. The through plane electrical conductivity was measured by
using 3522-50 LCR HiTESTER machine. EMI shielding effectiveness was analysed by using
Agilent N5224A Vector Network Analyser in the X-band (8.2-12.4 GHz) range as well as in Ku
band (12.4-18 GHz) range. Two different sets of rectangular shaped samples of sizes (22.86 mm
X 10.14 mm X 3 mm) and (15.8 mm X 7.9 mm X 3 mm) were connected between two
waveguide flanges of the vector network analyser.

3. Results and discussion

3.1 Morphological analysis of bucky paper

A FESEM image of oxidised refluxed MWCNT bucky paper is given in Figure 3(a). The
randomly distributed MWCNTs of several micrometres length form a porous network. These
randomly distributed CNTs provide the excellent pathway for charge carrier transportation
resulting into high in plane electrical conductivity. Figure 3(b) represents the HRTEM image of
MWCNTs. It gives the inside features which represents the presence of iron catalyst trapped
inside the tube during synthesis and also provides their diameter distribution.

XRD analysis of bucky paper was carried out to determine the crystalline nature of MWCNTs.
Figure 3(c) represents the XRD spectrum of oxidised refluxed bucky paper. The first graphitic
peak of the spectrum at the 2θ angle of 26.18 degree corresponds to (002) crystallographic
plane. The interlayer spacing acquired from Bragg’s law is 3.41Å which is close to graphite.
The other peak (100) plane is for iron nanoparticles indicated in HRTEM image. Figure 3(d)
shows the Raman spectrum of bucky paper. Three most prominent peaks are obtained from this
spectra, i.e., D-band (1343cm-1), G-band (1580cm-1) and Gʹ-band (2700cm-1). The ratio of the
intensity of G-band and D-band corresponds to the quality of MWCNTs. The IG/ID from the
spectrum is 3.5 which represents the ordered graphitic structure.
 a b

1µm 100nm

c d

Figure 3 (a) Field emission SEM micrograph of oxidized refluxed bucky paper, (b) HRTEM
image of MWCNTs, (c) XRD pattern with scattering range of 10-80° and (d) Raman spectrum
of bucky paper

3.2 Dynamic mechanical analysis

The viscoelastic behaviour of bucky paper reinforced epoxy laminar composite has been studied
through DMA. In DMA, linear variable differential transformer (LVDT) controlled sinusoidal
force is applied, and the response of the input is measured as shown in Figure 4. DMA measures
the characteristic properties of the material like storage modulus, loss modulus, tanδ which are
helpful in predicting the behaviour of the material with varying forces and temperature. In this
study, oxidised refluxed CNT bucky paper impregnated epoxy laminar composites are used, and
the behaviour after incorporating CNTs in the resin is studied with the use of DMA.
 Figure 4 Half section top view and front view of DMA

Storage modulus (E′) is proportional to the energy stored per cycle during elastic
deformation. Figure 5(a) shows the variation in the E′ as a function of the temperature for
various laminar composites. The storage modulus of pure epoxy is 2.24 GPa at a temperature of
35°C. The change in E′ represents the adhesion of the filler and polymer matrix which
corresponds to mechanical properties of the composite [41]. The storage moduli of 16Ply and
20Ply composites are 2.70 GPa, and 4.01 GPa, respectively and showed an overall improvement
of 20% and 79% respectively. When 0.05 wt. % CNTs are dispersed in the epoxy the storage
modulus further increases to 4.84 GPa. It is observed from the result that the storage modulus of
composite increases with increasing the loading of CNTs. This significant improvement in
storage modulus is attributed to stiffening effect of CNTs due to their excellent mechanical
properties. Superior matrix-tube interfacial interaction due to π-π conjugate bonding between
epoxy and MWCNTs can be regarded as another reason for this significant enhancement[42].

Loss modulus (E″) is a viscous response of the material that represents the energy
dissipation tendency of the material, i.e., internal friction [43-45]. Therefore, it is also termed as
viscous modulus. Figure 5(b) and (c) represents the loss modulus and tanδ curves of laminar
composites. The loss modulus of laminar composites is much higher than that of pure epoxy in
every case. In case of 16Ply, bucky papers are coated with epoxy which is not offering much
resistance to polymer chain motion, therefore the peak shifted towards left at lower temperature
compared to pure epoxy.

a b

Figure 5 Dynamic mechanical properties of laminar composite (a) storage modulus with
temperature, (b) loss modulus with temperature and (c) Tanδ with temperature and inset shows
Tanδ of pure epoxy showing its T g

But when the numbers of layers are increased in the same volume (20Ply), CNTs start offering
resistance and the peak shifted towards higher temperature. It is clearly observed that in case of
20Ply.05 secondary network structure is made by the nanotube dispersed in addition to the
primary cross-linked structure of bucky paper. Dispersed CNTs are offering resistance to the
mobility of epoxy chain at elevated temperature therefore the peak value of 20Ply.05 composite
is reduced considerably.

3.3 Electrical conductivity and electromagnetic interference shielding measurement

Figure 6(a) shows the effect of bucky paper stacking on the room temperature electrical
conductivity of the laminar composite. To diminish the contact resistance with measuring
electrodes, sample were coated with Dotite D-550 silver paste on both side is shown in Figure
6(b), which is used for analysis of through plane electrical conductivity as shown inset Figure
6(b). As the number of epoxy coated plies increases the conductivity decreases due to the
interfacial resistance offered by electrically insulating epoxy. A small fraction of MWCNTs
(0.05 wt. %) is dispersed to overcome this problem. On incorporation of 0.05 wt. % of
MWCNTs electrical conductivity shoots up to the one order higher as compared to composites
without dispersed CNTs. As shown in the inset of Figure 6(a) the conductivity of the 20Ply
composite is 0.013 Scm-1 which shoots to 0.116 Scm-1 (792% improvement). This is due to the
formation of a secondary network within the epoxy as observed in the FESEM images. Figure
6(c-e) are FESEM images at different magnifications of the fractured surface of the 20Ply.05
laminar composite at different magnifications in which layer by layer composition of oxidised
refluxed bucky paper and epoxy is visible. The dark portions separated by bright thin lines are
bucky paper and cured epoxy resin as shown in Figure 6(c, d). From these micrographs, it is
observed that there is a brittle fracture in the composite. Figure 6(e) showed the magnified
micrograph of CNTs in one layer of bucky paper and it is observed that vacuum impregnation
played an important role in impregnating the bucky paper by epoxy resin. The layers are getting
entangled with each other after the application of load. In Figure 6(f), the secondary network of
CNTs can be discernable at higher magnification (5000 X), which provides the conductive path.

This secondary network of nanotubes provides extra path for the mobility of charge
carrier which resulted in enhanced electrical conductivity. Formation of the conductive network
due to both bucky paper (primary network) and CNTs (secondary network) is responsible for
trapping electromagnetic radiations and hence good EMI shielding properties are expected.
 a
bb
Sample name

c d

e f

Figure 6 (a) log of electrical conductivity of laminar composite, (b) image of laminar composite for
conductivity measurement and SEM micrographs of laminar composite at (c) 150X showing laminar
behaviour, (d) 2K X, (e) 10K X showing sandwiched bucky paper and (f) 5K X magnification
showing 0.05wt.% dispersed CNTs in epoxy.
Electromagnetic interference (EMI) shielding is the process of protecting electronics against
unwanted electromagnetic radiations by surrounding them with some conductive and magnetic
materials. It is measured in terms of SE, which is the ratio of the transmitted power density to
the incident power density. The EMI protection offered by any shield is the results of reflection
from the material surface (SER), the absorption of electromagnetic radiations (SEA), and the
multiple internal reflections of electromagnetic radiations (SEM) [46-48].

(1)

Where Pt and Pi are transmitted and incident electromagnetic radiations, respectively. When the
absorption component is more than -10 dB, losses due to multiple reflections can be neglected.
Thus the SE can be expressed as [48, 49]

(2)

and can be expressed in terms of transmittance and reflectance as [46, 48]

(3)

(4)

In the present study, we measured the wide frequency range EMI shielding effectiveness of
laminar composites. Figure 8(a, b), (c, d) and (e, f) represents the variation of SE due to
reflection, absorption and total SE in X band and Ku band respectively. There are several
studies on EMI shielding based on dispersed CNTs in polymers and making the plain-structured
composite out of it. Moreover in most of these studies EMI SE of composite increases with
increased conductivity [23, 50, 51].

The total SE of 16Ply composite is -20.7 dB (10.3GHz) and -33.5 dB (15.2GHz) in mid
frequency range of X band and Ku band respectively. After increasing the CNTs amount in the
form of bucky paper plies, the SE increases. The SE of 20Ply composite is -36.8 dB and -37.5
dB in mid frequency range of X and Ku band respectively. Effect of dispersing only 0.05 wt. %
CNTs in epoxy is noticeable in 20Ply.05 laminar composite. The maximum SE of 20Ply.05
composite reached to -54.2 dB and -52.7 dB (>99.999% attenuation) at the same mid
frequencies of X and Ku bands respectively. Dispersed CNTs in the epoxy endorse a secondary
network entangled with primary bucky paper. Therefore charge carrier mobility now takes place
by the combination of tunnelling throughout the epoxy polymer and hopping along MWCNTs
of the hybrid interconnected network as described by schematic (Figure 7). For further
investigating the shielding mechanism of the laminar composite, SE T resolved into an
absorption loss (SEA) and reflection loss (SER) as shown in Figure 8(a-d). SEA shows an
increased pattern by increasing the CNTs. It is observed that SE R of 20Ply.05 composite is -5.7
dB and -8.90 dB, the SEA component is -48.5 dB and -43.7 dB in the same frequency range as
above in X and Ku band respectively. It is apparent that SE in the layered structure is higher
than the plain structure in the same CNT loading as the individual bucky paper effectively stops
radiation to pass through, in comparison to the dispersed CNT in the matrix. This behaviour of
composites can also be explained in terms of skin effect.

Improved charge carrier

transportation by secondary
phase CNTs network in epoxy

Bucky Paper

Epoxy+.05wt.% CNT

Bucky Paper

Laminar composite of Confined CNT

bucky paper and epoxy conductive network

Figure 7 Schematic of role played by secondary CNT network for improving EMI shielding in
bucky paper reinforced laminar composite.
 a b

c d

e f

Figure 8 Electromagnetic interference SE and their components in a larger frequency range of

X and Ku band, (a) SEA in X band, (b) SEA in Ku band, (c) SER in X band, (d) SER in Ku band,
(e) SET (T=R+A) in X band and (f) SET in Ku band.

Skin effect is the property of a conducting material by virtue of which it allows the high
frequency EM waves to penetrate few mm distance to its incident surface [52, 53]. If the
incident EM waves possess high frequency, the EM waves are restricted to a very thin layer
near the conductor surface. The depth at which the intensity of incident wave drops to1/ of its
original value is termed as skin depth (δ) which can be represented as

(11)

a b

Figure 9 Deviation of skin depth of laminar composite, (a) with frequency range of X band (b)
with frequency range of Ku band and (c) with bucky paper plies

Where f is the frequency, µ is the magnetic permeability, σ is the electrical conductivity and t is
the thickness of the composite material. Figure 9(a, b) relates the skin depth with varied
frequency, and Figure 9(c) indicates the skin depth at different compositions of bucky paper
plies. It is observed from the Figure 9(a-c) that the skin depth decreases with increased
frequency and MWCNTs. The decrease in value of skin depth suggests that by the incorporation
of bucky paper and nanotubes in the epoxy matrix comparatively thin sample is required to
block the desired level of electromagnetic radiations. Skin depth is an absorption loss based
quantity, therefore, it shows reduced behaviour at a higher frequency. In the case of 20Ply.05,
the secondary network of dispersed CNTs increases the absorption loss in a wide frequency
range which helps in increasing the shielding. An absorption dominant value of SE T reached to
more than -50 dB which is higher than suggested range of -20 to -30 dB for commercial
application [52].

In short, CNTs dispersed resin reinforced bucky paper composites played a very important role
in improving electrical conductivity and hence electromagnetic shielding properties over the
wide frequency range. In addition to this, the excellent dynamic mechanical properties have
been achieved which enhances the suitability of these composites in demanding applications
like automobile and aerospace.

4. Conclusion

Large size (35cm Χ 35cm) bucky papers have been prepared by vacuum filtration and these
have been used as reinforment for making laminar composite. A significant enhancement in
dynamic mechanical properties (storage modulus, tanδ) has been achieved. An overall
improvement of ~ 116% in storage modulus and 23.1°C in tanδ over pure epoxy were achieved.
But this laminar fashion of reinforced bucky paper reduces the through plane electrical
conductivity with addition of number of bucky paper plies. The interfacial resistance offered by
insulating epoxy was the reason of this reduced electrical conductivity. Therefore, a secondary
network of MWCNTs was provided in epoxy by incorporating 0.05 wt. % MWCNTs. This
secondary network of MWCNTs when communicated with MWCNT bucky paper, offers the
tremendous through plane electrical conductivity. The electrical conductivity of 20ply.05 was
improved by 792% over 20ply laminar composite.

Further, the wide frequency range electromagnetic interference shielding analysis has been
carried out. In addition to improved electrical conductivity, the absorption dependent SE
reached to -54.2 dB and -52.7 dB (>99.999% attenuation) at the mid frequencies of X-band
(10.3GHz) and Ku band (15.2GHz) respectively. Due to its excellent thermomechanical and
electrical properties, these composites can be used in EMI shielding for automobile, aerospace,
electric circuit board industries, etc.
5. Acknowledgment

We would like to thank Mr. M. Saravanan for FESEM measurement and Mr. Jay Tawale for
SEM measurement.

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Graphical abstract

Improved charge carrier

transportation by secondary
phase CNTs network in epoxy

Bucky Paper

Epoxy+.05wt.% CNT

Bucky Paper

Laminar composite of Confined CNT

bucky paper and epoxy conductive network