Journal Pre-Proofs

Journal Pre-proofs
Fabrication of Heterostructure Composites of Ni-Zn-Cu-Ferrite-C3N4-Poly(vi‐

nylidene fluoride) Films for the Enhancement of Electromagnetic Interference
Shielding Effectiveness
Tanmoy Chakraborty, Shivam Sharma, Tanumoy Debnath, Abhik Sinha

Mahapatra, Abhyavartin Selvam, Sandip Chakrabarti, Soumyaditya Sutradhar
PII: S1385-8947(20)33805-5
DOI: https://doi.org/10.1016/j.cej.2020.127683
Reference: CEJ 127683
To appear in: Chemical Engineering Journal
Received Date: 4 July 2020

Revised Date: 21 October 2020
Accepted Date: 5 November 2020
Please cite this article as: T. Chakraborty, S. Sharma, T. Debnath, A. Sinha Mahapatra, A. Selvam, S.
Chakrabarti, S. Sutradhar, Fabrication of Heterostructure Composites of Ni-Zn-Cu-Ferrite-C3N4-Poly(vinylidene
fluoride) Films for the Enhancement of Electromagnetic Interference Shielding Effectiveness, Chemical
Engineering Journal (2020), doi: https://doi.org/10.1016/j.cej.2020.127683
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Fabrication of Heterostructure Composites of Ni-Zn-Cu-Ferrite-C3N4-Poly(vinylidene
fluoride) Films for the Enhancement of Electromagnetic Interference Shielding
Effectiveness
Tanmoy Chakraborty1, Shivam Sharma1, Tanumoy Debnath1, Abhik Sinha Mahapatra2,
Abhyavartin Selvam 3, Sandip Chakrabarti3, Soumyaditya Sutradhar1*

1
Department of Physics, Amity University Kolkata, Kolkata-700135, India
2
Department of Physics, JIS University, Kolkata-700109, India
3
Amity Institute of Nanotechnology, Amity University Uttar Pradesh, U.P.-201303, India
In this report the emphasis has been given on the influence of carbon nitride (C3N4)
semiconducting fillers for the enhancement of the electromagnetic interference shielding
effectiveness. This is the first ever report where the inexpensive composite nanomaterials of Ni-
Zn-Cu-Ferrite-C3N4-Poly(vinylidene fluoride) are fabricated by very simple solution casting
method. Structural and chemical studies have confirmed the presence of all the required phase of
the component materials in the heterostructure composite films. The magnetic NZCF
nanoparticles are responsible for the generation of the high magnetic loss in terms of domain
wall resonance. Also, C3N4 semiconducting fillers all around the NZCF nanoparticles and the
interactions between these binary nanofillers and the β-phase reach PVDF matrix are responsible
for the generation of polarization loss, conduction loss and eddy current loss by their interactions
with the electromagnetic (EM) wave of GHz frequency range. The presence of these binary
nanofillers (Ni-Zn-Cu-Ferrite-C3N4) inside the matrix of PVDF are responsible for the
improvement of the shielding effectiveness due to absorption and shielding effectiveness due to
reflection. High value of total shielding effectiveness of -71.5 dB and -88 dB has been observed
1
corresponding to the X-band and Ku-band for these NZCF-C3N4-PVDF composite films. Such
high value of attenuation of >99.999999% and the corresponding wide bandwidth of NZCF-
C3N4-PVDF composite films offers a completely new insights for the fabrication of microwave
absorber to combat against electromagnetic pollution.
KEYWORDS: Ferrite nanoparticles, C3N4, PVDF film, electroactive property,
Maxwell-Wagner-Sillers interfacial polarization, microwave absorption.
*Corresponding author’s e-mail: sds.phy1@gmail.com (Dr. Soumyaditya Sutradhar).
1. Introduction
In recent time, the significant technological improvement on radio/microwave frequency
have attracted the interest of researchers as it is useful for many important applications in the
field of defence sectors, security sectors, medical sectors, communication sectors and many more
[1-8]. The essential and high demand of radio/microwave devices in our everyday life has
manifested a completely new area of concern, called electromagnetic (EM) pollution, related to
the various issues of humans, animals and plant health on our planet. As the most effected
beneficiary of these RF/microwave devices, the human race, animals and plants are also facing
some serious problems due to the excessive exposure of this electromagnetic pollution such as it
causes eye problem, affect different parts of brain, creates many problems to pregnancy [9-11]. It
also degrades the nutrients quality of food products. The uncontrolled microwave radiation can
also affect plants by producing abnormal chromosomal activity, DNA destruction, decrease of
growth, malfunctioning of seed germination and many others [12-14]. Now, the time has come
when we need to look after the darkness of the excessive exposure of the radio
frequency/microwave radiations on us behind the luster of various electromagnetic devices used
to bring the ultimate comfort to us by reducing the burdens of human at work place and at our
2
living area. In order to reduce the electromagnetic pollution from our environment a material
with sufficiently high value of electromagnetic interference (EMI) shielding effectiveness (SE) is
inevitable. Now, the shielding effectiveness in terms of both shielding effectiveness due to
reflection (SER) and shielding effectiveness due to absorption (SEA) of electromagnetic radiation
in the RF/microwave region would be sufficiently high for a material that has sufficiently high
magnetic (permeability) loss or dielectric (permittivity) loss or the simultaneous presence of both
the loss factors [15-18]. In this direction, very recently our research group has published few
articles on magnetic nanofillers-PVDF heterostructure composite films where both the magnetic
loss in terms of domain wall resonance, natural/exchange resonance and the dielectric loss in
terms of polarization loss have been observed [19-22]. In those articles the various forms of
magnetic loss factors have been appeared in the composite film samples due to the presence of
cubic ferrites such as Ni-Zn-Cu-ferrite and Mn-Zn-ferrite and the hexagonal ferrites such as M-
type barium hexaferrite and strontium hexaferrite nanoparticles [23-26]. Also, the various forms
of dielectric loss/polarization loss factors have been appeared in the composite film samples due
the presence of polar -phase of modified PVDF matrix in the composite structure. Thus, the
enhancement of the magnetic responses of the magnetic nanofillers and the enhancement of the
dielectric responses of polar -phase improved PVDF matrix can attribute more SE just by
producing more interaction with the magnetic field vectors and electric field vectors present in
the incident EM radiation. Now, the improved SE of the composite films is sufficient enough to
combat against the EM pollution in the RF/microwave region. So far, the discussion has made it
clear to us that the improvement of the total magnetic loss contribution and the improvement of
the total dielectric loss contribution can enhance the SE of the composite films very significantly.
Keeping this in mind in the present report we have tried to improve the SE of the composite
3
films by the improvement of the magnetic loss contribution and the dielectric loss contribution of
the composite films. In this report we have incorporated the semiconducting fillers of C3N4 in the
matrix of PVDF along with the magnetic nanofillers of Ni-Zn-Cu-ferrite. It was our expectation
that if the SE of a composite material depends on the magnetic loss and dielectric loss of the
material then any possible enhancement of any one of these two loss factors or the possible
enhancement of both of them can enhance the SE of the composite films successfully with large
bandwidth.
The magnetic nanofillers such as Ni-Zn-Cu-ferrite with its sufficiently high magnetic
moment can be an interesting material for EM shielding effectiveness due to its high
permeability and moderately permittivity, but the sufficiently high Snoek’s limit of this magnetic
material restricts their use as an efficient EM shielder in the RF/microwave frequency region
[27]. The semiconducting fillers of C3N4 of band gap energy ~ 2.7 eV in association with the
magnetic nanoparticles such as Ni-Zn-Cu-ferrite can improve the EM shielding effectiveness of
this NZCF-C3N4 composite nanomaterials just by allowing the flow of current loops inside the
composite structures at RT, called eddy current, since semiconducting C3N4 filler can modulate
its charge conduction property depending on temperature and doping [28]. This is to be
mentioned here that the fabrication of a composite material with good shielding effectiveness in
terms of reflection (SER), absorption (SEA) and total shielding effectiveness (SET), a good
dielectric and magnetic response is very crucial, especially the complex relative permittivity (ε*)
and complex relative permeability (μ*) play the most significant role. Here in this present study
C3N4 has been chosen due to its large aspect ratio, flexibility and its ability to modulate its
charge conduction property depending on temperature and doping. Also, C3N4 here acts as a
charge source as a result of which there is more charge accumulation at the interfaces which
4
enhances the dielectric response, which is clearly evident in section 3.5 of the present article.
This eddy current inside the composite structures of NZCF-C3N4 may be appeared due to the
magnetic flux linked with the Ni-Zn-Cu-ferrite and it leads to the large absorption of EM
radiation in the RF/microwave frequency region. Among all the different fillers materials,
semiconducting filler material, C3N4 can be the most interesting filler material because of its
large aspect ratio and flexibility. Thus, below the percolation threshold these semiconducting
fillers of C3N4 along with the magnetic nano-fillers can improve the overall loss factors of this
composite structure with enhanced shielding effectiveness. Now, inside the polar PVDF matrix
the heterogeneous dispersion of conducting and magnetic nanoparticles leads to the synergistic
absorption of microwave radiation by these composite films.
2. Experimental Section
2.1. Materials
Ni-Zn-Cu-ferrite (NZCF) magnetic nanoparticles with the stoichiometry of
Ni0.50Zn0.30Cu0.20Fe2O4 were prepared by a simple sol-gel technique. For this sol-gel preparation
of NZCF magnetic nanoparticles the list of metal salts were nickel (II) acetate tetrahydrate
Ni(CH3COO)2.4H2O (Sigma Aldrich, 99%), zinc (II) acetate dihydrate Zn(CH3COO)2.2H2O
(Sigma Aldrich, 99%), copper (II) acetate monohydrate Cu(CH3COO)2.H2O (Sigma Aldrich,
99%), iron (III) nitrate nonahydrate Fe(NO3)3.9H2O (Merck Germany, 99%), and the precursor
salts were taken in the solvent of anhydrous ethyl alcohol (C2H5OH). The synthesis of C3N4
nano-sheets were prepared by solid state reaction method, where melamine (C3H6N6) was used
as the precursor material. Also, in the present report the transparent PVDF gel was prepared by
the sol-gel method, where N,N-dimethyl formamide (DMF, Merck, India) was taken as the
5
solvent for PVDF pellets [molecular weight Mw: 275000 (hpc), Mn: 107000, Aldrich,
Germany].
2.2. Synthesis of Ni-Zn-Cu-ferrite (NZCF) nanoparticles
Ni-Zn-Cu-ferrite (NZCF) magnetic nanoparticles of different domain size were prepared
by a simple sol-gel technique. The stoichiometry of Ni0.50Zn0.30Cu0.20Fe2O4 was chosen for the
present study. The detail of the preparation of the as-prepared sample has been mentioned in our
earlier publication [19]. After the formation of the as-prepared solid flake, the sample was
mortared to convert the flake into the solid powder. Finally, the dried powder was sintered at 400
o
C in the tube furnace for 6 hours and the sample was designated as NZCF.
2.3. Synthesis of C3N4 semiconducting fillers
In the present report the semiconducting C3N4 fillers were prepared by following one-step
solid state reaction method. The desired product was obtained via heat treatment of 10 g
melamine in a 7 ml curved bottom silica crucible and partially covering it with the cap. The
crucible with the precursor was annealed in the presence of air using a hot air furnace at 500 oC
for 4 hours with a heating rate of 3 oC/min. The crucible containing C3N4 was then cooled to
room temperature before collecting the powdered sample. A colour change was observed from
white to faded yellow indicating the effective condensation of melamine resulting in a high yield
of C3N4 with negligible loss in precursor. The as-synthesized yellow sample was finely grounded
using mortar and pestle before introducing it to NZCF, creating NZCF-C3N4 composite.
2.4. Synthesis of NZCF-C3N4 nanocomposite
The composite of NZCF-C3N4 nanocomposites has been prepared by the solid-state
reaction method. At first, both the synthesized magnetic NZCF nanoparticles and C 3N4 were
mixed with proper proportion in an organic solvent and the homogeneous mixture of NZCF and
6
C3N4 was prepared using ultrasonic bath sonicator. It is to be mentioned here that, in the present
report two different proportions magnetic NZCF nanoparticles and C3N4 such as, 70 wt% of
NZCF nanoparticles with 30 wt% of C3N4 and 50 wt% of NZCF nanoparticles with 50 wt% of
C3N4 have been selected for the preparation of two different sets of NZCF-C3N4 heterostructure
nanocomposites (NFC73 and NFC55) and the details of the sample specifications have been
given in Table 1. After several minutes of sonication process the homogeneous mixture was
dried on a glass plate in the vacuum desiccator at RT. The dried mixture was then grounded
thoroughly in order to make the homogeneity of the mixture even better. After an hour of
grinding process, the mixture was poured in the organic solvent to make the well dispersed
solution. This solution was then sonicated again and the whole course of this entire process was
repeated for 3-4 times. Finally, the dried and homogeneous mixture of NFC73 and NFC55
nanocomposites were sintered at 400 oC. After the sintering process a uniform composite
structures of NFC73 and NFC55 nanocomposites have been formed which is then considered as
a potential nano-fillers inside the matrix of PVDF for EM wave shielding applications.
2.5. Synthesis of NZCF-C3N4-PVDF composite films
The detail of the similar kind of synthesis procedure corresponding to the composite gels
of NZCF-C3N4-PVDF for two sets of NZCF-C3N4 composite nanofillers i.e., NFC73 (70 wt% of
NZCF nanoparticles with 30 wt% of C3N4) and NFC55 (50 wt% of NZCF nanoparticles with 50
wt% of C3N4), has been discussed in our earlier publication [19]. The entire process was
reproduced for two different sets of NZCF-C3N4-PVDF composite gels for the preparation of
two different polymer composite films. In the present report two different weight fractions (20
and 30 wt%) corresponding to the NFC73 and NFC55 composite nanomaterials were considered
in order to get four different polymer composite films such as NFCP732 (20 wt% NFC73
7
nanofillers loaded PVDF matrix), NFCP733 (30 wt% NFC73 nanofillers loaded PVDF matrix),
NFCP552 (20 wt% NFC55 nanofillers loaded PVDF matrix), NFCP553 (30 wt% NFC55
nanofillers loaded PVDF matrix), respectively. The thick NFC73/NFC55-PVDF composite gels
were further processed under ultrasonic vibration for 3-4 hours and the homogeneously dispersed
NFC73/NFC55 nanofillers-PVDF composite gels were casted on the warm and clean glass
substrates. At 80 oC the DMF solution get evaporated off slowly and the solid film structure of
NFC73/NFC55-PVDF composite films were peeled off from the glass substrates. The bare
PVDF film was also produced by following the same solution casting method. The thicknesses
of the bare PVDF film as well as NFCP732, NFCP733, NFCP552 and NFCP553 composite
films were measured, and the measured values of the thicknesses of the resultant composite films
along with the details of the sample specifications have been given in Table 1.
Table 1 Detail of sample specifications and average thickness of PVDF and composite films
Sample Specification Average thickness
(μm)
NFC73 70 wt% of NZCF with 30 wt% of C3N4 ---
NFC55 50 wt% of NZCF with 50 wt% of C3N4 ---
PVDF PVDF without the loading of nanofillers 177.3
NFCP732 20 wt% NFC73 nanofillers loaded PVDF matrix 152.3
2.6. Characterization techniques
8
The XRD patterns of NZCF nanoparticles, C3N4 nanofillers, pure PVDF, NFCP732,
NFCP733, NFCP552 and NFCP553 composite films were recorded in Bruker’s Advanced D8
diffractometer with Cu Kα radiation (λ = 0.15425 nm) in the range of 2θ from 10 to 80o. The
surface morphologies of all samples were obtained by field emission scanning electron
microscopy (FESEM, INSPECT F50 of FEI, Netherland). FTIR measurement of NFCP732,
NFCP733, NFCP552 and NFCP553 composite films was recorded in SHIMADZU, IR Prestige-
21 (Japan). Magnetic response of some selected samples at RT was recorded by a
Superconducting Quantum Interference Device (SQUID) magnetometer (MPMS XL 7, Quantum
Design). Electrical conduction mechanism was investigated by dielectric measurement using
Agilent 4294A Precision Impedance Analyzer. For this measurement the composite films were
cut into rectangular shape and the flat surfaces of the composite films were coated with
conductive silver paint (TED PELLA) and two metal wires were connected on the flat surfaces
of the composite films. The metal wires were connected to the opposite polarities of the applied
alternating electric field and the dielectric investigation was performed by using Agilent 4294A
Precision Impedance Analyzer. In order to get temperature dependent dielectric response study,
the composite samples were placed inside a hot air oven and the metal leads of the composite
films were taken out. The metal leads were connected with the opposite terminals of Agilent
4294A Precision Impedance Analyzer device and the alternating electric field was applied across
the composite films for temperature dependent dielectric response study. Shielding effectiveness
(SE) study of the composite films in the microwave region of frequency (X- and Ku-bands) was
measured by using Agilent E8363B PNA series Network Analyzer. Fig. 1 shows the free-
standing behavior and flexibility of all the film samples such as PVDF, NFCP732, NFCP733,
NFCP552 and NFCP553. The composite films such as NFCP732, NFCP733, NFCP552 and
9
NFCP553 were cut into the outline of the ﬂange dimensions corresponding to the X-band and
Ku-band and placed inside the waveguide flanges of the PNA microwave network analyzer
(Agilent E8363B) for microwave SE measurement. It is to be mentioned here that no holding
materials such as wax or paraffin have been considered for this purpose. Now, for shielding
effectiveness (SE) study two scattering (S) parameters, i.e., S11 (reflection coefficient) and S21
(transmission coefficient) would be considered. In this measurement, the thicknesses of
NFCP732, NFCP733, NFCP552 and NFCP553 composite films were 152.3, 127.1, 122.8 and
291.1 μm, and the areas of NFCP732, NFCP733, NFCP552 and NFCP553 composite films were
6.1 and 3.6 cm2 , respectively, for X- and Ku-bands.
Fig. 1 Images of free-standing nature and flexibility of (a) PVDF, (b) NFCP732, (c) NFCP733,
(d) NFCP552 and (b) NFCP553 composite films.
3. Result and discussions
3.1. Crystallographic phase analysis
In this article X-ray diffractogram (XRD) of all the samples are depicted in Fig. 2. Figs
2(a), (b) and (c) depict the crystallographic phases of NZCF nanoparticles, C3N4 and PVDF,
respectively. From the given 2(a), (b) and (c) all the crystallographic phases corresponding to
NZCF nanoparticles, C3N4 and PVDF have been identified and all the displayed phases have
10
been matched well with the crystallographic phases of the respective samples given in their
JCPDS files [29-32]. In Fig. 2(a) all the crystallographic phases corresponding to the planes
(220), (311), (440), (422), (511) and (400) have been observed for the polycrystalline NZCF
nanoparticles. In Fig. 2(b) the two most prominent crystallographic phases of C3N4
semiconducting fillers corresponding to its γ-phase have been observed at 13o and 28o for the
planes (100) and (002). In the present article the non-polar α-phase crystallization at 18.6o and
26.9o for the planes (110) and ((201)(310)), polar -phase crystallization at 20.1o and 36.2o for
the planes ((110)(200)) and ((020)(101)) and the polar γ-phase crystallization at 38.7o for the
plane (211) of bare PVDF have been identified in Fig. 2(c). It is to be mentioned here that,
impurity phase has not been identified in the given XRD patterns, but some undefined peaks are
there. These peaks have been appeared due to the presence of structural mismatching between
NZCF nanoparticles, C3N4 nanofillers and PVDF matrix. From Figs. 2(a), (b) and (c) it is quite
clear that all the individual materials (NZCF nanoparticles, C3N4 nanofillers and PVDF matrix)
have different crystal structures and these different nature of crystal structures are responsible for
the generation of some undefined or noise peaks in the XRD pattern of the composite films
(NFCP552, NFCP553, NFCP732 and NFCP733) given in Figs. 2(d-g). Figs. 2(d), (e), (f) and (g)
have been provided in this article to display the crystallographic phases of NFCP552, NFCP553,
NFCP732 and NFCP733 composite films. A careful investigation of these composite films under
X-ray diffractogram shows that the crystallographic phases of NFCP552, NFCP553, NFCP732
and NFCP733 have been matched quite satisfactorily with the crystallographic phases of the
component materials i.e. NZCF nanoparticles, C3N4 and PVDF respectively, present in the
resultant composite films. Thus, this XRD analysis will help us to understand the formation of
the composite form of the resultant materials with proper multi-phase state and it also helps us to
11
understand the simultaneous existence of all the component materials in NFCP552, NFCP553,
NFCP732 and NFCP733 composite films. The average crystallite diameter of NZCF
nanoparticles has been estimated from the broadening of the 100% intense peak (311) given in
Fig. 2(a), by applying the Debye-Scherrer equation [33]
λ
(1)
 θ
Here, D is the average crystallite size, λ is the incident X-ray wavelength, θ is the Braggs angle
corresponding to the peak (311) and the corresponding full width at half maximum (FWHM) is
designated as . The average crystallite diameter of ~ 34 nm for NZCF nanoparticles has been
observed by the XRD analysis of Fig. 2(a). The variation of peak intensity of the composite films
(NFCP552, NFCP553, NFCP732 and NFCP733) has also been observed in this XRD analysis.
This variation of peak intensity appears due to the variation of the loading percentage of NZCF-
C3N4 composite nanofillers inside the matrix of PVDF. Also, the formation of polar -phase and
γ-phase crystallizations of the resultant composite films indicate that NZCF-C3N4 composite
nanofillers have formed successful interfaces in interaction with the PVDF matrix. This
interaction is responsible for the formation of all trans-planar zig-zag (TTTT) conformation
inside the NZCF-C3N4-PVDF composite films. The formation of this electroactive all trans-
planar zig-zag (TTTT) conformation in these NZCF-C3N4-PVDF composite films makes them a
good responder for EMI shielding effectiveness in the microwave/GHz frequency range.
12
Fig. 2 XRD patterns of (a) NZCF nanomaterials, (b) C3N4 nanofillers, (c) PVDF and the
composite films of (d) NFCP732, (e) NFCP733, (f) NFCP552 and (g) NFCP553.
3.2. FESEM analysis
Fig. 3(I)(a-l) depicts the surface morphology of some selected NZCF-C3N4-PVDF composite
films (NFCP552 and NFCP732). Figs. 3(I)(a) and (d) show that the surface morphology of
NFCP552 and NFCP732 composite films are mostly spherulite in nature with the presence of
prominent bubble type structures. Also, the presence of radial lamellar structure has been found
in both composite films, but the fractional contribution of the radial lamellar structure in the
composite films is less. It has already been mentioned in our previous articles that the presence
of spherulite structure of bubble type in nature over the surface of NFCP552 and NFCP732
13
composite films indicates the presence of polar/electroactive β-phase crystallization of PVDF
matrix, whereas, the radial lamellar structure over the surface of NFCP552 and NFCP732
composite films is attributed to non-polar α-phase [19, 20]. The greater fractional contribution of
spherulite structure of bubble type in nature for both NFCP552 and NFCP732 as compared to the
radial lamella structure reveal that the polar/electroactive β-phase is quite prominent and
dominant for NFCP552 and NFCP732 composite films. Figs. 3(I)(b) and (e) of the given
micrographs clearly show that the nanofillers are present inside the PVDF matrix. These
nanofillers are either NZCF nanofillers or NZCF-C3N4 composite nanofillers. The insertion of
NZCF-C3N4 nanocomposite materials inside the matrix of PVDF is responsible for the formation
of nanofiller-PVDF interfaces inside NFCP552 and NFCP732 composite films and the formation
of such interfaces improves the overall electroactivity of the composite films and therefore, the
greater polar/electroactive β-phase of NFCP552 and NFCP732 composite films has been
developed. Figs. 3(I)(c) and (f) also reveal the presence of C3N4 layer structure inside PVDF
matrix. In the present study, the energy dissipative spectroscopy (EDX), as well as elemental
area mapping of NFCP552 composite film have been done as a representative among the other
NZCF-C3N4-PVDF composite structures. The EDX and elemental area mapping of NFCP552 are
shown in Figs. 3(g) to (l), respectively. The presence of nickel (Ni), zinc (Zn), copper (Cu), iron
(Fe) and oxygen (O) ions in the NFCP552 composite film corresponding to NZCF nanofillers of
the NZCF-C3N4-PVDF composite materials is confirmed by the EDX and elemental area
mapping study. Also, the peaks relating to gold (Au) in the EDX study has been observed due to
the presence of gold coating over the surface of NFCP552 composite film during the preparation
of the samples for FESEM imaging. The carbon and nitrogen peaks have not been considered in
EDX study since the FESEM observation was conducted keeping NFCP552 composite film over
14
the surface of carbon tape which can make the carbon (C) peak corresponding to both C3N4 and
carbon tape indistinguishable. Also, the elemental area mapping of NFCP552 composite film
shows a nearly uniform distribution of all the ions, namely nickel (Ni), zinc (Zn), copper (Cu),
iron (Fe) and oxygen (O), inside the composite film. Along with the microstructural study the
existence of polar β-phase and non-polar α-phase in NFCP552 and NFCP732 composite films
have also been substantiated in the crystallographic phase analysis and chemical analysis (section
3.1. and 3.3.). From this morphological analysis it is quite clear that both magnetic NZCF
nanoparticles and the conductive C3N4 layer structures are present simultaneously inside the
NFCP552 and NFCP732 composite films and it is expected that these two components and more
specifically the insertion of C3N4 semiconducting fillers inside the matrix of PVDF will put some
addition impact to improve the shielding effectiveness of absorption (SEA) and the shielding
effectiveness of reflection (SER) of NFCP552 and NFCP732 composite films. Though, the detail
investigation of the shielding effectiveness has been done in the later section (section 3.6.) but
the anticipation made in this discussion is true for all four NZCF-C3N4-PVDF composite films
(NFCP552, NFCP553, NFCP732 and NFCP733) taken into consideration in this article. Also, in
the present study the FESEM micrograph of NZCF-C3N4 binary nanofillers has been displayed in
Fig. 3(II). The micrograph of NZCF-C3N4 binary nanofillers clearly shows the presence of both
NZCF nanofillers and C3N4 laminated sheet in the composite films. Therefore, the presence of
NZCF-C3N4 binary nanofillers micro clusters inside the pocket of the laminated composite
structures and surrounded by the non-conducting matrix of PVDF is very much clear and distinct
in the given FESEM micrographs.
15
Fig. 3(I) FESEM images of (a), (b), (c) NFCP552 and (d), (e), (f) NFCP732 composite films, (g)
EDX image of NFCP552 and area mapping of NFCP552 shows the distribution of (h) Ni, (i) Zn,
(j) Cu, (k) Fe and (l) O atoms of NZCF nanoparticles inside the structure of NFCP552 composite
film and (II) FESEM image of NZCF-C3N4 binary nanofillers composite materials.
16
3.3. FTIR analysis
The FTIR study of the composite films have been displayed in Fig. 4(I) and the presence
of non-polar α-phase and the polar β-phase of the composite films have been substantiated in this
discussion. Fig. 4(I)(a) displays the presence of non-polar α-phase and the polar β-phase in
PVDF and the corresponding peaks are also assigned in the given figure. The characteristic
peaks of non-polar α-phase of PVDF corresponding to CF2 waging, CF2 bending, CF2 bending
and skeletal bending, CH2 rocking and the characteristic peaks of polar β-phase of PVDF
corresponding to CF2 stretching, CF2 waging, CH2 rocking, CF2 stretching and skeletal C-C
stretching have been listed and given in Table 2 [34-37]. Now, in Figs. 4(I)(b) to (e) for NZCF-
C3N4-PVDF composite films (NFCP552, NFCP553, NFCP732 and NFCP733) all the
characteristic peaks of non-polar α-phase and polar β-phase of PVDF are very much prominent
and the peaks are also listed in the given Table 2. Though, the variation of peak intensity due to
the variation of loading percentages of NZCF-C3N4 composite nanofillers has been found in the
given Figs. 4(I)(b) to (e). The presence of various characteristic peaks of C3N4 semiconducting
fillers have also been confirmed in the given Fig. 4(II) for all the NZCF-C3N4-PVDF composite
films (NFCP552, NFCP553, NFCP732 and NFCP733) and the peaks have been listed in the
given Table 2 [38, 39]. It is to be mentioned here that the several strong bands have been
observed for all the composite films within the range of 2000-1100 cm-1, signify the presence of
stretching modes of CN heterocycles. The presence of these strong bands of NFCP552,
NFCP553, NFCP732 and NFCP733 composite films clearly indicate that C3N4 semiconducting
fillers are present inside the structure of PVDF. Now, the presence of both NZCF nanoparticles
and C3N4 semiconducting fillers are responsible for the formation of interfaces between the
NZCF-C3N4 composite nanofillers and the PVDF matrix. It has been reported in many articles
17
that C3N4 is a conducting material, so it is expected to get the accumulation of the charge
particles at the interfaces between the NZCF-C3N4 nanoparticles and the PVDF matrix. At the
interface it is also expected to get the interaction between the conduction electrons of NZCF-
C3N4 composite nanofillers and the CH2 groups of PVDF matrix with a positive surface charge
density. This electrostatic interaction between the NZCF-C3N4 composite nanofillers and the
PVDF matrix leads to the formation of aligned chains with all-trans-planar zig-zag (TTTT)
conformation of all the NZCF-C3N4-PVDF composite films (NFCP552, NFCP553, NFCP732
and NFCP733), which on the other hand improves the fractional contribution of polar β-phase of
PVDF in the composite films as compared to the non-polar α-phase [40-42]. In Fig. 5 the
formation of this all-trans-planar zig-zag (TTTT) conformation of NZCF-C3N4-PVDF composite
films has been displayed right form the synthesis of the composite nanofillers (NZCF-C3N4). It is
to be mentioned here that the formation interfaces between the NZCF-C3N4 composite
nanofillers and the PVDF matrix and thereby the improvement of the fractional contribution of
polar β-phase of PVDF in the composite films enhances the resultant polarization effect. The
overall improvement of the polarization effect in NZCF-C3N4-PVDF composite films has been
substantiated in the dielectric discussion (section 3.5.), which on the other hand justifies the
influence of the semiconducting filler component of C3N4 inside the heterostructure composites
of Ni-Zn-Cu-Ferrite-Poly(vinylidene fluoride) systems for the fabrication of the improved radar
absorbing material.
18
Fig. 4 (I) FTIR spectra of (a) PVDF, (b) NFCP552, (c) NFCP553, (d) NFCP732 and (e)
NFCP733 composite films in the range of 1200-400 cm-1 and (II) FTIR spectra of (a)
NFCP552, (b) NFCP553, (c) NFCP732 and (d) NFCP733 composite films in the
range of 2000-1100 cm-1.
19
Table 2 FTIR peaks corresponding to the α-phase and β-phase of PVDF, NFCP552, NFCP553,
NFCP732 and NFCP733 composite films and CN-absorption band of NFCP552,
NFCP553, NFCP732 and NFCP733 composite films
Sample α-phase β-phase CN-absorption band
name (cm-1) (cm-1) (cm-1)
PVDF 497 520 ----
540 610
621 846
769 1081
816
898
982
NFCP552 same as above same as above 1290
1340
1437
1685
NFCP553 same as above same as above same as above
20
Fig. 5 Schematic diagram of the synthesis of NZCF-C3N4-PVDF composite films and the
proposed polar β-phase formation mechanism of NZCF-C3N4-PVDF composite films.
3.4. Magnetic response study
In this article the magnetic response of NZCF-C3N4-PVDF composite films have been
investigated. In order to understand how much these composite films are effective for different
applications in the field of electromagnetic radiation, the magnetic response study of two
representative NZCF-C3N4-PVDF composite films (NFCP553 and NFCP733) at RT has been
presented as a function of external magnetic field of maximum field strength 50000 Oe. The M-
H loops of these two representative composite films (NFCP553 and NFCP733) have been
displayed in Fig. 6, where, Fig. 6(a) displayed the M-H loop of NFCP553 composite material
21
and Fig. 6(b) displayed the M-H loop of NFCP733 composite material. In both the composite
films (NFCP553 and NFCP733) a clear hysteresis loop has been observed at RT which is a clear
evidence of having magnetic ordering in the representative composite films. It has already been
discussed in the experimental section (section 2.4.) that NFCP733 consist larger loading
percentage of NZCF nanofillers as compared to NFCP553. So, it is expected to get a better
magnetic response in NFCP733 as compared to NFCP553. In Fig. 6 it is quite clear that the M-H
loops of both NFCP553 and NFCP733 are not saturated even when the applied magnetic field
strength was 50000 Oe. This type of behavior of the magnetic composite films undoubtedly
proves the presence of super paramagnetic (SPM) nature of NFCP553 and NFCP733 composite
films. Also, Fig. 6 shows that the M-H loop of NFCP733 is tending more towards the saturation
near 50000 Oe as compared to the NFCP553 along with larger magnetization and coercivity. The
extracted magnetic information like, maximum magnetization, coercivity, and retentivity of
NFCP553 and NFCP733 have been listed in Table 3. The extracted maximum magnetization of
NFCP553 and NFCP733 are ~ 1.9 and 9.7 emu/g, respectively. The high value of maximum
magnetization of NFCP733 as compared to NFCP553 has been observed due to the presence of
higher loading percentage of NZCF magnetic nanofillers in the matrix of PVDF for NFCP733 as
compared to NFCP553. Also, the extracted value of coercivity of NFCP553 and NFCP733 are ~
23 and 24 Oe, respectively and the extracted value of retentivity of NFCP553 and NFCP733 are
~ 0.033 and 0.190 emu/g, respectively. The magnified image of the hysteresis loops of NFCP553
and NFCP733 have also been displayed in the inset of the given Fig. 6. The variation of
maximum magnetization and coercivity of these magnetic composite films appears due to the
variation of the NZCF loading percentage in the matrix of PVDF. From the magnetic response
study of these two representative composite films one thing can be confirmed that the other two
22
composite films (NFCP552 and NFCP732) are also magnetic in nature even at RT. This
magnetic nature of the composite films signifies that all the composite films consist magnetic
dipoles at RT and when these magnetic dipoles interact with the magnetic field vector of EM
radiation attribute shielding effectiveness due to absorption and the detail of this discussion has
been given in the shielding effectiveness study (section 3.6.). From the Figs. 6(a) and (b) it is
quite clear that the sufficiently high maximum magnetization and coercivity of the composite
films make them a very good candidate for different magnetic applications as well as the most
potential composite system for the specific application in radar radiation absorption to combat
against the pollution of excessive exposure of EM radiation in the GHz frequency range.
Fig. 6 Static magnetic loops of (a) NFCP553 and (b) NFCP733 composite films.
23
Table 3 Various magnetic parameters of NFCP553 and NFCP733 composite films
Sample Saturation magnetization Coercivity Retentivity
(emu/g) (Oe) (emu/g)
NFCP553 1.9 23 0.033
NFCP733 9.7 24 0.190
3.5. Dielectric response study
Dielectric response of NZCF-C3N4-PVDF composite films have been investigated in the
present report and the corresponding dielectric permittivity of the composite films (NFCP732,
NFCP733, NFCP552 and NFCP553) have been calculated. This observation is very important in
order to understand the influence of C3N4 semiconducting fillers on the dielectric permittivity of
NZCF-C3N4-PVDF composite films. In this report dielectric permittivity of NZCF-C3N4-PVDF
composite films (NFCP732, NFCP733, NFCP552 and NFCP553) has been estimated in the
frequency range of 40 Hz to 106 Hz/1 MHz with the increasing temperature from 30 oC to 100
o
C. Real part of dielectric permittivity (ε′) of NZCF-C3N4-PVDF composite films (NFCP732,
NFCP733, NFCP552 and NFCP553) has been estimated by applying the formula [43, 44]
ε′ (2)
Fig. 7(I) shows the real part of dielectric permittivity (ε′) of the composite films in the
frequency range of 40 Hz to 106 Hz at three different temperatures (30, 50 and 100 oC). In Figs.
7(I)(a) and (d) real part of dielectric permittivity of NFCP732, NFCP733, NFCP552 and
NFCP553 composite films have been displayed at RT in the frequency range of 40 Hz to 106 Hz
as compared to the PVDF. It is quite clear from these observations that the dielectric permittivity
of all the composite films has been enhanced as compared to the PVDF and more interestingly
24
the dielectric permittivity of NFCP552 and NFCP553 composite films has been enhanced
enormously as compared to the PVDF and this enhancement of dielectric permittivity has been
observed undoubtedly due to the development of the polar β-phase of the PVDF matrix in
NZCF-C3N4-PVDF composite films as well as the development of interfacial dipolar
polarization at the interfaces of NZCF-C3N4-PVDF composite films corresponding to Maxwell-
Wagner-Sillers interfacial polarization effect [49-52]. Also, this interfacial dipolar polarization
of Maxwell-Wagner-Sillers type has been influenced significantly due to the presence of C3N4
semiconducting fillers in the matrix of PVDF. It is to be mentioned here that the dielectric
permittivity of NZCF-PVDF composite films has already been reported in our previous articles
and it has been found in one of the articles that the nanofillers of magnetic NZCF inside the
matrix of PVDF can alter the dielectric permittivity of NZCF-PVDF composite films only
moderately as compared to PVDF [19, 20]. The room temperature dielectric permittivity of
NZCF-PVDF composite films has been found to vary from 12 to 24, whereas the dielectric
permittivity of PVDF has been found 15.5 [19]. Also, in the present case, nearly same dielectric
permittivity has again been observed for PVDF. The detail of the dielectric permittivity of the
composite films as a function of frequency for different types of polarization has been provided
in our previous articles [19, 20, 43, 44]. The present study clearly shows that the dielectric
permittivity of NFCP552 and NFCP553 have been enhanced enormously as compared to the
PVDF. However, the dielectric permittivity of NFCP732 and NFCP733 is slightly more than that
of PVDF at RT. Now, in NFCP552 and NFCP553 the loading percentage of C 3N4
semiconducting fillers inside the PVDF matrix is greater as compared to NFCP732 and
NFCP733 (see Table 1). The presence of C3N4 semiconducting fillers can act as the charge
source at RT at the interfaces inside the PVDF matrix and thereby can influence the dielectric
25
polarization of the composite films in presence of the external alternating electric field. In
NFCP552 and NFCP553 composite films, the greater loading percentage of C3N4
semiconducting fillers inside the matrix of PVDF as compared to the NFCP732 and NFCP733
can provide more conduction charges at the interfaces of the NZCF-C3N4-PVDF composite films
and this can make the dielectric permittivity significantly high for NFCP552 and NFCP553 as
compared to NFCP732 and NFCP733 as well as PVDF. With the increase in temperature from
30 oC to 100 oC, C3N4 semiconducting fillers inside NFCP552 and NFCP553 composite films
can contribute more conduction electron at the interfaces and thereby improves the dielectric
permittivity of these composite films largely as displayed in Figs. 7(I)(b), (c), (e) and (f)
respectively. This conduction charge contribution by the C3N4 semiconducting fillers at RT
inside the matrix of PVDF improves the resultant polarization effect of the composite films and
it could help us to get better response in the field of magneto-dielectric applications. Also,
according to the Debye theory, the real part of complex permittivity can be related to temperature
as [45, 46],
(3)
(4)
where is the real part of complex permittivity, is the high frequency limit of permittivity,
is the static permittivity, ω is the angular frequency, is the activation energy, and
represent pre-factor and temperature dependent relaxation time and k is the Boltzmann’s
constant. From both the equations (3) and (4), we can say that when there is an increase in
temperature there is a decrease in the relaxation time which in turn enhances the real part of
complex permittivity of the composite samples, as evident from Fig. 7 (I). Fig. 7(II) shows the
imaginary part of dielectric permittivity (ε′′) of the composite films in the frequency range of 40
26
Hz to 106 Hz at three different temperatures (30, 50 and 100 oC). In Figs. 7(II)(a) and (d), ε′′ of
NFCP732, NFCP733, NFCP552 and NFCP553 composite films have been displayed at RT in the
frequency range of 40 Hz to 106 Hz as compared to the PVDF. Imaginary part of dielectric
permittivity (ε′′) of NZCF-C3N4-PVDF composite films (NFCP732, NFCP733, NFCP552 and
NFCP553) has been estimated by applying the formula [43, 44]
ε′′ = ε′ × tan (5)
In Figs. 7(II) (a), (b) and (c) the high value of ε′′, specifically for NFCP552 and
NFCP553 composite films has been observed at comparatively low frequency region for all three
temperatures as compared to the PVDF and the reduction of ε′′ with the increase in frequency
also validate the presence of multiple types of dielectric polarization effects inside the structure
of NFCP552 and NFCP553 composite films. Thus, at different frequency region the contribution
of different dielectric polarization effects gets changed. It is to be mentioned here that this high
value of ε′′ for NFCP552 and NFCP553 composite films has been attributed mainly due to the
presence of C3N4 semiconducting fillers inside the composite films. The greater charge
accumulation at the interfaces by the C3N4 semiconducting fillers can generate greater heat
energy at the cost of the electrical energy corresponding to the external alternating electric field.
The enhancement of the imaginary part of complex permittivity with increasing temperature can
be explained with the Debye theory, according to which imaginary part of complex permittivity
is related to temperature as,
(6)
(7)
27
where, is the imaginary part of complex permittivity, and are loss due to relaxation
polarization and electrical conductivity respectively, Eg is the band gap energy and is
temperature dependent electric conductivity. As C3N4 is a semiconducting filler inside the
composite structures, with the increase in temperature its carrier concentration increases, due to
this both relaxation and conduction effects act on imaginary permittivity [47, 48]. This is clearly
visible with the enhancement of in Fig. 7(II), where the value of has been enhancement
due to the increase in temperature. It has also been found in Figs. 7(II)(d), (e) and (f) that this
effect is comparatively less significant for NFCP732 and NFCP733 and more significant for
NFCP552 and NFCP553. Now, the loss of electrical energy in form of heat energy inside the
NZCF-C3N4-PVDF composite films (NFCP732, NFCP733, NFCP552 and NFCP553) is
responsible for the enhancement of the shielding effectiveness of absorption of NZCF-C3N4-
PVDF composite films.
28
Fig. 7 (I) Variation of real part of dielectric constant (εʹ) with frequency of PVDF, NFCP552 and
NFCP553 composite films at (a) 30 oC, (b) 50 oC and (c) 100 oC and PVDF, NFCP732 and
NFCP733 composite films at (d) 30 oC, (e) 50 oC and (f) 100 oC and (II) variation of imaginary
part of dielectric constant (εʹʹ) with frequency of PVDF, NFCP552 and NFCP553 composite
films at (a) 30 oC, (b) 50 oC and (c) 100 oC and PVDF, NFCP732 and NFCP733 composite films
at (d) 30 oC, (e) 50 oC and (f) 100 oC.

29
In this article Fig. 8(I) shows the loss tangent (tanδ) of NZCF-C3N4-PVDF composite
films (NFCP732, NFCP733, NFCP552 and NFCP553) and PVDF in the frequency range of 40
Hz to 106 Hz at three different temperatures (30, 50 and 100 oC). The tanδ of NZCF-C3N4-PVDF
composite films has been estimated by applying the formula [53]
(8)
In Fig. 8(I) the variation of dielectric loss tangent (tan ) as a function of frequency and
temperature has been appeared due to the presence of induced dipolar polarization inside the
structure of NZCF-C3N4-PVDF composite films and the loss tangent (tan ) in the present case
has been influenced mostly due to the presence of C3N4 semiconducting fillers inside the matrix
of PVDF. From the tan study it is quite clear to us that all the composite films are highly
responsive in the frequency range of 40 Hz to 106 Hz at three different temperatures (30, 50 and
100 oC), the value of tan decrease with increase of frequency but with the increase of loading
percentage of C3N4 semiconducting fillers inside the matrix of PVDF the value of tan increase
significantly. Also, it has been noticed that the value of tan is larger in the present composite
films (NZCF-C3N4-PVDF) as compared to the NZCF-PVDF composite films, published in our
earlier reports [19]. The detail of the dielectric loss tangent (tan ) of the composite films as a
function of frequency has been provided in our previous articles [19, 20]. The significant change
that we have identified in the present study, is the significant modulation of tan in presence of
C3N4 semiconducting fillers along with both NZCF nanofillers and PVDF matrix. This C3N4
semiconducting fillers were not present in NZCF-PVDF composite films and it is present in
NZCF-C3N4-PVDF composite films. Now in case of NZCF-C3N4-PVDF composite films the
tan is higher than that of NZCF-PVDF composite films because in the former composite
structure C3N4 acts as a 2-D semiconducting material and this semiconducting material improves
30
the polarization loss corresponding to the space charge polarization at the interfaces as well as
the conduction loss inside the composite structures. It is also observed that tan of NFCP552 and
NFCP553 composites are more as compared to the NFCP732 and NFCP733 composites. Among
all the composite structures, NFCP552 and NFCP553 composites have a higher concentration of
C3N4 as compared to NFCP732 and NFCP733 composites (see Table 1). The greater
concentration of C3N4 inside the PVDF matrix might have led to the enhancement of effective
interfaces and charge accumulation inside the composite structures and thereby improves the
polarization loss of NFCP552 and NFCP553 composites as compared to NFCP732 and
NFCP733 composites observed in Fig. 7(II) along with the improvement of the conduction loss
mentioned earlier, which leads to the enhancement of tan of NFCP552 and NFCP553
composites as compared to NFCP732 and NFCP733 composites. Thus, the presence of C3N4
semiconducting fillers inside the matrix of PVDF is actually responsible for the enhancement of
the tan of the composite films at all three different temperatures and the improvement of the
tan of NZCF-C3N4-PVDF composite films can make these NZCF-C3N4-PVDF composite films
suitable for the shielding effectiveness in the microwave region of frequency. In this article Fig.
8(II) shows the ac conductivity (σac) of NZCF-C3N4-PVDF composite films (NFCP732,
NFCP733, NFCP552 and NFCP553) and PVDF in the frequency range of 40 Hz to 106 Hz at
three different temperatures (30, 50 and 100 oC). The σac of NZCF-C3N4-PVDF composite films
has been estimated by applying the formula [53]
σac = 2π (9)
Fig. 8(II) shows the low value of σac of all NZCF-C3N4-PVDF composite films
(NFCP732, NFCP733, NFCP552 and NFCP553) and PVDF at low frequency region
corresponding to all three different temperatures and the value of σac has been enhanced largely
31
at high frequency region mostly for NFCP552 and NFCP553 composite films. Firstly, the
observed variation of σac is short range conductivity in nature and this type of conductivity can
be found when the charge carriers move inside the material structure under the influence of
external alternating electric field. It is now clear to us that C3N4 semiconducting fillers inside
PVDF matrix can act as the charge source at RT and thereby it can provide charge carriers at the
interfaces of the composite films. This entire process can improve the dipolar polarization
effects. Now, the dipolar polarizations inside NZCF-C3N4-PVDF composite films can generate
short-range σac in the frequency range of 40 Hz to 106 Hz at all different temperatures, though,
with the increase in temperature from 30 oC to 100 oC, this short-range σac get decreased as
shown in Fig. 8(II). The variation of short-range σac in the lower frequency range has been
appeared due to the interfacial polarization effect of NZCF-C3N4-PVDF composite films and it
has been enhanced at high frequency range due to presence of other types of dipolar polarization
effects such as ionic polarization, electronic polarization, which are temporary in nature. Thus,
this short-range σac in the frequency range of 40 Hz to 106 Hz depends on both Maxwell-
Wagner-Sillers interfacial polarization as well as other types of dipolar responses due to the
presence of and influenced by the C3N4 semiconducting fillers inside the matrix of PVDF, which
is on the other hand also effective at high frequency region. Thus, from the dielectric response
study, it is quite clear that the incorporation of C3N4 semiconducting fillers with different loading
percentage inside PVDF matrix generates various dipolar effects due to which the EMI shielding
ability of NZCF-C3N4-PVDF composite films is expected to be more in the GHz frequency
range.
32
Fig. 8 (I) Variation of tangent loss (tanδ) with frequency of PVDF, NFCP552 and NFCP553
composite films at (a) 30 oC, (b) 50 oC and (c) 100 oC and PVDF, NFCP732 and NFCP733
composite films at (d) 30 oC, (e) 50 oC and (f) 100 oC and (II) variation of ac conductivity (σac)
with frequency of PVDF, NFCP552 and NFCP553 composite films at (a) 30 oC, (b) 50 oC and (c)
100 oC and PVDF, NFCP732 and NFCP733 composite films at (d) 30 oC, (e) 50 oC and (f) 100
o
C.
33
3.6. Shielding effectiveness study
In order to get a proper understanding about the usefulness of the composite films
(NFCP732, NFCP733, NFCP552 and NFCP553) for shielding effectiveness against
electromagnetic radiation as well as to understand the importance of different component
materials and their contributions for the same, the shielding effectiveness study has been
conducted in this report for X-band and Ku-band of microwave radiation. Microwave radiation
belongs to the range of 300 MHz to 300 GHz of frequency and X-band and Ku-band of
microwave radiation belong to the frequency range of 8-12 GHz and 12-18 GHz, respectively.
This frequency range i.e., 8-18 GHz is technically known as super high frequency (SHF) and
this SHF region, more specifically 8-18 GHz frequency region, is important for Radar
applications. In the present article the shielding effectiveness of the composite films has been
considered for shielding effectiveness for absorption (SEA) phenomena, shielding effectiveness
for reflection (SER) phenomena and shielding effectiveness for multiple reflections (SEMR)
phenomena [54]. However, SEMR for the composite films (NFCP732, NFCP733, NFCP552 and
NFCP553) can be ignored due to the large difference between the skin depth of the EM wave for
these composite films and the thicknesses of the composite films. Therefore, the overall
shielding effectiveness of the composite films can be displayed in three different ways and they
are shielding effectiveness for absorption (SEA) phenomena, shielding effectiveness for
reflection (SER) phenomena and the total shielding effectiveness (SET) phenomena due to the
simultaneous contribution of SEA and SER. In this article the SET of the composite films has been
estimated by using the equation below [55, 56]
(10)
34
On the other hand, the estimations of SEA and SER, in order to get the idea about SET of
the composite films as mentioned in equation 6, the equations given below have been considered
[57]
(11)
(12)
Here S11 and S21 are the reflection coefficient and transmission coefficient, respectively and they
are the part of scattering (S) parameters. The shielding effectiveness for absorption (SEA)
phenomena, shielding effectiveness for reflection (SER) phenomena and the total shielding
effectiveness (SET) phenomena of the composite films (NFCP732, NFCP733, NFCP552 and
NFCP553) have been displayed in Figs. 9, 10 and 11, respectively. Figs. 9(I) and (II) reveal the
SEA of NFCP732, NFCP733, NFCP552 and NFCP553 composite films for X-band and Ku-band
in the total frequency range of 8-18 GHz. In this measurement a high value of SEA has been
observed for all the NZCF-C3N4-PVDF composite films. The maximum value of SEA nearly -44
dB has been observed for NFCP552 at a matching frequency of ~ 11.9 GHz for X-band and
maximum value of SEA nearly -61 dB has been observed for NFCP552 at a matching frequency
of ~ 14.1 GHz for Ku-band corresponding to the SHF band. It is to be mentioned here that, in our
previous publication we have reported the shielding effectiveness for absorption (SEA)
phenomena of Ni-Zn-Cu-ferrite-PVDF composite film and -49.7 dB of maximum SEA at a
matching frequency of 13.2 GHz has been observed [19]. Here, in the present work the SEA of
all the NZCF-C3N4-PVDF composite films has been found greater as compared to the previously
published report. Now, in comparison to work published earlier and the present work it is quite
clear to us that the maximum value of SEA for the present work is not only greater than that of
the previously published work on Ni-Zn-Cu-ferrite-PVDF composite film, but the overall value
35
of SEA of all the NZCF-C3N4-PVDF composite films (~ -45 dB within 8-12 GHz and ~ -61 dB
within 12-18 GHz) has been enhanced as compared to the Ni-Zn-Cu-ferrite-PVDF composite
film (~ -39 dB within 8-12 GHz and ~ -49.7 dB within 12-18 GHz) [19]. In both the cases, even
in presence of similar type of magnetic nanomaterials the sufficiently high value of SEA for the
present work has been observed due to the presence of semiconducting filler component i.e.,
C3N4 in the matrix of PVDF. Shielding effectiveness for absorption (SEA) phenomena mainly
depends on the interaction between the magnetic field vector of incident EM radiation with
magnetic dipoles and the interaction between the electric field vector of incident EM radiation
with induced electric dipoles present is the system. These two types of interactions are
responsible for the enhancement of shielding effectiveness for absorption (SEA) phenomena by
converting the incident EM radiation of microwave in nature into heat energy. These interactions
lead to the resonance of magnetic dipoles and induced electric dipoles present inside the structure
of NZCF-C3N4-PVDF composite films at the matching frequency of the incident EM radiation in
the frequency range of 8-18 GHz and enhances SEA of the composite films. Inside the matrix of
PVDF, C3N4 semiconducting fillers can provide conduction charges at RT at the interfaces.
These accumulated charges can generate induced electric dipoles when they are exposed to the
electric field vector of the incident EM radiation. Under the influence of the alternating electric
field vector of the incident EM radiation these induced electric dipoles can flip and thereby can
also produce resonance when the natural frequency of the induced electric dipoles matches well
with the frequency of the alternating electric field vector of the incident EM radiation. This
matching of both the frequencies leads to the formation of the resonance of the induced electric
dipoles and thereby improves the absorption of EM radiation which finally converts into the
thermal energy. This effect appears mainly due to the presence of C3N4 semiconducting fillers
36
inside the matrix of PVDF and it can also improve the SEA of NZCF-C3N4-PVDF composite
films as compared to the Ni-Zn-Cu-ferrite-PVDF composite film. Also, the presence of C3N4
semiconducting fillers component inside the matrix of PVDF in combination with the NZCF
magnetic nanofiller can generate eddies of conduction electrons inside the structure of PVDF
[58]. It is to be mentioned here that these C3N4 semiconducting fillers act as the conduction
charge source for different conduction purposes, but in the present case the long-range
conductivity inside the matrix of PVDF due to the presence of C3N4 semiconducting fillers is not
expected since these semiconducting fillers are surrounded and separated by the non-conducting
PVDF matrix. However, these conduction electrons can move in a circular path at different
pockets inside the PVDF matrix in presence of the magnetic flux due to the presence of magnetic
NZCF nanofillers and magnetic field vector of incident EM radiation. Therefore, inside PVDF
matrix these NZCF-C3N4 composite nanofillers can generate small eddies and thereby the eddy
current loss of incident EM radiation by absorption. So, at the interfaces not only the induced
electric dipoles are formed due to the presence of NZCF-C3N4 composite nanofillers but small
eddies of bounded conduction electrons are also formed due to the presence of both C 3N4
semiconducting fillers and NZCF nanofillers inside the matrix of PVDF for the present
composite films (NFCP732, NFCP733, NFCP552 and NFCP553). The simultaneous presence of
these two effects in the composite films can improve SEA of NZCF-C3N4-PVDF composite films
as compared to the Ni-Zn-Cu-ferrite-PVDF composite film. Figs. 10(I) and (II) reveal the SER of
NFCP732, NFCP733, NFCP552 and NFCP553 composite films for X-band and Ku-band in the
total frequency range of 8-18 GHz. Fig. 10 shows that the shielding effectiveness for reflection
(SER) phenomena of NZCF-C3N4-PVDF composite films is also sufficiently high and nearly
same for all the NZCF-C3N4-PVDF composite films. Usually, high reflection phenomenon
37
depends on the matching of the frequency of the incident EM radiation with the plasmonic
oscillation related to the surface conduction electron. This effect will be found maximum for the
materials that consist large conduction electron at the surface and these surface conduction
electrons related plasma oscillation. In the present case, moderate amount of conduction charges
are found right below the surface of the NZCF-C3N4-PVDF composite films due to the presence
of the C3N4 semiconducting fillers and this effect is even significant in the present case due to
the presence of large surface to volume ratio of NZCF-C3N4 composite nanofillers. Now, the
interaction between the electric field vector of the incident EM radiation and the conduction
electron can produce high value of shielding effectiveness for reflection (SER) phenomena for all
NZCF-C3N4-PVDF composite films (NFCP732, NFCP733, NFCP552 and NFCP553) [55].
Though, it has been observed in the present case that SER of NZCF-C3N4-PVDF composite films
is less as compared to SEA, since the conductivity of C3N4 semiconducting fillers is not very
high. In Fig. 10, maximum SER of -33 dB has been found for NFCP732 at a matching frequency
of ~ 11 GHz, though, all other NZCF-C3N4-PVDF composite films also show nearly equal
amount of SER at same matching frequency. Also, at 14.9 GHz and at 15.9 GHz of frequency,
nearly -34 dB of SER have been observed for NFCP733 and NFCP552, respectively. Thus, all the
composite films are good candidate for the shielding effectiveness for reflection (SER)
phenomena. These two phenomena are responsible for the overall enhancement of the total
shielding effectiveness (SET) phenomena of NZCF-C3N4-PVDF composite films and thereby the
reduction of transmission of the EM radiation of microwave/GHz frequency is expected. Figs.
11(I) and (II) reveal the SET of NFCP732, NFCP733, NFCP552 and NFCP553 composite films
for X-band and Ku-band in the total frequency range of 8-18 GHz. In the present study, SET of
NFCP732, NFCP733, NFCP552 and NFCP553 composite films has been enhanced enormously.
38
The individual enhancement of SEA and SER make this SET high for NFCP732, NFCP733,
NFCP552 and NFCP553 composite films. In Fig. 11 a very high value of SET nearly -71.5 dB
has been observed for NFCP732 corresponding to the X-band and at a matching frequency of 9.5
GHz and a very high value of SET nearly -88 dB has been observed for NFCP552 corresponding
to the Ku-band and at a matching frequency of 14.1 GHz. Thus, the presence of larger loading
percentage of C3N4 semiconducting fillers inside the structure of NZCF-C3N4-PVDF composite
films helps the composite films to provide better response of SET at comparatively high
frequency region. In this direction few articles have been reported in recent time where various
binary nanofillers have been incorporated in the polymer matrix in order to fabricate an efficient
laminated composite microwave absorber [57, 60-65]. These articles have been listed out in
Table 4 in the present report to show the competitiveness of NZCF-C3N4-PVDF composite films
with some recent state of the art composite materials where the binary nanofillers have been
considered. Therefore, undoubtedly it can be conferred that these high shielding effectiveness
corresponding to the absorption (SEA) phenomena, reflection (SER) phenomena and the total
shielding effectiveness (SET) phenomena of the present composite films not only resulted due to
the presence of NZCF magnetic nanofiller with the PVDF matrix but the unique idea of
introduction of C3N4 semiconducting fillers materials inside the matrix of PVDF along with
NZCF magnetic nanofiller has made all these NZCF-C3N4-PVDF composite films highly
efficient for the fabrication of advanced microwave absorbers to fight against the pollution of
excessive exposure of EM radiation in the GHz frequency range.
39
Fig. 9 Shielding effectiveness by absorption (SEA) of NFCP732, NFCP733, NFCP552 and
NFCP553 composite films in the frequency range of (I) 8-12 GHz of X-band and (II)
12-18 GHz of Ku-band.
40
Fig. 10 Shielding effectiveness by reflection (SER) of NFCP732, NFCP733, NFCP552 and
NFCP553 composite films in the frequency range of (I) 8-12 GHz of X-band and
(II) 12-18 GHz of Ku-band.
41
Fig. 11 Total Shielding effectiveness (SET) of NFCP732, NFCP733, NFCP552 and NFCP553
composite films in the frequency range of (I) 8-12 GHz of X-band and (II) 12-18
GHz of Ku-band.
42
Table 4 Competitiveness of some nanofillers and binary nanofillers-PVDF/other polymer based
composite materials for EMI shielding effectiveness
Samples Thickness Frequency EMI SEA/SET Ref no.
(μm) (GHz) (dB)
PVDF/rGO-MDA-FeCo 5000 18 -41 9
/MWCNT (10 wt% rGO-MDA
-FeCo, 5 wt% MWCNT
FeCo-MWCNT-PVDF 5000 18 -39 13
with 10 wt% of FeCo and
5 wt% of MWCNT
Ni-Zn-Cu-Ferrite-PVDF 161.2 - 252.6 13.2 -49.7 21
with 5 - 25 wt% of ferrite
Mn-Zn-Cu-Ferrite-PVDF 175.0 - 286.4 11.5 -33.5 22
with 5 - 25 wt% of ferrite
Natural rubber-Barium 1000 1 - 12 -75.0 26
Hexaferrite-CN with 20
wt% of Barium hexaferrite
Graphene/CNT/PVDF 100 18.6 - 26.5 -27.6 54
5 wt% CNT & 10 wt% graphene
Ni/Co2Z/PVDF 2000 8.2 - 12.4 -67 55
with Ni:Co2Z = 0.7:0.3
Co2U-type-hexaferrite-PVDF 120 - 190 14.2 -83 present
with 10 and 20 wt% of nanofiller report
43
4. Conclusion
In this article, for the first time we have prepared the magnetic NZCF-polar PVDF composite
films in presence of C3N4 semiconducting fillers by a very simple solution casting method and
the influence of C3N4 semiconducting fillers on the shielding effectiveness of the magnetic
nanofiller-PVDF/NZCF-PVDF composite films has been studied. Structural, microstructural and
chemical investigations have been found in support of the fabrication of NZCF-C3N4-PVDF
composite films with proper phase, improved surface morphology and various absorption bands
corresponding to the α-phase, β-phase of PVDF and CN absorption bands of C3N4
semiconducting fillers. Magnetic and dielectric investigations reveal the presence of high
magnetic loss factor and high dielectric loss factor due to the simultaneous presence of NZCF
magnetic nanofillers and the C3N4 semiconducting fillers inside the matrix of PVDF. The
presence of significant amount of magnetic and dielectric responses in NZCF-C3N4-PVDF
composite films plays the most important role for the improvement of shielding effectiveness
due to SEA, SER and SET. A very large SET has been found nearly -71.5 dB for NFCP732 within
8-12 GHz and nearly -88 dB for NFCP552 within 12-18 GHz. Thus, indisputably it can be
concluded that the high value of total shielding effectiveness (SET) of the present composite
films not only appeared due to the presence of NZCF magnetic nanofiller with the PVDF matrix
but the exceptional idea of consideration of C3N4 semiconducting fillers inside the matrix of
PVDF along with NZCF magnetic nanofiller has made all the NZCF-C3N4-PVDF composite
films highly efficient for the fabrication of microwave absorber to fight against electromagnetic
pollution.
44
Acknowledgement
Dr. Soumyaditya Sutradhar and all the co-authors would like to acknowledge Amity University
Kolkata for providing all supports for the smooth conduction of this research work. All the
authors are grateful to Amity University Kolkata for the same.
Notes: The authors declare no competing financial interest.
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Fabrication of Heterostructure Composites of Ni-Zn-Cu-Ferrite-C3N4-Poly(vi‐

Tanmoy Chakraborty, Shivam Sharma, Tanumoy Debnath, Abhik Sinha

To appear in: Chemical Engineering Journal

Received Date: 4 July 2020

© 2020 Elsevier B.V. All rights reserved.

fluoride) Films for the Enhancement of Electromagnetic Interference Shielding

Tanmoy Chakraborty1, Shivam Sharma1, Tanumoy Debnath1, Abhik Sinha Mahapatra2,

Abhyavartin Selvam 3, Sandip Chakrabarti3, Soumyaditya Sutradhar1*

semiconducting fillers for the enhancement of the electromagnetic interference shielding

Zn-Cu-Ferrite-C3N4-Poly(vinylidene fluoride) are fabricated by very simple solution casting

absorber to combat against electromagnetic pollution.

KEYWORDS: Ferrite nanoparticles, C3N4, PVDF film, electroactive property,

Maxwell-Wagner-Sillers interfacial polarization, microwave absorption.

*Corresponding author’s e-mail: sds.phy1@gmail.com (Dr. Soumyaditya Sutradhar).

In recent time, the significant technological improvement on radio/microwave frequency

frequency/microwave radiations on us behind the luster of various electromagnetic devices used

magnetic nanoparticles such as Ni-Zn-Cu-ferrite can improve the EM shielding effectiveness of

absorption of microwave radiation by these composite films.

Ni-Zn-Cu-ferrite (NZCF) magnetic nanoparticles with the stoichiometry of

Ni(CH3COO)2.4H2O (Sigma Aldrich, 99%), zinc (II) acetate dihydrate Zn(CH3COO)2.2H2O

2.2. Synthesis of Ni-Zn-Cu-ferrite (NZCF) nanoparticles

Ni-Zn-Cu-ferrite (NZCF) magnetic nanoparticles of different domain size were prepared

2.3. Synthesis of C3N4 semiconducting fillers

2.4. Synthesis of NZCF-C3N4 nanocomposite

The composite of NZCF-C3N4 nanocomposites has been prepared by the solid-state

2.5. Synthesis of NZCF-C3N4-PVDF composite films

Sample Specification Average thickness

NFC73 70 wt% of NZCF with 30 wt% of C3N4 ---

NFC55 50 wt% of NZCF with 50 wt% of C3N4 ---

PVDF PVDF without the loading of nanofillers 177.3

NFCP732 20 wt% NFC73 nanofillers loaded PVDF matrix 152.3

NFCP733 30 wt% NFC73 nanofillers loaded PVDF matrix 127.1

NFCP552 20 wt% NFC55 nanofillers loaded PVDF matrix 122.8

NFCP553 30 wt% NFC55 nanofillers loaded PVDF matrix 291.1

2.6. Characterization techniques

microscopy (FESEM, INSPECT F50 of FEI, Netherland). FTIR measurement of NFCP732,

21 (Japan). Magnetic response of some selected samples at RT was recorded by a

Superconducting Quantum Interference Device (SQUID) magnetometer (MPMS XL 7, Quantum

Design). Electrical conduction mechanism was investigated by dielectric measurement using

(Agilent E8363B) for microwave SE measurement. It is to be mentioned here that no holding

(transmission coefficient) would be considered. In this measurement, the thicknesses of

6.1 and 3.6 cm2 , respectively, for X- and Ku-bands.

(d) NFCP552 and (b) NFCP553 composite films.

3. Result and discussions

3.1. Crystallographic phase analysis

Fig. 2(a), by applying the Debye-Scherrer equation [33]

3.2. FESEM analysis

in the given FESEM micrographs.

stretching modes of CN heterocycles. The presence of these strong bands of NFCP552,

conformation of all the NZCF-C3N4-PVDF composite films (NFCP552, NFCP553, NFCP732

formation of this all-trans-planar zig-zag (TTTT) conformation of NZCF-C3N4-PVDF composite

of Ni-Zn-Cu-Ferrite-Poly(vinylidene fluoride) systems for the fabrication of the improved radar

range of 2000-1100 cm-1.

NFCP732 and NFCP733 composite films and CN-absorption band of NFCP552,

NFCP553, NFCP732 and NFCP733 composite films

Sample α-phase β-phase CN-absorption band

name (cm-1) (cm-1) (cm-1)