pubs.acs.

org/acsaelm Article

Multilayer Structures of a Zn0.5Ni0.5Fe2O4‑Reduced Graphene Oxide/

PVDF Nanocomposite for Tunable and Highly Efficient Microwave
Absorbers
Majed Amini, Milad Kamkar, Farhad Rahmani, Ahmadreza Ghaffarkhah, Farhad Ahmadijokani,
and Mohammad Arjmand*
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sı Supporting Information

ABSTRACT: Attenuating electromagnetic waves with an absorption-dominant mechanism is still an

arduous challenge, despite the recent progress in fabricating advanced electromagnetic interference
(EMI) shields. In this study, EMI shielding materials with an outstanding absorption performance were
developed. As such, in the first step, we report a practical method for synthesizing magnetic
Zn0.5Ni0.5Fe2O4 (ZnNiFe) nanoparticles. The magnetic hysteresis loop reveals that the synthesized
magnetic nanoparticles are superparamagnetic with a saturation magnetization of 75.8 emu/g. Thereafter,
we propose an EMI absorber using a multilayer assembly of polyvinylidene fluoride sheets containing low
concentrations of reduced graphene oxide (rGO) and ZnNiFe. It is shown that the EMI shielding
effectiveness increases from 23.93 to 29.05 dB, and the shielding by reflection decreases from 6.5 to 0.5
dB. This happens as the number of layers increases from two to nine at a fixed total thickness of 1.8 mm
and filler loadings of 1 wt % rGO and 5 wt % ZnNiFe. More importantly, the nine-layer sample shows an
absorption coefficient of A = 0.91, which translated into absorption of more than 91% of the incident
wave. To the best of our knowledge, this is the highest ever reported absorbance for a polymer-based
EMI shield. It is hypothesized that the superior absorbance of the nine-layer structure originates from (1)
multiple internal reflections inside the shield due to the presence of numerous conductive layers and (2) supermagnetic properties of
ZnNiFe nanoparticles, leading to enhanced magnetic loss.
KEYWORDS: poly(vinylidene fluoride), reduced graphene oxide, Zn0.5Ni0.5Fe2O4, multilayer structure,
electromagnetic interference shielding, absorption

1. INTRODUCTION Literature has witnessed the advent of numerous engineered

The proliferation of complex electronic devices has been
intertwined with their susceptibility to electromagnetic
interference (EMI). EMI could result in malfunctions and
system failure in many different areas (e.g., military, aerospace
electronics, medicine, mass transit systems, industrial touch
screens, and navigation).1−3 As such, the demand for high-
quality and robust EMI shielding materials has skyrocketed to
avoid electronic systems failure. EMI shielding can be achieved
through two main mechanisms of reflection and absorption.
Although reflection serves as a barrier, undesirably reflected
electromagnetic waves might create secondary pollution,
disturbing the operation of neighboring equipment and
harming human health.4 However, the absorption mechanism
attenuates the incident waves by converting them to heat
energy across the shielding materials. The dominant
absorption mechanism avoids secondary pollution and, thus,
is well suited to advanced applications where reflection should
be minimal. These include the electronics in a 5G network,
stealth aeroplanes, ultrasensitive electronics, radars, and
military sectors.5,6
materials for EMI shielding. High electrical conductivity is a
pivotal factor in achieving appreciable EMI shielding
effectiveness (SE); hence, metals and conductive polymer
composites (CPCs) are among the materials widely used as
EMI shields.5 Nonetheless, the high electrical conductivity is
associated with a high reflection of EM waves. That is,
although metals and CPCs showcase appreciable EMI SE, their
dominant shielding mechanism is reflection. This restrains
their application as shields in sensitive electronics in advanced
aerospace and defense industries. For example, shields made
from thick Ti 3 C 2 T x /reduced graphene oxide (rGO), 7
Ti3C2Tx/poly(3,4-ethylenedioxythiophene):poly(styrene sulfo-
nate) (PEDOT:PSS),8 rGO/polydimethylsiloxane (PDMS),9
and poly(ether-block-amide)/carbon nanotubes (CNTs)10
Received: September 29, 2021
Accepted: November 25, 2021
Published: December 13, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acsaelm.1c00940

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Table 1. Comparison of Total Shielding Effectiveness (SET), Absorption Loss (SEA), Reflection Loss (SER), and A for
Shielding Composites Containing Magnetic Fillers Reported in the Literature
filler concentration thickness SET SEA SER
sample preparation technique (wt %) (mm) (dB) (dB) (dB) A refs
copper nanowire−polystyrene solution mixing 15.5 0.21 35 19 16 0.80 21
phenolic resin/graphene solution mixing 49 0.4 41.84 35.42 6.42 >0.50 22
oxide−Fe2O3−carbon fiber
polyaniline−graphene/Fe3O4 chemical oxidation 50 2.5 ∼33 26 6.3 ∼0.24 23
polythiophene/Ni0.5Zn0.5Fe2−xCexO4 emulsion 34 29 5 ∼0.33 24
nanoparticle polymerization
polyvinyl chloride (PVC)/graphene−Fe3O4 melt mixing 8 1.8 13 5 8 >0.4 25
chitosan/graphene−Fe3O4 solution mixing 70 0.3 ∼38 ∼25 ∼12 ∼0.10 26
polyvinyl alcohol (PVA)/graphene−Fe3O4 solution mixing 35 0.3 15 27
epoxy/Fe2O3−carbon fiber solution mixing 40 1.0 51.5 47.5 4 ∼0.50 28
polyamide/PA−NiFe2O4 solution mixing 40 0.041 42.5 29
polystyrene/graphene−Fe3O4 solution mixing 3.2 (vol %) ∼30 ∼24 ∼6 ∼0.30 30
PVDF/GNP−Ni nanoparticle−CNT solvent casting 11 0.6 46 34 12 0.80 17
PA/nickel nanoparticle solution mixing 3.07 (vol %) 2.50 50.6 0.91 31
PDMS/Fe3O4@rGO−gold nanoparticle solution mixing 2.0 30.5 ∼25 ∼5 0.75 32

Table 2. Comparison of SET, SEA, SER, and A for Multilayer Shielding Composites
filler
number concentration thickness SET SEA SER
sample of layers (wt %) (mm) (dB) (dB) (dB) A refs
PVDF/CNT−polycarbonate−Fe3O4 3 6 0.9 64 33
PVDF/CNTs−cobalt particle 12 0.3 35.3 26.2 9.1 ∼0.10 34
polymethyl methacrylate (PMMA)/graphene nanoplatelet (GNP)−Ni 3 40 2.5 62 ∼57 ∼5 ∼0.32 35
nanoparticle
PEDOT:PSS/graphene−CNT−Fe3O4 3 10 0.6 133.22 ∼120 ∼10 ∼0.10 36
polyethylene oxide (PEO)/CNT−cellulose−Fe3O4 9 30 0.024 30.3 18.45 11.54 0.10 37
PVDF/GNP−Ni nanoparticle−CNT 6 11 0.6 46 ∼34 ∼12 0.2 17
PVDF/CNT−Mn−Fe−carbon fiber−Ni particle 3 5 0.6 50 38
PVDF/graphene−Ni nanoparticle 8 20 0.5 43.3 31.7 11.5 >0.5 39
GO/poly(-hydroxybenzoate-co-DOPO-benzenediol dihydrodiphenyl ether 11 35 0.235 37.92 ∼30 ∼7 ∼0.40 40
terephthalate-boron nitride)/maleated
styrene−ethylene−butylene−styrene
polyurethane/Fe3O4@rGO−MWCNT 4 11.2 0.8 35.9 ∼31 ∼4 0.73 41

showed excellent EMI SE of 52, 60.5, 45, and 41 dB,
respectively; however, the reflection of all the mentioned
shields was above 70%, causing the emission of disrupting
waves to the atmosphere.
The research community has sought to manipulate the
shielding mechanisms of CPCs while it is not an option in
metals with the dominant reflection mechanism. Despite
recent progress, the reflection coefficient (R) in CPCs is still
high, and the development of EMI absorbers is an ongoing
challenge.11 For monolithic materials such as metals, shielding
by reflection is proportional to the ratio of electrical
conductivity and magnetic permeability, whereas shielding by
absorption is commensurate with the ratio of electrical
conductivity, magnetic permeability, and thickness. These
relationships serve as a cornerstone to design high-perform-
ance polymer shields with low reflection and high absorption.
Thus, low-conductivity magnetic fillers can be implemented in
the design of polymeric shields to achieve composites with low
reflection and high absorption features. This is due to the
positive impact of magnetic permeability on reducing the
reflection and enhancing the absorption.12,13
Absorption (A) and reflection (R) coefficients are critical
parameters to EMI shielding mechanisms. For instance, Zhang
et al.14 developed Fe3O4@MWCNT/PMMA nanocomposites
with an EMI SE of 25.11 dB and an R of 0.47 in the X-band. In
other studies, A values of 0.26 and 0.66 have been reported for
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CNT/rGO foam15 and thermoplastic polyurethane /rGO
nanocomposites,16 respectively (see Table 1 for more details).
As EMI SE of 20 dB is a minimum requirement for commercial
applications such as notebooks and desktop computers, it can
be inferred that all the data for studies compiled in Table 1
have an acceptable SE. Nevertheless, none of these studies
were successful in achieving an absorption of more than 80%.
This could be attributed to the high electrical conductivity of
the magnetic nanoparticles, contributing to the shielding by
reflection.
Another approach for boosting the wave absorption
mechanism is utilizing the multilayer strategy. Multilayer
assembly has emerged as a successful approach in improving
the EM energy dissipation through increasing the SE values via
multiple internal reflections. For example, in a recently
published work by Park et al.,17 a three-layer sandwich system
of polyvinylidene fluoride (PVDF)-based nanocomposite
containing graphene nanoplatelets, nickel, and CNTs was
devised for shielding application. Although the authors utilized
magnetic nanoparticles in the structure of their multilayer
shields, they failed to improve the absorption performance.
This can be due to the high electrical conductivity of the
employed magnetic nanoparticles. Table 2 shows a compre-
hensive comparison of the literature related to the multilayer
structure shields. A search through the literature shows that the
fabrication of a polymer-based EMI absorber (A > 0.9) is yet
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ACS Applied Electronic Materials
Figure 1. Schematic of the rGO synthesis steps.
to be achieved, even with a multilayer structure and in the
presence of magnetic nanoparticles.18,19 Therefore, the
simultaneous use of low-conductivity magnetic fillers and
multilayer structures hold promise to address this challenge.
The current research study aims to develop superabsorbent
shields (absorbing more than 90% of the wave) via
simultaneous utilization of low-conductivity magnetic fillers
and multilayer structuring. To this end, a novel magnetic
nanoparticle (Zn0.5Ni0.5Fe2O4), with excellent resistivity,
permeability, and saturation magnetization values, and rGO,
with high conductivity, were synthesized by precipitation and
modified Hummers method, respectively. Afterward, the effect
of the configuration of the PVDF/rGO−Zn0.5Ni0.5Fe2O4
multilayer shields by changing the number and order of the
layers at constant filler loadings and thicknesses were
investigated. According to the literature, Zn0.5Ni0.5Fe2O4 has
strong magnetic properties and extremely low conductivity.20
Therefore, by leveraging the conductive and magnetic
properties of the synthesized nanomaterials conjugated with
a multilayer assembly approach, we were able to achieve a total
EMI SE of 29.05 dB (at the thickness of 1.8 mm and nine-
layer) and an A of 0.91, which, to the best of our knowledge, is
the highest ever reported value for A (see Figure 6d).
2. MATERIALS AND METHODS
2.1. Materials. Natural flake graphite was purchased from Asbury
Graphite Company. H2SO4, H3PO4, KMnO4, H2O2, ethanol,
hydrazine, NiCl2·6H2O, Zn(NO3)2·6H2O, Fe(NO3)3·9H2O, NaOH,
HCl, and dimethylformamide (DMF) were provided by Sigma-
Aldrich. PVDF (Kynar 740) was purchased from Arkema Co. All of
the materials were used as received without any further purification.
2.2. Methods. 2.2.1. Preparation of Graphene Oxide Using the
Modified Hummers Method. Graphene oxide (GO) was synthesized
using the modified Hummers method from natural flake graphite.42
The synthesis details are given in the Supporting Information. Figure
1 illustrates the synthesis procedure of rGO from natural flake
graphite.
2.2.2. Preparation of Zn0.5Ni0.5Fe2O4 Magnetic Nanoparticle. The
Zn0.5Ni0.5Fe2O4 magnetic nanoparticle was synthesized through the
following steps: first, 1.2495 g of Zn(NO3)2·6H2O, 0.9983 g of NiCl2·
6H2O, and 6.7872 g of Fe(NO3)3·9H2O were dissolved in 100 mL of
deionized water at room temperature.20,43 Then, the solution was
stirred for 1 h using a magnetic stirrer. The pH of the solution was
adjusted to ≈10.5 by adding 0.5 M NaOH. After 30 min of stirring at
80 °C, the resulting precipitate was filtered, washed with DI water
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three times, and dried in an oven at 80 °C overnight. The solid
samples were calcined under airflow at 800 °C for 3 h.
2.2.3. Preparation of PVDF/rGO−Zn0.5Ni0.5Fe2O4 Nanocompo-
site. In the first step, PVDF pellets were dissolved in DMF under
stirring using a shear mixer (2000 rpm) at 60 °C. Next, the rGO
suspensions were added to the solution and dispersed using a probe
sonicator for 10 min at 100 W. Finally, the solution was film-cast at 80
°C to obtain a uniform film. In the postmixing stage, the
nanocomposite was transferred to a melt mixer (Alberta polymer
asymmetric minimixer, 2 mL) and further mixed at 220 °C and 120
rpm for 5 min. This process was conducted to ensure the uniform
dispersion of rGO in the PVDF matrix. The same procedure was
followed to fabricate PVDF/Zn0.5Ni0.5Fe2O4 nanocomposites and
hybrid samples. In these samples, both fillers were added to DMF
simultaneously, at a concentration of 1 and 5 wt % for rGO and the
magnetic nanoparticle, respectively. The PVDF nanocomposites
containing various rGO and Zn0.5Ni0.5Fe2O4 contents are denoted
as PVDF/rGO-Y% and PVDF/ZnNiFe-Y%, respectively. All samples
were compression-molded at 220 °C and 5 ksi for 5 min to fabricate
sheet-like specimens, with thicknesses ranging from 0.2 to 1.8 mm and
different configurations (single-layer and multilayer). To prepare the
multilayer samples, various layers (two and nine layers) with
particular arrangements were loaded on the mold and then pressed
at 100 °C and 1 ksi for 2 min. The two-layer nanocomposites contain
one conductive layer (1 wt % rGO) with a thickness of 0.8 mm and
one magnetic layer (5 wt % ZnNiFe) with the thickness ranging from
0.2 to 1.0 mm. Moreover, the nine-layer nanocomposite has four
conductive layers and five magnetic layers, where the thickness of
each layer is 0.2 mm, and the concentrations of the fillers are 1 and 5
wt % for rGO and ZnNiFe, respectively. The details of the samples’
names, combinations, and configurations are given in the Supporting
Information, Figure S1. The nomenclature of samples and their
specifications are listed in Table 3.
2.3. Characterizations. The phase identification and crystallinity
of the sample were studied by XRD analysis on a Bruker D8 FOCUS
XRD instrument with a Cu Kα radiation source, operating at 40 kV
and 30 mA in a scanning range of 2θ = 10−60°. The microstructure
and morphology of the prepared samples were studied using scanning
electron microscopy (SEM, MIRA3-TESCAN-3-XMU, Czech Re-
public). EDX elemental analysis was carried out by an EDX analyzer
(Oxford Instruments, United Kingdom). The FTIR spectra of the
samples were recorded on a Nicolet-S20 Fourier spectrometer in the
range of 400−4000 cm−1. The crystallinity of GO was further
investigated using the TEM analysis. The Raman spectra of GO and
rGO samples were measured via a Raman analyzer (Thermo Scientific
Nicolet Almega XR dispersive Raman spectrometer). The saturation
magnetization of Zn0.5Ni0.5Fe2O4 was measured at room temperature
using a vibrating sample magnetometer (VSM) (Lake Shore 7400). A
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Table 3. Specifications and Nomenclature

ZnNiFe rGO total
concentration concentration thickness of the thickness of the thickness number of
sample name (wt %) (wt %) PVDF−rGO layer (mm) PVDF−ZnNiFe layer (mm) (mm) layers
PVDF/rGO-0.8-0.5% 0.5 0.8 0.8 1
PVDF/rGO-0.8-1% 1
PVDF/rGO-0.8-3% 3
PVDF/rGO-0.8-5% 5
PVDF/rGO-1.4-0.5% 0.5 1.4 1.4
PVDF/rGO-1.4-1% 1
PVDF/rGO-1.4-3% 3
PVDF/rGO-1.4-5% 5
PVDF/rGO-2.0-0.5% 0.5 2.0 2.0
PVDF/rGO-2.0-1% 1
PVDF/rGO-2.0-3% 3
PVDF/rGO-2.0-5% 5
PVDF/ZnNiFe-0.2-1% 1 0.2 0.2 1
PVDF/ZnNiFe-0.2-3% 3
PVDF/ZnNiFe-0.2-5% 5
PVDF/ZnNiFe-0.2-7% 7
PVDF/ZnNiFe-0.2-10% 10
PVDF/ZnNiFe-0.6-1% 1 0.6 0.6
PVDF/ZnNiFe-0.6-3% 3
PVDF/ZnNiFe-0.6-5% 5
PVDF/ZnNiFe-0.6-7% 7
PVDF/ZnNiFe-0.6-10% 10
PVDF/ZnNiFe-08-1% 1 0.8 0.8
PVDF/ZnNiFe-0.8-3% 3
PVDF/ZnNiFe-0.8-5% 5
PVDF/ZnNiFe-0.8-7% 7
PVDF/ZnNiFe-0.8-10% 10
PVDF/ZnNiFe-1-1% 1 1.0 1.0
PVDF/ZnNiFe-1-3% 3
PVDF/ZnNiFe-1-5% 5
PVDF/ZnNiFe-1-7% 7
PVDF/ZnNiFe-1-10% 10
PVDF/rGO-ZnNiFe-0.8 5 1 0.8 1
(hybrid)
PVDF/rGO-ZnNiFe-1 1.0
(hybrid)
PVDF/rGO-ZnNiFe-1.4 1.4
(hybrid)
PVDF/rGO-ZnNiFe-1.6 1.6
(hybrid)
PVDF/rGO-ZnNiFe-1.8 1.8
(hybrid)
PVDF/rGO-ZnNiFe-1 5 1 0.8 02 1.0 2
(2-layer)
PVDF/rGO-ZnNiFe-1.4 0.6 1.4
(2-layer)
PVDF/rGO-ZnNiFe-1.6 0.8 1.6
(2-layer)
PVDF/rGO-ZnNiFe-1.8 1.0 1.8
(2-layer)
PVDF/rGO-ZnNiFe-1.8 5 1 0.2 (4) 0.2 (5) 1.8
(9-layer)

Thermo Fisher iCAP 6000 ICP-AES instrument was used to trace the properties in the X-band frequency range (8.2−12.4 GHz). S-
Zn, Ni, and Fe contents of the synthesized magnetic nanoparticle. The
Parameters are used to calculate the shielding parameters in a two-
electrical conductivity of the compression-molded nanocomposites
was measured using two different conductivity meters. A Loresta GX port EMI shielding setup. S11 and S22 are reflected over the incident
resistivity meter (MCP-T700 model, Mitsubishi Chemical Co., Japan)
voltage magnitude, whereas S21 and S12 are transmitted over the
was used for conductive samples with electrical conductivities of more
than 10−4 S/cm, and a Hiresta UX resistivity meter (MCP-HT800 incident voltage magnitude in ports 1 and 2, respectively. The SET,
model, Mitsubishi Chemical Co., Japan) was employed for insulative
SER, and SEA values of materials were obtained through the following
samples with electrical conductivities less than 10−4 S/cm. A Keysight
vector network analyzer was used to measure EMI shielding equations

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Figure 2. (a) Magnetic hysteresis loops of the synthesized Zn0.5Ni0.5Fe2O4 nanoparticles at room temperature, (b) XRD patterns of different
samples, (c) Raman spectroscopy of GO and rGO, and (d) FTIR patterns of different samples.

1 1 frequency sweep test mode. This test was performed in the angular
SE R = 10 log = 10 log
1−R 1 − |S11|2 (1) frequency range of 600 to 0.1% at a strain amplitude of 1%.

1−R 1 − |S11|2 3. RESULTS AND DISCUSSION

SEA = 10 log = 10 log
T |S21|2 (2) 3.1. Nanomaterial Characterizations. 3.1.1. Magnet-
EMI SE = SE R + SEA (3)
ization Measurement. The specific magnetization value of
Zn0.5Ni0.5Fe2O4 nanoferrite is shown in Figure 2a. The
A=1−R−T (4) magnetic hysteresis loop exhibited the S-type shape, which is
where A, R, and T are absorbance, reflectance, and transmittance typical of spinel ferrites. The magnetization of Zn0.5Ni0.5Fe2O4
coefficients, respectively. Rheological measurements were performed nanoparticles increased by enhancing the external magnetic
using an Anton Paar MCR 102 rheometer equipped with a 25 mm field strength and reached a maximum value of ≈76 emu/g.
diameter parallel plate geometry at a gap size of 0.8 mm and in However, the magnetization did not get saturated under the
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Figure 3. (a,b) FESEM of the synthesized Zn0.5Ni0.5Fe2O4 nanoparticles, (c) EDX spectrum of Ni0.5Zn0.5Fe2O4 nanoparticles, (d) surface particle
size distribution histogram of Zn0.5Ni0.5Fe2O4 nanoparticles, (e) FESEM image of rGO, (f) EDX spectrum of rGO, and (g,h) TEM images of rGO.

applied external magnetic field of 16.5 kOe. The nonsaturated intercluster antiferromagnetic interactions along with the
hysteretic behavior can be attributed to the possible strong ferromagnetic ones inside the clusters. The magnetic hysteresis
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loop revealed that the synthesized material is superparamag-
netic with the saturation magnetization (Ms) of 75.8 emu/g,
remanence (Mr) of 13.9 emu/g, and coercive force (Hc) near
to zero. In such a structure, A2+ and B3+ cations occupy the
octahedral or tetrahedral sites depending on their lattice
environments. A and B refer to cations with charge numbers of
+2 and +3, respectively. Incorporating diamagnetic Zn2+ ions
into the NiFe2O4 structure improved the total magnetization
by migrating Fe3+ ions from octahedral sites to the tetrahedral
sites, which increased the magnetic moment and ended in
improved total magnetization.20,44
3.1.2. XRD Analysis. The XRD analysis showed a sharp
diffraction peak at 2θ ≈ 11° (001) for GO, corresponding to a
d-space of 0.866 nm due to the introduction of oxygen-
containing functional groups during the oxidation process (see
Figure 2b). The absence of diffraction peak at 2θ ≈ 26° proved
the complete oxidation of graphite. This peak corresponds to a
d-space of 0.335 nm; thus, 0.866 nm for GO showed a good
exfoliation. The rGO sample exhibited a broad diffraction peak
at 2θ ≈ 25° with a corresponding interlayer spacing of 0.350
nm, indicating successful GO reduction. A glance over the
diffraction pattern of the Zn0.5Ni0.5Fe2O4 sample revealed that
all detectable peaks are indexed to the highly crystalline
Zn0.5Ni0.5Fe2O4 structure (JCPDS: 00-008-0234). Regarding
reference patterns, the diffraction peaks of PVDF are
detectable in the XRD patterns of the nanocomposites. The
peaks at about 2θ = 17.87, 18.39, 20.12, 36.19, and 38.63° and
2θ = 18.47, 20.16, 36.34, and 38.78° are assigned to the α
phase (JCPDS 00-042-1650) and β phase (00-038-1638) of
monoclinic PVDF, respectively.
3.1.3. Raman Analysis. The Raman spectrum of GO and
rGO are depicted in Figure 2c. As shown, GO well-defined
peaks at 1347 and 1569 cm−1, which correspond to the D and
G bands of graphene, confirms the synthesis of well-exfoliated
GO from graphite. The GO also showed an ID/IG ratio of 0.99,
after employing phosphoric acid as a defect-preventing agent,
which binds to vicinal diol and inhibits the production of
carbonyl functional groups. In addition, rGO showed D and G
bands at similar positions to GO’s, but with higher peak
intensities. The ID/IG ratio for rGO (0.91) was lower than that
for GO (0.99), demonstrating the improved crystallinity of GO
after reduction. Generally for GO, the 2D peak is the second
order of the D peak and appears around 2710 cm−1. No defects
are required for 2D band activation, and the 2D peak is always
present for GO and rGO. Depending on the number of layers,
the intensity of the 2D peak changes, and the narrower the
peak, the fewer would be the graphene layers.
3.1.4. FTIR Analysis. The FTIR analysis is illustrated in
Figure 2d. The characteristic peaks located at 764, 796, 976,
1149, and 1210 cm−1 are assigned to the nonpolar α-phase of
PVDF. Moreover, the absorption peaks appearing at 1274 and
841 cm−1 characterize the polar β phase of PVDF. The
characteristic peaks of GO occurred at 1170−1200, 1680−
1720, 3300−3400, and 1490−1620 cm−1, assigned to the
stretching vibrations of C−O, CO, O−H, and CC,
respectively. These carbon−oxygen functional groups were
also observed in rGO; however, their characteristic peaks are
significantly weakened. The vibration frequency peaks at 600−
700, 1410, 1600−1700, and 3400−3800 cm−1 can be
recognized from the FTIR spectra of magnetic samples.45,46
The absorption peak in the region of 600−700 cm−1 is the
typical characteristic vibration in the spinel structure,
attributed to the stretching mode of Fe−O at tetrahedral
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sites. The detection of this characteristic peak confirmed the
formation of a well-crystallized Zn0.5Ni0.5Fe2O4 spinel phase,
previously approved by the XRD analysis. The characteristic
band at 764 cm−1 corresponds to the nonpolar α phase in
PVDF, and the two vibrational bands at 1194 and 1234 cm−1
are attributed to the β phase, respectively.47−49
3.1.5. Morphology and Elemental Studies. The micro-
graph images and the corresponding EDX elemental analysis
results of Zn0.5Ni0.5Fe2O4 nanoparticles and rGO sheets are
shown in Figure 3. As can be seen in Figure 3a,b, the magnetic
sample exhibited homogeneous and spherical nanoparticle
morphology, with the sizes ranging mainly from 30 to 90 nm.
The EDX spectrum and dot-mapping of Zn0.5Ni0.5Fe2O4
nanoparticles demonstrated the presence of Fe, Zn, Ni, and
O elements and without any impurities in their structure. In
addition, Ni/Zn or Fe/Ni ratios determined by the chemical
analysis were close to those used in the synthesis precursors.
These results demonstrate the ability of the precipitation
method in controlling the size and dispersion of species,
endorsing the successful synthesis of the magnetic sample (see
Figure 3c,d). The SEM micrograph of a vacuum-filtered rGO
micrometer-thick film given in Figure 3e showed the expansion
of layers featuring smooth edges and surfaces. To prepare this
film, the synthesized GO was first filtered using a vacuum-
assisted method and then reduced with hydrazine, as described
in the Supporting Information. The EDX spectrum of rGO
showed characteristic peaks of O and C elements. GO has a
carbon/oxygen (C/O) atomic ratio of ∼1.3, while this ratio for
rGO is 2.22. The increased C/O ratio of rGO is due to the
reduction of oxygen-containing functional groups. No extra
peaks were detected within the detection limit of EDX
spectroscopy, validating the successful synthesis of rGO. The
layered and 2D structure of the as-synthesized rGO was
confirmed by the TEM image of nanosheets (Figure 3g,h).
This observation proved the hypothesis made in the XRD
results about the exfoliation of layers.50,51 The dispersion
quality of the nanoparticles in the PVDF matrix was assessed
by optical microscopy (see Figure S2), and was quantified via
transparency and agglomerate area ratio. Further details
regarding the assessment of the dispersion quality based on
this technique can be found in the Supporting Information and
our previous works.
3.2. Electrical Conductivity and EMI Shielding
Performance. SE, also known as total shielding effectiveness
(SET), is routinely used to assess the efficiency of different
EMI shields. The sum of reflection loss (SER) and absorption
loss (SEA) can be used to calculate SET, as stated in eq 3.
Understanding EMI shielding mechanisms and affecting
parameters is critical to design advanced EMI shield
compsoites. When an electromagnetic wave strikes a shield,
the electrons and other charged particles inside the shield
respond to the incident wave by generating a dispersed or
induced field. This interaction of the incident wave with the
surface mobile charge carriers is translated to reflect the
electromagnetic waves. Therefore, most of the materials that
are employed as EMI shields tend to be conductive, due to
their high density of mobile charge carriers. Aside from
reflection, incident wave dissipation in the form of heat
(absorption) and multiple reflections of electromagnetic waves
within an EMI shield also contribute to the shielding efficacy.
PVDF is electrically insulative with extremely low electrical
conductivity of ∼10−14 S/cm. Although the incorporation of 5
wt % of ZnNiFe nanoparticles slightly improved the electrical
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Figure 4. (a) Electrical conductivity of single-layer PVDF/rGO, PVDF/ZnNiFe, and their hybrid systems, (b) EMI SE (average SET, SEA, and
SER) and R of single-layer, two-layer, and hybrid PVDF/filler nanocomposites with different thicknesses, (c) R and A of the PVDF/filler
nanocomposites, (d) T of the PVDF/filler nanocomposites. The single-layer/two-layer nanocomposites containing various rGO and ZnNiFe
contents are denoted as PVDF/rGO/ZnNiFe-Y-X%, where Y is the thickness and X% is the filler concentration. The hybrid samples are shown as
PVDF/rGO−ZnNiFe-Y, where Y is the thickness. In the case of hybrid samples, the concentration of rGO and ZnNiFe is 1 and 5 wt %,
respectively.

conductivity, the PVDF/ZnNiFe nanocomposite was still in
the insulative zone, its electrical conductivity was 4.26 × 10−9
S/cm (see Figure 4a). The inferior electrical conductivity of
the PVDF/ZnNiFe nanocomposite can be attributed to the
low inherent electrical conductivity and small surface area of
the magnetic nanoparticles conjugated with their inability to
form a 3D interconnected network structure. This is also
shown by the rheological results (see Figure S3).52,53 However,
according to Figure 4a, with the introduction of only 0.5 wt %
of rGO, the electrical conductivity of the PVDF/rGO
nanocomposite surged to the conductive region, that is, 6.87
× 10−3 S/cm. By increasing the loading of rGO nanosheets up
to 1 wt %, the network structure was further enhanced, and
more conductive paths were formed throughout the PVDF/
rGO sample, contributing to the sharp enhancement of the
electrical conductivity (1.41 × 10−2 S/cm). However, in the
hybrid samples, introducing magnetic nanoparticles to the
conductive PVDF/rGO nanocomposite reduced the electrical
conductivity. For example, when 5 wt % of a magnetic
nanoparticle was added to PVDF/rGO-1-1%, the electrical
conductivity of the nanocomposite decreased from 1.41 × 10−2
to 1.05 × 10−4 S/cm, as shown in Figure 4a. This reduction in
the electrical conductivity of the samples can be attributed to
the poor conductivity of the ZnNiFe nanoparticles/clusters,
disrupting the continuous conductive network of the nano-
5521
sheets to some extent. This is in complete agreement with the
rheological results in which both dynamic moduli decreased
upon the addition of ZnNiFe to the PVDF/rGO nano-
composites (see Figure S3).
Apart from electrical conductivity, the EMI shielding
characteristics of a material can also be improved via increasing
the thickness or engineering the macrostructure of the
fabricated shields. Figure S4 shows the EMI SE of single-
layer conductive nanocomposites at various rGO concen-
trations and film thicknesses. As the filler concentration
increases, the EMI SE rises. However, the high price and the
synthesis complexity of the rGO nanosheets limit their
application at high loadings. Besides, in terms of industrial
applications, optimizing the thickness of the conductive
nanocomposites is of utmost importance for reducing the
cost and total weight of the shields. In order to address these
challenges, in the rest of this study, we utilized conductive
nanocomposites that contain only 1 wt % of rGO for
developing multilayer EMI shields. In addition, the total
thickness of the rGO nanocomposite layer was kept at 0.8 mm
(i.e., two-layer samples include just one conductive layer with a
thickness of 0.8 mm, and nine-layer EMI shields consist of four
conductive layers with a thickness of 0.2 mm each). More
details regarding samples’ labels are offered in Table 3. We will
show that even at this relatively low rGO concentration and
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Figure 5. (a−d) Values of SER, SEA, and SET for hybrid PVDF/rGO−ZnNiFe nanocomposites with different thicknesses and (e−h) values of SER,
SEA, and SET for two-layer PVDF/rGO−ZnNiFe nanocomposites with different thicknesses. The results are over the X-band frequency range. The
two-layer/hybrid nanocomposites are denoted as PVDF/rGO−ZnNiFe-Y, where Y is the thickness. In the case of two-layer/hybrid samples, the
concentration of rGO and ZnNiFe is 1 and 5 wt %, respectively.

small film thicknesses, the rGO nanocomposites can be
combined with ZnNiFe magnetic counterparts to fabricate
multilayer structures that meet the shielding requirements for
commercial applications, that is, SET > 20 dB.
The effects of magnetic nanoparticle concentration and the
thickness of the prepared single-layer magnetic nanocompo-
sites on EMI SE are shown in Figure S5. Due to the poor
electrical conductivity of the magnetic nanocomposites, they
5522
present inferior shielding performance. The EMI SE of the
magnetic nanocomposites at the lowest concentration (1 wt
%) of the nanoparticles is about 0.61 dB. This value reached to
2.84 dB by increasing the nanoparticle concentration to 5 wt
%. However, this amount decreased as the nanoparticle
concentration further increased from 5 to 10 wt %, which
can be attributed to the poor dispersion of nanoparticles in the
matrix at extremely high concentrations. Large agglomerates
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Figure 6. (a) Values of SER, SEA, and SET for two-layer PVDF/rGO−ZnNiFe nanocomposite, (b) values of SER, SEA, and SET for nine-layer
PVDF/rGO−ZnNiFe nanocomposite, (c) average SET, SEA, and SER of the two- and nine-layer structure PVDF−filler nanocomposites with the
same thickness (1.8 mm) and same filler concentration of rGO (1 wt %) and ZnNiFe (5 wt %), and (d) comparison of A of the current work with
those of the literature.14,17,35,37,41,62−69 The results are over the X-band frequency range.

were detected in various regions of the PVDF/ZnNiFe (10 wt
%) nanocomposite, corroborated by optical images and
rheological measurements (see Figures S2b,c and S3).
Based on the results of Figure S5, the single-layer magnetic
nanocomposite holding 5 wt % magnetic nanoparticles
(featuring the highest EMI SE) was used to develop the
multilayer (two-layer and nine-layer) structured shields at a
constant total thickness of 1.8 mm. The EMI SE of the selected
single-layer magnetic and conductive nanocomposites used in
two-layer assemblies is shown in Figure S6.
In this study, the main purpose of fabricating the multilayer
EMI shields is to control the shielding mechanisms. As such, to
expound on the EMI shielding mechanism of the fabricated
PVDF/rGO−ZnNiFe multilayer shields, SET, SEA, SER, and
shielding coefficients (R and A) were measured and presented
in Figure 4b−d. Comparing the findings in Figures 4b and S4,
we can see that the SEA values are higher than the SER values
for all samples (single-layer, two-layer, and hybrid). It is
important to note that SER and SEA have been used in the
literature to evaluate the shielding mechanisms of various
materials. However, determining the dominant shielding
mechanism based on these parameters is not the correct
approach as SER and SEA are the ratios of the input or output
powers (relative quantities). As such, A and R should be
compared to investigate the shielding mechanisms.54,55
Figure 5 compares the total EMI SE of the hybrid PVDF/
rGO−ZnNiFe (Figure 5a−d) and two-layer PVDF/rGO−
ZnNiFe nanocomposites (Figure 5e−h). The dielectric loss
and magnetic loss occur due to rGO nanosheets and ZnNiFe
nanoparticles, respectively. To begin with, it is evident that SET
5523
of the two-layer nanocomposites is significantly higher than
that of the hybrid nanocomposite (i.e., mixed nanoparticles in
single-layer structure, see Figure S1, to clarify each structure).
The EMI SE value of the two-layer structure with a thickness
of 1.8 mm is 24 dB, about 35% higher than that of the hybrid
PVDF/rGO−ZnNiFe nanocomposites (17.45 dB) at the same
thickness. Our results showed that the network formation in
multilayer structure and hybrid nanocomposites were different.
Previous results support this claim in which the electrical
conductivity and rheological properties of the PVDF/rGO
nanocomposite decreased upon the addition of magnetic
nanoparticles. In other words, the conductive network
structure of the rGO nanosheets remains intact in the
multilayer assemblies, while, the magnetic nanoparticles
deteriorate the conductive network of the nanosheets in the
hybrid samples. That is, the conductive PVDF/rGO and
magnetic PVDF/ZnNiFe layers in the multilayer structure
attenuate the electric and magnetic components of the EM
waves to their utmost power, leading to superior SET of the
multilayer structure over the single-layer hybrid structure. In
addition, multiple internal reflections of the electromagnetic
waves between the conductive and magnetic layers further
contribute to the SET value of the multilayer shields.
The SET, SEA, and SER values of the two-layer PVDF/rGO−
ZnNiFe-1.8 film were found to be 23.93, 23.22, and 0.71 dB,
respectively, and the power coefficients shown in Figure 4c
revealed that A = 0.85 is considerably greater than R = 0.15,
meaning an absorption-dominant shielding mechanism. Hence,
the two-layer shields absorb a considerable portion of the
electromagnetic wave. A = 0.499 and R = 0.483 were obtained
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ACS Applied Electronic Materials
for the single-layer hybrid sample, indicating the lower ability
of this structure in absorption.
To further explain the shielding mechanisms, it is
hypothesized that there are several potential mechanisms
responsible for the enhanced absorption of the electromagnetic
waves in the multilayer structures. According to the
literature,56−59 the absorption mechanism is thought to be
mainly governed by two phenomena: (1) dipole polarization
and (2) interfacial polarization between the metal−organic
complexes and the matrix. However, the literature has shown
that interfacial polarization relaxes significantly over the X-
band frequency range; as such,55,60,61 we believe that the
contribution of the interfacial and dipole polarization
mechanisms is negligible. Therefore, it can be said that, in
the first layer of our multilayer samples, the PVDF/ZnNiFe
layer attenuates and absorbs the electromagnetic energy due to
hysteresis loss and magnetic domain resonance. Additionally,
the impedance matching of the ZnNiFe nanocomposites with
air plays a great role in the electromagnetic wave absorption. In
fact, negligible impedance mismatch between the first layer and
air minimizes the reflection mechanism. The incoming
electromagnetic wave then penetrated through the PVDF/
rGO layer with a strong reflectivity at the interface between the
PVDF/ZnNiFe and PVDF/rGO layers due to the high
impedance mismatch, leading to internal reflections. Multiple
reflections can either come from the layer’s interface or rGO
nanosheet surfaces, they can happen at two different scales. As
a result, the superior EMI shielding efficiency of PVDF/rGO−
ZnNiFe-1.8 multilayer nanocomposites is primarily due to
their unique multilayer structures combined with great
magnetic properties of ZnNiFe.
Multilayer strategy and the abovementioned mechanisms
have been proposed in many recent studies.55 However, the A
coe of our proposed nanocomposites supras all the existing
works in the literature. We believe that the outstanding
absorption performance of shield is a direct result of the
excellent insulating and supermagnetic properties of ZnNiFe
nanoparticles. The combined Ni−Zn ferrites exhibited
relatively high resistivity, permeability, and saturation magnet-
ization values. The characteristics listed above are tunable and
highly dependent on the quantity of Zn and the synthesis
procedure. The highest saturation magnetization of
NixZn1‑xFe2O4 ferrites, i.e., ∼80 emu/g, can be achieved
when x = 0.5. This amount for Fe3O4, zinc, and nickel is about
70, 45, and 50 emu/g, respectively.62 Hence, EM energy is
attenuated by magnetic losses, including normal resonance and
eddy current losses, due to the great magnetism of ZnNiFe
nanoparticles.
3.2.1. Effect of Number of Layers (Two-Layer vs Nine-
Layer). To further investigate the effect of macrostructure
design on the EMI shielding performance, the two-layer
PVDF/rGO−ZnNiFe and nine-layer PVDF/rGO−ZnNiFe at
the same filler concentration and thickness (1.80 mm) are
compared in Figure 6a−c. The nine-layer PVDF/rGO−
ZnNiFe nanocomposite demonstrated a superior EMI
efficiency, with a SET value of 29.05 dB. More importantly,
the fascinating and significant aspect is that SEA is greater than
28.6 dB; thus, SER is less than 0.5 dB. Accordingly, A = 0.91 of
the nine-layer PVDF/rGO−ZnNiFe nanocomposite was even
higher than that of the two-layer PVDF/rGO−ZnNiFe
nanocomposite (i.e., A = 0.85, see Figure 6c). Hence,
increasing the number of the layers further contributes to
the absorption mechanism, attributed to more multiple
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internal reflections as more layers are employed in the
structure of the shield.
In order to assess the contribution of the present work, A of
our nine-layer PVDF/rGO−ZnNiFe shield is compared with
the reported values of the literature in Figure 6d. It is quite
difficult to reach excellent EMI SE simultaneously with a low R
in the case of conductive polymer-based nanocomposites.
However, in this study, both EMI SE and A values of the
alternating multilayer PVDF/rGO−ZnNiFe films were con-
currently enhanced to high levels, which outstrips over most
reported nanocomposites in the literature. The comparison
results (Figure 6d) vividly illustrate that our proposed
approach is valuable and competitive. This is because it
drastically improves the absorption properties of the nano-
composite films for applications where reflection should be
minimal.
4. CONCLUSIONS
To conclude, we developed a simple and effective method to
synthesize supermagnetic nanoparticles and highly conductive
reduced graphene oxide (rGO) nanosheets. First, XRD,
FESEM, FTIR, EDX, ICP, and VSM analyses revealed that
the magnetic and conductive fillers were synthesized
successfully. Then, multilayer structures of PVDF−rGO and
PVDF−ZnNiFe nanocomposites were prepared with different
contents of the fillers at various thicknesses. The multilayer
(both two-layer and nine-layer) structuring strategy not only
did improve the EMI SE but also signified the absorption
mechanism by multiple internal reflections. As a landmark, the
PVDF/rGO−ZnNiFe nanocomposite (nine-layer) with a
thickness of 1.8 mm exhibited an EMI SE of 29.05 dB, with
a reflection of 0.5 dB. It is important to note that more than
91% of the incident wave was absorbed, placing our sample
among the best EMI absorbers. Integrating these excellent
performances in one material, that is, PVDF/rGO−ZnNiFe
multilayer film, reveals the tremendous potential to develop
highly efficient EMI shields for applications where reflection
should be minimal, such as stealth airplanes and sensitive
radars.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsaelm.1c00940.
Structure of the generated samples, characterization of
the nanocomposites (optical images), rheological
characterization of the fabricated nanocomposites, total
EMI SE of the fabricated nanocomposites, EMI SE of
the two-layer structure and hybrid PVDF−filler nano-
composites, and ICP−MS results (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Mohammad Arjmand − Nanomaterials and Polymer
Nanocomposites Laboratory, School of Engineering,
University of British Columbia, Kelowna V1V 1V7 British
Columbia, Canada; orcid.org/0000-0002-8812-5638;
Email: mohammad.arjmand@ubc.ca
https://doi.org/10.1021/acsaelm.1c00940
ACS Appl. Electron. Mater. 2021, 3, 5514−5527
ACS Applied Electronic Materials
Authors
Majed Amini − Nanomaterials and Polymer Nanocomposites
Laboratory, School of Engineering, University of British
Columbia, Kelowna V1V 1V7 British Columbia, Canada
Milad Kamkar − Nanomaterials and Polymer Nanocomposites
Laboratory, School of Engineering, University of British
Columbia, Kelowna V1V 1V7 British Columbia, Canada
Farhad Rahmani − Department of Chemical Engineering,
Faculty of Engineering, University of Kurdistan, 66177-
15175 Sanandaj, Iran
Ahmadreza Ghaffarkhah − Nanomaterials and Polymer
Nanocomposites Laboratory, School of Engineering,
University of British Columbia, Kelowna V1V 1V7 British
Columbia, Canada
Farhad Ahmadijokani − Nanomaterials and Polymer
Nanocomposites Laboratory, School of Engineering,
University of British Columbia, Kelowna V1V 1V7 British
Columbia, Canada
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaelm.1c00940
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors acknowledge the support of the Natural Sciences
and Engineering Research Council of Canada (NSERC)
[funding reference number ALLRP 555586-20]. Dr. Arjmand
appreciates the support from the Canada Research Chairs
program. We are thankful to Prof. U. Sundararaj and Ms. Elnaz
Erfanian for their assistance with optical imaging. The authors
acknowledge the Syilx Okanagan Nation for the use of their
unceded ancestral traditional territory, the land on which the
research was conducted. The authors are grateful to Zentek
Ltd. for supporting this project.
■
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