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An Effective Design Strategy for the Sandwich Structure of PVDF/

GNP-Ni-CNT Composites with Remarkable Electromagnetic
Interference Shielding Effectiveness
Qing Qi, Li Ma, Biao Zhao, Sai Wang, Xiaobo Liu,* Yajie Lei,* and Chul B. Park*
Cite This: ACS Appl. Mater. Interfaces 2020, 12, 36568−36577 Read Online

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ABSTRACT: It is well-known that attractive electromagnetic interference (EMI) shielding performance depends on functional
(e.g., electrical and magnetic) fillers and structural designs. This paper presents a novel three-layered sandwich structure of
poly(vinylidene fluoride) (PVDF)-based nanocomposites, consisting of graphene nanoplatelets (GNP), nickel (Ni), and carbon
nanotubes (CNT). The unique three-layered sandwich structure of GNP-Ni-CNT exhibited excellent EMI shielding ability due to
the several interfaces of the multilayered structure with electric loss by the conductive fillers and magnetic loss by the magnetic filler.
The overall shielding performance could be further improved by increasing the overall thickness and the number of layers. With a
fixed thickness of 0.6 mm, the shielding effectiveness of the PVDF/GNP-Ni-CNT three-layered and six-layered structure composite
at 15 GHz was 41.8 and 46.4 dB, respectively. These results provide a useful strategy to prepare various EMI shielding materials with
a sandwich structure, presenting tremendous opportunities to design and manufacture advanced EMI shielding materials and
equipment.
KEYWORDS: conductive polymer composite,
poly(vinylidene fluoride)/graphene nanoplatelets (GNP)/nickel (Ni)/carbon nanotubes (CNT) composite film, electric conductivity,
electromagnetic interference shielding, mechanical properties

1. INTRODUCTION
Due to widespread use of mobile communication devices and
electronic equipment, electromagnetic interference (EMI)
pollution has become an unavoidable problem.1,2 Electro-
magnetic (EM) waves not only introduce signal distortion and
cause malfunction of electronic devices but also affect the
health of humans.3,4 Therefore, the creation of EMI shielding
materials has become increasingly important and, through the
innovation and efforts of researchers, polymer-based composite
EMI shielding materials consisting of insulating polymers and
fillers have been found. Due to the versatility, light weight,
adjustable, and corrosion resistance characteristics of these
materials, market demand has experienced tremendous
growth.5,6
To obtain high EMI shielding effectiveness (SE), the EMI
shielding materials typically utilize not only conductive
carbonaceous derivatives such as carbon nanotubes (CNTs)
and graphene but also magnetic fillers such as ferrite and
metals.7,8 Numerous researchers have studied the effects of
these conductive and magnetic fillers on the EMI shielding
mechanisms, namely absorption, reflection, and multiple
internal reflection9 with focus on strong absorption character-
istics. For example, Zhan et al. prepared Fe3O4@ reduced
graphene oxide/natural rubber composite exhibiting an EMI
SE of 15−45 dB.10 Yuan et al.11 prepared reduced graphene
oxide (RGO) coated Fe3O4@SiO2@polypyrrole film, and an
average EMI SE value of 32 dB was obtained. Dalal et al.12
Received: June 10, 2020
Accepted: July 20, 2020
Published: July 20, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsami.0c10600

36568 ACS Appl. Mater. Interfaces 2020, 12, 36568−36577
ACS Applied Materials & Interfaces
prepared RGO/PbTiO3 nanocomposites, and the value of SEA
EMI SE reached 46.1 dB. Zhao et al.7 prepared poly(vinylidene
fluoride) (PVDF)/CNT-nickel (Ni)-chain composites and
PVDF/graphene nanoplatelets (GNP)-Ni-chain composites.
Both of these composites exhibited very high EMI efficiency of
57.3 and 55.8 dB, respectively.
The performance of polymer-based EMI shielding materials
is not only related to the electrical and magnetic properties of
fillers but also to the internal structure of the composites.
Because the efficiency of reflection and absorption of EM
waves is mainly determined by the amounts of the conductive
and magnetic fillers, increasing the filler content is an essential
method to increase the EMI SE.13−15 However, adding too
much filler will negatively affect the material cost, the weight,
the mechanical properties, and so on. Thus, it has become a
trend to design unique structures to improve the EMI SE while
using low filler loading. Some efforts have been made to
manufacture functional composites with different structures
that have relatively good EMI SE. For example, Zhao et al.
investigated the thickness effect of the PVDF/GNP foam on
the EMI performance and obtained an EMI SE of 37.4 dB with
10 wt % GNP at a thickness of 3.0 mm.16 Zhang et al. prepared
a poly(ethylene oxide)/CNT composite with a multilayer
structure having an EMI SE of 35 dB at a thickness of 0.15
mm.17 Yu et al.5 prepared ultrahigh-molecular-weight-poly-
ethylene/CNT composites with oriented segregated con-
ductive networks with an EMI SE reaching 33.5 dB.15,18
In this study, novel three-layered PVDF/GNP-Ni-CNT
composites were prepared with the same filler content but
different structures and their EMI shielding properties were
investigated. The three-layered PVDF/GNP-Ni-CNT compo-
sites exhibited excellent EMI shielding ability as well as high
mechanical properties. The unique order of GNP-Ni-CNT (or
CNT-Ni-GNP) of three-layered sandwich structure compo-
sites turned out to exhibit the highest EMI SE compared to
other configurations of GNP-Ni-GNP, CNT-Ni-CNT, GNP-
CNT-Ni, CNT-GNP-Ni, Ni-CNT-GNP, and Ni-GNP-CNT.
The superiority of the magnetic (Ni) layer between the two
different conductive layers was ascribed to electric loss and
magnetic loss. The overall shielding performance could be
further improved by increasing the thickness of the EMI
shielding layer and the number of layers.
2. MATERIALS AND METHODS
2.1. Materials. PVDF with molecular weight 300,000−330,000 g
mol−1 was obtained from Solvay. Figure S2 shows its morphology.
The NC7000 MWCNTs were supplied by Nanocyl SA. GNPs were
purchased from Deyangene Carbon Technology Co., Ltd. and used as
received. Caledon Laboratories Ltd. provided N,N-dimethylforma-
mide (DMF). The Ni powder (#268283, Sigma-Aldrich) with a
diameter of ≤1 μm was bought from Sigma-Aldrich. Figure S3 shows
its morphology.
2.2. Preparation of PVDF/GNP-Ni-CNT Composite Films.
PVDF/GNP-Ni-CNT composite films were prepared using solvent
casting and then compression molding. A schematic illustration of the
steps is shown in Figure 1. First, each filler was uniformly dispersed in
a DMF solution by ultrasonication, and PVDF was fully dissolved in
DMF at a temperature of 80 °C by magnetic stirring. These two
separately prepared mixtures, i.e., filler + DMF and PVDF + DMF,
were combined together with mechanical stirring under sonication for
30 min. To prevent the fillers from sinking in our experiment, we
evaporated some of the DMF solution in the glass bottle without a lid
under magnetic stirring for 2 h at 80 °C. Then, we poured the viscous
and sticky DMF + PVDF+filler mixture on a glass plate. Then, we
evaporated the DMF from the solution on the glass plate by leaving it
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Figure 1. Schematic diagram of the sandwich structure PVDF/GNP-
Ni-CNT composite film.
for 12 h at 80 °C. When we checked each layer using SEM, the fillers
were all uniformly dispersed across the ∼200 μm thickness. All the
three fillers of GNP, Ni, and CNT were processed this way to create a
PVDF/GNP composite layer, PVDF/Ni composite layer, and PVDF/
CNT composite layer, separately. Finally, the three different layers
were put together to make a three-layered sandwich structure by hot
pressing. The hot-pressing process involved placing the sample in a
rectangular 16 mm × 8 mm mold and putting it in a press at a
temperature of 200 °C for 3 min to wait for the composite to fully
melt and then applying a pressure of 10 MPa. In order to expel the air
in the sample, pressure was applied and quickly released three times
after which the pressure was held at 10 MPa for 3 min, followed by
removing the sample and cooling at room temperature.
In order to investigate the effect of the layer order on the EMI
shielding properties, PVDF/GNP, PVDF/CNT, and PVDF/Ni
composites were prepared with the same mass fraction of 8.25 wt
% (9 phr per 100 PVDF). Then, PVDF/GNP, PVDF/CNT, and
PVDF/Ni films with different thicknesses of 0.1, 0.2, 0.4, and 0.8 mm
were prepared. The research consisted of three parts. First, the
influence of different orders of PVDF/GNP, PVDF/CNT, and
PVDF/Ni films on the EMI shielding efficiency of a three-layered
PVDF/GNP-Ni-CNT sandwich structure was investigated. Two
millimeter-thick films of PVDF/GNP, PVDF/CNT and PVDF/Ni
were hot pressed with different orders but with the same weight
content of the fillers. A series of PVDF/GNP-Ni-CNT three-layered
sandwich structure composites were created with different orders of
the PVDF/filler composite layers: i.e., GNP-CNT-Ni, GNP-Ni-CNT,
and Ni-GNP-CNT. All the 0.6 mm three-layered sandwich structure
PVDF/GNP-Ni-CNT composites had the same weight content of
2.75 wt % GNP, 2.75 wt % CNT, and 2.75 wt % Ni. Second, to
research the influence of thickness on this unique sandwich structure
PVDF/GNP-Ni-CNT composite, three-layered and six-layered
structures of PVDF/GNP-Ni-CNT were hot pressed with different
thicknesses of PVDF/GNP, PVDF/CNT, and PVDF/Ni layers. The
three-layered sandwich structure PVDF/GNP-Ni-CNT composites
with different thicknesses had same weight content of 2.75 wt % GNP,
2.75 wt % CNT, and 2.75 wt % Ni. Third, the influence of different
structures of PVDF/GNP-Ni-CNT composites with the same weight
content of 2.75 wt % GNP, 2.75 wt % CNT, and 2.75 wt % Ni were
prepared. They were PVDF/GNP-Ni-CNT blend, three-layered
PVDF/GNP-Ni-CNT, and six-layered PVDF/GNP-Ni-CNT compo-
sites with the same 0.6 mm thickness.
2.3. Characterization. To observe the morphologies of CNTs
and the graphene nanoplatelets, transmission electron microscopy
(TEM, Tecnai G2 F20 S-TWIN) was used. An X-ray diffractometer
(XRD, Rigaku Ultima IV) was used to verify the crystal structure and
sample phases. The fracture morphologies of the PVDF/GNP-Ni-
CNT films were measured by field-emission scanning electron
microscope (FE-SEM, JEOL JSM-7001F). The conductivities of the
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Figure 2. (a) XRD patterns and (b) FTIR spectra of the PVDF, PVDF/Ni, PVDF/GNP, PVDF/CNT, and PVDF/GNP-Ni-CNT composites.

PVDF/fillers composites were tested by a four-probe method.
Samples with a size of ∼15.79 mm × 7.89 mm × 0.3−2.4 mm
were tested by the waveguide method via a vector network analyzer
(VNA, Agilent N5227A) in the Ku-band frequency range of 12.4−
18.0 GHz. The parameters S11 (reflection coefficient data) and S21
(transmission coefficient data) of the samples were recorded and used
to calculate the EMI SE. Because of the negative values of the
measured S11 and S21, the total EMI SE (SET), the coefficients of
reflection (SER), and the coefficients of absorption (SEA) of materials
were expressed as in the following equations:19−21
1 CNTs and GNPs, their TEM images are shown in Figure 3a,b,
SER = 10 Lg
1 − |S11|2 (1)
phase. The α-phase can be observed at the absorption bands at
765, 793, and 974 cm−1, and the peaks at 840, 870, 1177, and
1275 cm−1 were assigned to the β-phase.11 The bands at 870,
1177, and 1275 cm−1 were assigned to CH2, and the bands at
1070 and 1402 cm−1 were the stretching vibration of CF2.25
From the FTIR spectra, it can be inferred that the PVDF and
PVDF/filler composites had both α-phase and β-phase.16 The
result is also in correspondence with the XRD results.
3.2. TEM and SEM Morphologies. To reveal the size of

1 − |S11|2
SEA = 10 Lg
|S21|2 (2)
SET = SER + SEA (3)

R = |S11|2 , T = |S21|2 , A = 1 − R − T (4)

The tensile properties of PVDF/fillers were tested by a universal
tester (Instron 5576, Instron, USA, n = 5 for each group).

3. RESULTS AND DISCUSSION

3.1. XRD and FTIR of PVDF/Filler Composites. To
demonstrate the successful preparation of PVDF/GNP-Ni-
CNT composites, the XRD patterns and FTIR spectra of the
PVDF, PVDF/Ni, PVDF/CNT, PVDF/GNP, and PVDF/
GNP-Ni-CNT composites are shown in Figure 2. All the
PVDF/filler composites and the pure PVDF have several
diffraction peaks at 17.6, 18.3, 19.9, and 26.51°, corresponding
to the planes of (100), (020), (110), and (021), respectively,
and also the reflection of the non-polar α-phase polymorph.22
There are three characteristic peaks at 2θ = 44.31, 51.78, and
76.36°, corresponding to (111), (200), and (220), respectively,
which can be assigned to Ni (JCPDS file card no. 04-0850).23 Figure 3. TEM images of (a) CNT and (b) GNP. SEM micrographs
The typical peak at 26.39° of the (002) plane belonged to the of the (c) three-layered PVDF/GNP-CNT-Ni composite. (d) PVDF/
GNP layer. (e) PVDF/Ni layer. (f) PVDF/CNT layer.
GNP and CNTs. The peaks at 20.15° was detected in the
curve of the PVDF, PVDF/Ni, PVDF/GNP, PVDF/CNT, and
PVDF/GNP-Ni-CNT nanocomposites, which are of the β- and it was found that the diameter of the CNTs is ∼10−20
crystalline phase. It is well-known that the PVDF β-crystalline nm. Crumpling or wrinkling of thin GNPs was also observed.
phase could cause dipole polarization under an alternating EM The SEM images of the three-layered sandwich structure of the
field and enhance the EM absorption properties.24 Thus, the PVDF/GNP/CNT/Ni composites with three different layers
presence of the β-crystalline form in PVDF and PVDF/filler can be clearly seen in Figure 3c. The dispersion quality of
can improve the EMI shielding properties. To determine the CNT, GNP, and Ni particles in the PVDF and the
difference between PVDF and PVDF/filler composites, the microstructure images of the PVDF/GNP layer, PVDF/Ni
FTIR spectra of PVDF and PVDF/filler are shown in Figure layer, and PVDF/CNT layer of the PVDF/GNP-Ni-CNT
2b. It can be seen that the PVDF and PVDF/filler composites composite are shown in Figure 3d,e. Good, random dispersion
had two different crystalline forms, i.e., the α-phase and β- of GNP, Ni, and CNT in the PVDF matrix can be seen. In the
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Figure 4. (a) Electrical conductivity PVDF/Ni and PVDF/GNP-Ni-CNT blends and PVDF/CNT and PVDF/GNP composites. (b) Average SET,
SEA, and SER, and (c) power of 0.2 mm-thick PVDF, PVDF/Ni, PVDF/CNT, and PVDF/GNP composites.

Figure 5. (a) EMI SE of the three-layered sandwich structure PVDF/filler composite with a thickness of 0.6 mm. (b) Average SET, SEA, and SER of
the three-layered PVDF/fillers composites. (c) R & A coefficient of the three-layered PVDF/fillers composites. (d) T coefficient of the three-
layered PVDF/fillers composite. (e) Scheme of three-layered PVDF/filler composites with a sandwich structure and the conclusions.

PVDF/8.25 wt %-GNP and PVDF/8.25 wt %-CNT composite
layers, more multilayered GNP or CNT bundles can be found
in the PVDF matrix.
3.3. Electrical Conductivity and EMI Shielding
Properties of PVDF/Filler Composites. The EMI shielding
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performance of composites is closely related to their electrical
properties. It is known that increasing the electrical
conductivity helps the reflection of electromagnetic radiation
from the surface.9 Meanwhile, with an increase in the
conductive filler content, the electrical conductivity is
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increased.26,27 To explore how the introduction of three
different types of filler with different features will affect the
electrical conductivity, the conductivities of PVDF/8.25 wt
%-Ni, PVDF/2.75 wt %-CNT-2.75 wt %-GNP-2.75 wt %-Ni,
PVDF/8.25 wt %-CNT, and PVDF/8.25 wt %-GNP
composites were measured, and the results are shown in
Figure 4. It was found that PVDF/filler composite with the
same weight content and a different filler structure had a
different conductivity: conductivity of PVDF/CNT (1D) <
conductivity of PVDF/GNP (2D). This phenomenon can be
explained by the electrical networks that were formed not only
in the same layers but also between different layers with the
PVDF/filler material with larger conductive networks exhibit-
ing higher electrical conductivity.28 To further understand the
EMI shielding performance of three-layered PVDF/GNP-Ni-
CNT composites, the EMI shielding properties of the PVDF,
PVDF/Ni, PVDF/CNT, and PVDF/GNP films with a 0.2 mm
thickness were investigated. From Figure 4b,c, it can be seen
that SET (PVDF/Ni) < SET (PVDF/CNT) < SET (PVDF/
GNP), R (PVDF/Ni) < R (PVDF/CNT) < R (PVDF/GNP),
and their EMI properties are proportional to their electrical
conductivities.
3.4. EMI Shielding Properties of Three-Layered PVDF/
Filler Composites. It is well-known that the electrical
conductivity has a large effect on the microwave attenuation.29
This can be used to analyze the EMI shielding mechanism of
the PVDF/GNP-Ni-CNT three-layered sandwich structure
composites. The electrical conductivity of carbon-based
composites is lower than that of the metal EMI shielding
materials because the surface of the carbon-based composites
has no free electrons. For this reason, the EM waves reflected
from the surface will be less in the carbon-based materials, and
the attenuation of penetrated EM waves would be much
higher.26 The total EMI SE of the three-layered sandwich
structure PVDF/fillers composites (0.6 mm) can be found in
Figure 5a. PVDF/GNP and PVDF/CNT layers were used to
produce electrical loss, and the PVDF/Ni layer was used to
produce magnetic loss.
First, it is clear that the SET of the three-layered sandwich
structure composites is much higher than that of the plain
structured composite at all frequencies. The three-layered
sandwich structures achieved an EMI SE of 30−41 dB, which
was a large increase of 47−95% compared to the plain
structure of the PVDF/GNP-Ni-CNT blend composite. The
difference between the three-layer sandwich structured and
plain structured composites is that the former has more
extensively connected networks than the latter. The electrical
conductivity of the composite in Figure 4 provides strong
support for this.
Second, the effect of the three layers’ order on the EMI SE
was investigated while maintaining the same amount of filler in
each layer. For convenience, each PVDF/filler composite is
identified by its special filler order in the composite. For
example, the string “PVDF/GNP-Ni-CNT” in Figure 5a refers
to a three-layered PVDF/GNP-Ni-CNT composite with
PVDF/GNP as the first layer, PVDF/Ni as the second layer,
and PVDF/CNT as the third layer. The order of the three
types of layer was changed to compare the EMI SE of PVDF/
GNP-Ni-CNT, PVDF/CNT-Ni-GNP, PVDF/Ni-GNP-CNT,
PVDF/CNT-GNP-Ni, PVDF/Ni-CNT-GNP, and PVDF/
GNP-CNT-Ni composites with the same filler contents. The
composite with the highest EMI SE was PVDF/GNP-Ni-CNT
for which the value of SET can be as high as 40.5 dB. It can also
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be concluded that SEGNP‑Ni‑CNT ≈ SECNT‑Ni‑GNP > SECNT‑GNP‑Ni
≈ SE N i‑GNP‑CNT ≈ SE GNP‑CN T‑Ni ≈ SE N i‑CNT‑GNP >
SEPVDF/GNP‑Ni‑CNT blend. This trend of the EMI shielding
performance is the same as in the research of Zheng et al.30
This phenomenon can be attributed to the special order of
PVDF/GNP-Ni-CNT with the two outer layers having high
electrical conductivity, and the middle layer being the magnetic
loss layer. This unique structure can increase the SER,
apparently because of the unique order of different layers.
According to a previous report,31 using A and R to evaluate the
EMI shielding properties of materials is more intuitive than
using SEA and SER. It is clear from Figure 5c,d that the R values
of PVDF/filler composites were much higher than the A values
in the frequency range of 12.4−18.0 GHz. It can be concluded
that reflection played a major role in the total EMI SE, and
after the first reflection, absorption played a major role, which
is consistent with other reports.32−34 To clarify the different
behaviors of PVDF/GNP and PVDF/CNT, the EMI shielding
properties of PVDF/CNT-Ni-CNT and PVDF/GNP-Ni-GNP
were also investigated. It is interesting to find that their SE
values with the same weight content of fillers were lower than
for PVDF/GNP-Ni-CNT. The higher SE could be attributed
to the kinds of fillers, different fillers of GNP (2D), CNT
(1D), and Ni (0D), and they can form a large number of
heterogeneous interfaces, interfacial polarization loss, coherent
multiple reflections, and impedance rather than two kinds of
fillers. In the PVDF/GNP-Ni-CNT and PVDF/CNT-Ni-GNP
composites, the first PVDF/GNP (or PVDF/CNT) layer will
reflect more microwaves, the middle layer will increase the
magnetic loss, and then the third layer can both reflect
microwaves to the middle layer and increase the absorption of
microwaves. Only this unique structure with PVDF/Ni in the
middle layer possessed excellent EMI shielding efficiency. This
can be attributed not only to the electric dipoles’ interaction
with the electromagnetic fields in the radiation but also to the
reflection of the unique multilayer sandwich structure of the
PVDF/GNP-Ni-CNT composite.35
It was interesting to note a dramatically increased absorption
when we compared the EMI SEA of the individual layers and
that of the three-layer composites. Figure 4b,c shows that the
PVDF/CNT and PVDF/GNP layers exhibited strong
reflection because of the percolated conductive fillers’ high
conductivity. Even when either of these layers became the first
of the three-layer composites, the high conductivity would
result in a high reflection of the incoming microwave.
However, with the layered structure, the penetrated microwave
will be absorbed significantly by the layered structure through
multiple reflection, and therefore, the absorption became
significantly increased, as shown in Figure 5b.
From the research of Danlée et al.,36 they found that the
arrangement of the layers also plays an important role for
maximum absorption. The structure is built from alternating
films of dielectric polymer and conducting layers. As waves
propagate through multiple layers, reflections will increase, but
they will occur inside the multiple layers. Due to the reduced
reflected power, the conductivity gradient of the conductive
layer leads to a higher total absorption. Their report also
supports our research results that the unique multilayer
structure composed of alternating conductive and magnetic
layers exhibited higher absorption. To the phenomenon of
SECNT‑GNP‑Ni ≈ SENi‑GNP‑CNT ≈ SEGNP‑CNT‑Ni ≈ SENi‑CNT‑GNP,
we can find that all the samples have the same structure, the
PVDF/CNT and PVDF/GNP layer are pressed together, and
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Figure 6. (a) EMI SE; (b) SET, SEA, and SER; and (c) R & A coefficients of the three-layered sandwich structure PVDF/GNP-Ni-CNT composite
at various film thicknesses at 17 GHz.
Figure 7. SEM micrographs of the (a) PVDF/GNP-CNT-Ni blend composite, (b) three-layered PVDF/GNP-CNT-Ni composite, and (c) six-
layered PVDF-GNP/CNT-Ni composite with a thickness of 0.6 mm.
the conductivities of them are similar. Despite the three-layer
structure, these structures were not built from alternating films
of conductive and magnetic layers, and their structure can be
seen as a two-layer structure consisting of a conductive layer
and a magnetic layer. Therefore, their absorptions were lower
than the absorption of the PVDF/GNP-Ni-CNT or PVDF/
CNT-Ni-GNP composites.
The effect of film thickness on the EMI SE of sandwich
structure PVDF/GNP-Ni-CNT composites was also inves-
tigated, and the results are shown in Figure 6. Different
thicknesses (0.3, 0.6, 1.2, and 2.4 mm) of PVDF/GNP-Ni-
CNT were prepared using the same method as illustrated in
Figure 1. From Figure 6b, the SET, SEA, and SER of sandwich
structure PVDF/GNP-Ni-CNT composites was increased with
an increase in the film thickness. The PVDF/GNP-Ni-CNT
composite had an SET of 33.4 dB at 0.3 mm, and the SET was
increased to 47.8 dB at 1.2 mm. Meanwhile, it is found that
PVDF/GNP-Ni-CNT composite with 2.4 mm thickness
exhibited EMI shielding performance with frequency selectiv-
ity. The value of SET can reach 56.0 dB at a frequency of 17
GHz. This phenomenon was also reported by Song et al. where
two parallel graphene nanosheet layers act as the confinement
to trigger resonance.5 In this work, this phenomenon can be
explained by the wave’s propagation and reflection being
changed when microwaves pass through a multilayer structure.
The PVDF/GNP and PVDF/CNT layers can effectively
entrap the incoming EM waves and gradually attenuate them
by random multireflection and scattering.37 With an increase in
the sample thickness, the frequency selective phenomenon
became more apparent and can be ascribed to the microwave
length of the Ku band. The improvement in SE of a composite
material with a sandwich structure is due to constructive
interference between two parallel shielding layers and depends
on the thickness of the wave transmission layer d (d = nλ/4, n
= multiple).30 By analyzing the R and A coefficient values of
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the three-layer PVDF/GNP-Ni-CNT composites of various
thicknesses in Figure 6c, it can be concluded that the reflection
mechanism was the main contribution to the EMI shielding
performance. Compared with other polymer composites, these
PVDF/GNP-Ni-CNT sandwich structure composites possess
the characteristics of a low filler content and high shielding
efficiency at a low thickness.
3.5. SEM Images of the PVDF/Filler Blend and Six-
Layered PVDF/GNP-Ni-CNT Composite. To compare with
the three-layered PVDF/GNP-Ni-CNT composites, the EMI
shielding properties of six-layered PVDF/GNP-Ni-CNT
composites were also investigated. To explore the influence
of multilayer reflection on the sandwich structure PVDF/
GNP-Ni-CNT composites with more layers, six-layered
PVDF/GNP-Ni-CNT composites were prepared using the
same method as illustrated in Figure 1. The thickness of each
layer was changed to 0.1 mm, and then two 0.3 mm PVDF/
GNP-Ni-CNT sandwiches were hot pressed together to obtain
a six-layered PVDF/GNP-Ni-CNT composite with the same
weight content of fillers as the three-layered PVDF/GNP-Ni-
CNT composite. The SEM pictures of PVDF/GNP-Ni-CNT
blend (i.e., without any layer structure) and six-layered PVDF/
GNP-Ni-CNT composites are shown in Figure 7. From the
SEM image of the PVDF/GNP-Ni-CNT blend composite
(Figure 7a), it is seen that the three different fillers were
scattered in the matrix. Compared with the PVDF/GNP-Ni-
CNT blend composite (Figure 7a), the three-layered and six-
layered structures were successfully prepared and each layer
was clearly distinguished.
3.6. EMI Shielding Properties of the PVDF/Filler
Blend and Six-Layered PVDF/GNP-Ni-CNT. To understand
how the different structure of PVDF/GNP-Ni-CNT compo-
sites affected the EMI SE, the PVDF/GNP-Ni-CNT blend
composite, the three-layered PVDF/GNP-Ni-CNT composite,
and the six-layered PVDF/GNP-Ni-CNT composite with the
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ACS Applied Materials & Interfaces
Figure 8. (a) EMI SE of the different PVDF/GNP-Ni-CNT composites with a thickness of 0.6 mm. (b) R and A coefficient of the PVDF/filler
composites at 15 GHz; (c) Scheme of six-layered PVDF/filler composites with a sandwich structure and the conclusions.
same filler content and the same thickness of 0.6 mm were
tested in the frequency range of 12.4−18.0 GHz. As Figure 8a
shows, the three types of PVDF/GNP-Ni-CNT composite
films exhibited different EMI SE values, and the PVDF/GNP-
Ni-CNT composite with the six-layer structure exhibited the
best EMI performance with an SET value of 46.0 dB. From
Figure 8b, the R of the six-layered PVDF/GNP-Ni-CNT
composite was higher than three-layered PVDF/GNP-Ni-
CNT; we can also find that reflection played a major role in
the total EMI SE. This would be ascribed to the enhanced
multilayer reflection with the introduction of more layers into
the composite.17,38 This was also researched by Weng et al.39
and Wang et al.14
From the previous analysis, it was concluded that the EMI
shielding properties of the PVDF/GNP-Ni-CNT three-layered
sandwich structure composites is mainly attributed to the
reflection mechanism. The schematic diagram of Figures 5e
and 8c show the explanations for the high EMI shielding
performance and the possible EM shielding mechanisms of the
three-layered and the six-layered sandwich structure PVDF/
GNP-Ni-CNT composites. First, the PVDF/GNP-Ni-CNT
composites with two different structures possess high electrical
conductivity. The conductivity was related to the energy
attenuation when the current was through conduction,
hopping, and tunneling mechanisms, which can jointly
promote microwave absorption of composites.27,40 Second,
the interfaces between the fillers and the PVDF matrix will
cause interfacial polarization loss in the electromagnetic
field.20,41 This loss was caused by the accumulated charge in
the interface and occurred in heterogeneous interfaces.42
Third, EM energy is attenuated by magnetic losses, including
natural resonance and eddy current losses due to the
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magnetism of nickel particles.43,44 Fourth, the special sandwich
structure of the PVDF/GNP-Ni-CNT composites, which put
the PVDF/Ni layer in the middle, also improved the
microwave absorption because the electromagnetic reflection
through the conductive layers on both sides increased the
magnetic loss of the intermediate layer. Moreover, special
three-layered and six-layered sandwich structures of PVDF/
GNP-Ni-CNT composite films can increase the multiple
reflection loss.45 Above all, it was concluded that the sandwich
and/or multilayered structure of the PVDF/GNP-Ni-CNT
composite film, and the unique order of different layers
improved the EMI shielding performance.
In order to further highlight the excellent shielding
performance, the type of structure, and mechanical properties
of the PVDF/GNP-Ni-CNT composites with a low filler
content, Figure 9 compares the performance of the PVDF/
GNP-Ni-CNT composites against some representative EMI
shielding PVDF-based composites with a higher filler content.
From Table S1, it can be seen that the three-layered PVDF/
GNP-Ni-CNT composites with different thicknesses and six-
layered PVDF/GNP-Ni-CNT composites prepared in this
work possess the most comprehensive properties, such as light
weight, high tensile strength, and excellent reflection-
dominated EMI shielding property. Especially, the SE/
thickness of three-layered PVDF/GNP-Ni-CNT composite
could reach 112 dB/mm. Compared with other PVDF-based
composite materials,7,9,34,46−48 the three-layered and six-
layered PVDF/GNP-Ni-CNT composites exhibited superior
EMI shielding properties with a lower filler content, and this
work offers the possibility of further application of high-
performance EMI shielding materials in the fields of
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ACS Appl. Mater. Interfaces 2020, 12, 36568−36577
ACS Applied Materials & Interfaces
Figure 9. Comprehensive comparison for the EMI performance of
PVDF/GNP-Ni-CNT composites with other PVDF-based compo-
sites reported in previous works reported by refs 7, 9, 34, 46−48. Data
are listed in Table S1 in the Supporting Information.
construction, aerospace, and electronics, which have special
requirements for good mechanical strength.
3.7. The Mechanical Properties of PVDF/Filler
Composites. At the same time, inferior mechanical properties
will limit the practical application of EMI shielding
composites.49 From Figure 10, it can be found that the
PVDF/fillers composites exhibit an excellent mechanical
performance. Due to the volume fraction of three kinds of
fillers, their mechanical properties were different. The tensile
strength of PVDF > tensile strength of PVDF/Ni > tensile
strength of PVDF/CNT > tensile strength of PVDF/GNP.
The trends of tensile elongation of three different layers were
the same with tensile strength. The obvious elongation
enhancement may be due to the sandwich structure.50 The
small decrease in tensile strength could be ascribed to the
pores and cracks along the path of GNP, CNT, or Ni in the
composite, which hinder the transmission of stress, resulting in
a decrease in mechanical properties.4 Nevertheless, sandwich
structure and multilayer structure PVDF/GNP-Ni-CNT
composites possess excellent mechanical properties.
4. CONCLUSIONS
In summary, three types of structure, PVDF/GNP-Ni-CNT
blends, three-layered PVDF/GNP-Ni-CNT composite, and
six-layered PVDF/GNP-Ni-CNT composite were prepared
with the same weight content of fillers. TEM, SEM, FTIR, and
XRD revealed that the different structures of PVDF/GNP-Ni-
CNT composites were obtained successfully. The effects of a
different order of the three layers of PVDF/GNP-Ni-CNT
composites on EMI shielding properties were first investigated,
Figure 10. (a) Tensile stress−strain curves and (b) the average tensile strength, the Young’s modulus, and the elongation at break of PVDF and
PVDF/filler composites.
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and the three-layered PVDF/GNP-Ni-CNT composites
possessed higher EMI SE. Then, the EMI SE of the PVDF/
GNP-Ni-CNT blend, three-layered PVDF/GNP-Ni-CNT
composite, and six-layered PVDF/GNP-Ni-CNT composite
was investigated. The unique six-layered structure with PVDF/
GNP-Ni-CNT layer order endowed the composites with an
excellent EMI SE. The SET values of the PVDF/GNP-Ni-CNT
blend, three-layered PVDF/GNP-Ni-CNT composite, and six-
layered PVDF/GNP-Ni-CNT composite at 0.6 mm thickness
were 20.7, 39.65, and 46.4 dB, respectively. With the effects of
the carbon materials (GNP and CNT), the magnetic material
(Ni), and the special multilayer structure of PVDF/GNP-Ni-
CNT composites, the main EMI SE was from absorption and
multilayer reflection. Meanwhile, both of the three-layered and
six-layered sandwich structure PVDF/GNP-Ni-CNT compo-
sites exhibited excellent mechanical properties. In summary,
the PVDF/GNP-Ni-CNT composites have high potential for
preparing high-efficiency EMI shielding materials with better
mechanical properties, providing materials to be widely used in
aerospace, automobile, sports, and electronic applications.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.0c10600.
Summary of the EMI shielding performance of typical
PVDF-based materials, microwave attenuation mecha-
nism of the three-layered PVDF/GNP-Ni-CNT sand-
wich structure film and the six-layered PVDF/GNP-Ni-
CNT sandwich structure film, and SEM micrograph of
pure PVDF and pure Ni (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Xiaobo Liu − Research Branch of Advanced Functional
Materials, School of Materials and Energy, University of
Electronic Science and Technology of China, Chengdu 610054,
China; Email: liuxb@uestc.edu.cn
Yajie Lei − Institute of Chemical Materials, China Academy of
Engineering Physics, Mianyang 621900, Sichuan, China;
Email: leiyajie2004@caep.cn
Chul B. Park − Microcellular Plastics Manufacturing
Laboratory, Department of Mechanical and Industrial
Engineering, University of Toronto, 5 King’s College Road,
Toronto M5S 3G8, Canada; orcid.org/0000-0002-1702-
1268; Email: park@mie.utoronto.ca
https://dx.doi.org/10.1021/acsami.0c10600
ACS Appl. Mater. Interfaces 2020, 12, 36568−36577
ACS Applied Materials & Interfaces
Authors
Qing Qi − Research Branch of Advanced Functional Materials,
School of Materials and Energy, University of Electronic Science
and Technology of China, Chengdu 610054, China;
Microcellular Plastics Manufacturing Laboratory, Department
of Mechanical and Industrial Engineering, University of
Toronto, 5 King’s College Road, Toronto M5S 3G8, Canada;
Institute of Chemical Materials, China Academy of Engineering
Physics, Mianyang 621900, Sichuan, China
Li Ma − Microcellular Plastics Manufacturing Laboratory,
Department of Mechanical and Industrial Engineering,
University of Toronto, 5 King’s College Road, Toronto M5S
3G8, Canada
Biao Zhao − Microcellular Plastics Manufacturing Laboratory,
Department of Mechanical and Industrial Engineering,
University of Toronto, 5 King’s College Road, Toronto M5S
3G8, Canada; School of Material Science and Engineering,
Zhengzhou University of Aeronautics, Zhengzhou, Henan
450046, China
Sai Wang − Microcellular Plastics Manufacturing Laboratory,
Department of Mechanical and Industrial Engineering,
University of Toronto, 5 King’s College Road, Toronto M5S
3G8, Canada
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.0c10600
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors would like to acknowledge financial support
provided by NSFC (project no. 51773028). The authors
gratefully acknowledge Solvay’s donation of PVDF, Nano-
Xplore’s donation of graphene nanoplatelets, and the financial
support of the Consortium for Cellular and Microcellular
Plastics (CCMCP). Q.Q. was sponsored by the China
Scholarship Council at the University of Toronto.
■
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