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materials

Article

Broadband Microwave Absorbing Composites with

a Multi-Scale Layered Structure Based on Reduced
Graphene Oxide Film as the Frequency
Selective Surface

Fang Ye *, Changqing Song, Qian Zhou, Xiaowei Yin, Meikang Han, Xinliang , Litong Zhang
Li and Laifei Cheng
Science and Technology on Thermostructural Composite Materials Laboratory, School of Materials,
Northwestern Polytechnical University, Xi’an 710072, China; songchangqing@gmail.nwpu.edu.cn (C.S.);
qianzhou@mail.nwpu.edu.cn (Q.Z.); songqiang511@nwpu.edu.cn (X.Y.);
hanmeikang@mail.nwpu.edu.cn (M.H.); 597438335@mail.nwpu.edu.cn (X.L.);
zhanglt@nwpu.edu.cn (L.Z.); chenglf@nwpu.edu.cn (L.C.)
* Correspondence: yefang511@nwpu.edu.cn; Tel.: +86-29-8849-5163

Received: 2 August 2018; Accepted: 6 September 2018; Published: 19 September 2018

Abstract: A broadband microwave absorbing composite with a multi-scale layered structure is

proposed, in which a reduced graphene oxide (RGO) film sandwiched between two layers of epoxy
glass fiber laminates serves as the frequency selective surface (FSS). RGO films with the desired
electrical properties were synthesized directly by hydrothermal reaction, vacuum filtration, and heat
treatment without subsequent processing. With the novel layer-by-layer structure ranging from
micro to macro scale, the optimized composite exhibits excellent microwave absorption performance
with a total thickness of 3.2 mm. Its reflection coefficient (RC) is less than ÿ10 dB in the entire X
and Ku band, reaching a minimum value of ÿ32 dB at 10.2 GHz and an average RC of ÿ22.8 dB
from 8 to 18 GHz. Enhanced microwave absorption of the composites is achieved through the
optimization of layer thickness in the sandwich structure to promote destructive interference.
Improved impedance matching by the introduction of FSS along with the polarization and
conduction loss of layered graphene films also contribute to the increased absorption.

Keywords: microwave absorption; reduced graphene oxide; frequency selective surface; multilayer
structure

1. Introduction

Extensive use of portable electronic instruments and wireless communication has resulted in a
serious electromagnetic (EM) interference pollution. Hence, the design and exploration of high-
absorption, broadband and lightweight microwave materials, are highly desired [1–5]. Microwave
absorbers with multilayer structures that can be easily tuned by tailoring the individual property of
materials, have been extensively studied [6–10]. However, broadening the absorption bandwidth of
reflection coefficient (RC) to under ÿ10 dB always comes with the unavoidable increase in thickness
of the composites [11,12]. It is still a challenging issue in the design of broadband absorbers with
low thickness.
Recently, frequency selective surface (FSS) has been proposed as broadband and thin
absorbers through the equivalent circuit mode [13,14]. Loaded with lumped components like
resistors and capacitors, FSS is usually fabricated with highly conductive materials such as metals
with periodic patterns and specific sheet resistances. However, these materials are usually thick and

Materials 2018, 11, 1771; doi:10.3390/ma11091771 www.mdpi.com/journal/materials

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Materials 2018, 11, 1771 2 of 12

heavy [15]. Reduced graphene oxide (RGO) is a new and promising electromagnetic microwave
absorption material, owing to its unique two-dimensional (2D) structure and remarkable properties,
such as low density, high specific surface area, tunable electrical conductivity and abundant functional
groups [16–19]. The tunability and frequency-independent surface impedance of graphene at
microwave band have been theoretically investigated and proven feasible as a FSS [20].
Huang et al. designed and fabricated graphene FSS patterns on flexible substrates with an effective absorption
bandwidth spanning from 10.4 GHz to 19.7 GHz, which is suitable for radar absorption applications [21].
However, the fabrication process of graphene FSS based composites is complex, time-consuming and
expensive. Additionally, FSS is usually on the surface of the composite and directly exposed to the air, which
increases the possibility of oxidation and degradation of the microwave absorption.

In this work, a thin and broadband microwave absorber is designed and fabricated by using
RGO films with layered structures as FSS patterns in a sandwich structure. This design can not only
protect RGO films, but also enhances the microwave absorption by optimizing the effective dielectric
constant and enhancing the microwave loss mechanism. RGO films with tunable properties, as the
unit cell of FSS, have been fabricated by a simple and cost-effective process involving hydrothermal
reaction, vacuum filtration, and heat treatment. Subsequently, they are composited with epoxy glass
fiber dielectric laminates to develop sandwich microwave absorbing structure. Based on the finite
integration simulations, the electrical property of RGO film and the thicknesses of upper and lower
dielectric laminates have been optimized. As a result, these RGO films serving as FSS not only
optimize the effective dielectric constant but also increase the polarization and conduction loss of the
electromagnetic wave. The layer-by-layer structure improves impedance matching, increases macro
heterogeneous interfaces and leads to increased absorption by facilitating destructive interference.
The synergistic effect of these factors results in excellent microwave absorption with a thickness of
3.2 mm over a wide absorption bandwidth ranging from 8–18 GHz. The proposed structure is superior
to most of the reported composites in terms of performance.

2. Simulation and Experiments

2.1. Materials

All chemicals were of analytical grade and used without further purification. Graphene oxide
(GO) was procured from (XF Nano Materials Tech Co., Nanjing, China). The epoxy glass fiber
laminate (FR4) was procured from (Tongwen Rubber and Plastic Co., Shanghai, China).

2.2. Design and Simulation

The design and optimization of the broadband microwave absorber was performed using the
finite integration technique on the CST Microware Studio 2014 package (CST-2015, CST Ltd.,
Darmstadt, Germany), in which unit cell boundary conditions were applied in the x and y directions.
A wave-guide port was used to generate transverse electromagnetic plane waves perpendicularly to the sample
plane, which propagates along the ÿz direction. The absorption could be calculated as A(ÿ) = 1 ÿ T(ÿ) ÿ R(ÿ),
2 2
where R(ÿ) = |S11| and T(ÿ) = |S21| are the reflectance and transmittance obtained from the frequency
dependent complex S-parameters, respectively. Since the backside is grounded by metallic plane, the
transmittance T(ÿ) is zero. Thus, the absorption can be reduced to A(ÿ) = 1 ÿ R(ÿ). In the simulation, circular
Phi
RGO films with a diameter of 39 mm () were selected as the unit absorber cell. They were arranged in a periodic
pattern and sandwiched between two FR4 dielectric laminates, as illustrated in Figure 1a. The unit cell was set
with periodic boundary conditions in the x–y plane and it was modeled as a resistive sheet with a desired sheet
resistance (Rs).
FR4 laminates were selected as the materials for both the upper and lower substrate, taking
impedance match into consideration. The thicknesses of the upper and lower dielectric layers are denoted as
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Materials 2018, 11, 1771 3 of 12

Materials 2018, 11, x FOR PEER 3 of 12

REVIEW d1 and d2, respectively. The dielectric constant of FR4 laminate was 4.3 and loss tangent was 0.05 as
, 11, x FOR PEER REVIEW 3 of 12 1b,c, which can act as a proper electromagnetic impedance matching material.
Materials shown in Figure 2018

Figure. 1 (a) Schematic of the fabrication of sandwich-structured microwave absorbing composites;

(b) the dielectric constant of epoxy glass fiber (FR4) laminate; (c) the dielectric loss of FR4 laminate;
(d) the electromagnetic
Figure. 1 (a) Schematicmeasurement system
of the fabrication used in this study; (e)
of sandwich-structured the schematic
microwave diagram
absorbing of the
composites;
Figure 1.
dielectric (a) Schematic
property of the
test equipment; fabrication
(f) the of sandwich-structured
schematic diagram(c) microwave
of the
the dielectric absorbing
electromagnetic composites;
reflection (b) (b)
the dielectric constant of epoxy glass fiber (FR4) laminate; loss of FR4 laminate;
the dielectric constant of epoxy glass fiber (FR4) laminate; (c) the dielectric loss of FR4 laminate;
coefficient (RC) test equipment.
(d) the electromagnetic measurement system used in this study; (e) the schematic diagram of the (d)
the electromagnetic measurement system used in this study; (e) the schematic diagram of the
dielectric property test equipment; (f) the schematic diagram of the electromagnetic reflection dielectric
property test
2.3. Preparation of equipment;
RGO (f) the schematic
of FSS) diagram of the electromagnetic reflection coefficient
coefficient (RC)
(RC) test equipment.testFilm (Unit
equipment. Cell

In a typical procedure, 0.2 g of graphene oxide (GO) was well-dispersed in 200 mL of ethylene 2.3.
Preparation
2.3.
FSS) glycolof(EG)
Preparation RGO ofFilm
RGO
(Baishi (Unit
Film
co. Cell of Tianjing,
(Unit
LTD, FSS)
Cell of China) with ultrasonic treatment. The solution was then
transferred into a 250 mL Teflon-lined stainless-steel autoclave and heated at 180 °C for 12 h. The
In
In aa typical
typicalprocedure,
procedure,0.20.2
g ofggraphene
of graphene
oxideoxide (GO)
(GO) was was well-dispersed
well-dispersed in 200 mLinof200 mL ofRGO
ethylene ethylene
colloidal
suspension
LTD, Tianjing,wasChina)
obtained after
withLTD, the solution
ultrasonic was naturally
treatment. cooled
wastothen
room temperature. glycol (EG) (Baishi co.
glycol (EG) (Baishi co. Tianjing, China)The solution
with ultrasonic treatment. The solution was then 10 mL RGO
suspension
transferred was
a 250 mL Teflon-lined
into prepared
a 250 and vacuum
mLstainless-steel
Teflon-lined filtered with
autoclave
stainless-steel and polyvinylidene
heated
autoclave 180difluoride
at heated
and ÿCatfor
180 (PVDF)
12°Ch.for
The transferred
12 RGO
h. into
The membranes
(Lesheng
obtained filter equipment
after the manufacturing
solution was
was obtained plant,
naturally cooled Haining, China) that had a pore size of colloidal suspension was
RGO colloidal suspension after thetosolution
room temperature.
was naturally 10cooled
mL to room temperature. 0.45 ÿm and a
diameter of 47 mm. Subsequently, the RGO film was fabricated with
prepared and vacuum filtered with polyvinylidene difluoride (PVDF) membranes a diameter of 39 RGO suspension was
10 mL RGO suspension was prepared and vacuum filtered with polyvinylidene difluoride (PVDF) mm
and washed
(Lesheng with
filter ethanol tomanufacturing
equipment remove the remaining solvent.
plant, Haining, To obtain
China) the highly
that had a pore conductive
size of 0.45 µm and a
membranes (Lesheng filter equipment manufacturing plant, Haining, China) that had a pore size of graphene sheets,
RGO films werethe
Subsequently, heat-treated
RGO film wasat 600 °C, 800 °C
fabricated withand 1000 °C of
a diameter for39
1h in Ar,
mm andmarked
washedas diameter of 47 mm.
0.45 ÿm and a diameter of 47 mm. Subsequently, the RGO film was fabricated with a diameter of 39 RGO-600,
RGO-800 and RGO-1000, respectively. RGO films without heat treatment
remove the remaining solvent. To obtain the highly conductive graphene sheets, are denoted
RGO as with ethanol to
mm and washed with ethanol to remove the remaining solvent. To obtain the highly conductive films
RGO-RT.
were heat-treated at 600 ÿC, 800 ÿC and 1000 ÿC for 1 h in Ar, marked as RGO-600, RGO-800 and
graphene sheets, RGO films were heat-treated at 600 °C, 800 °C and 1000 °C for 1 h in Ar, marked as RGO-1000,
respectively. RGO films without heat treatment are denoted as RGO-RT.
RGO-600,
of RGO-800
the Composite withand RGO-1000,
Sandwich respectively. RGO films without heat treatment are denoted as 2.4. Preparation
Structure
RGO-RT.
2.4. Preparation of the Composite with Sandwich Structure
Sixteen of the as-obtained RGO films were arranged periodically and parallel to the surface of the upper
and lower FR4 RGO
obtained laminates,
films according to theperiodically
were arranged simulation and
model in Figure
parallel 2a.surface
to the Four kinds
of of Sixteen of the as-
2.4. Preparation
commercial FR4oflaminates
the Composite with
with the Sandwich Structure
thicknesses of 1.0 mm, 1.4 mm, 1.8 mm, 2.2 mm and 2.6 mm
were the upper and lower FR4 laminates, according to the simulation model in Figure 2a. Four kinds of
used. The dimensions
the thicknesses
as-obtained 1.0 of
ofRGO mm,the1.4
films composites
were
mm, were
arranged
1.8 mm, 180mm
mmand×and
periodically
2.2 180 mm
mm × dto(the
2.6parallel thetotal thickness
surface of the Sixteen
of commercial of the
FR4 laminates with
composite).
were used.
the upper Inlower
The
and case of the
dimensions
FR4 RGO composites
of the
laminates, composites
according towith
the full
were coverage
180 mm
simulation ×between
model180 mm two
×d
in Figure dielectric
(the
2a. total
Four layers,
thickness
kinds 36 of
of of RGOpieces
the
square
commercial
films
RGOwith FR4with
laminates
dimensions
composites offull mmwith
× 30the
30coverage mmthicknesses
formed
between twothe of 1.0layers,
mm,as1.4
composite,
dielectric mm,in1.8
shown
36 pieces mm,composite).
Figure 2.2 mm and 2.6 mm
In case were of
of the
2b.
RGO square films with dimensions of 30 mm × 30 mm formed the composite, as shown in Figure 2b.
used. The dimensions of the composites were 180 mm × 180 mm × d (the total thickness of the composite). In
case of the RGO composites with full coverage between two dielectric layers, 36 pieces of RGO square films
with dimensions of 30 mm × 30 mm formed the composite, as shown in Figure 2b.

Figure
Figure 2.
2. Composites with RGO
Composites with RGOfilms
filmsinin(a)
(a)periodic
periodic array,
array, (b)(b)
fullfull coverage.
coverage.

2.5. Characterization and Measurement

The morphology of the samples were characterized using field emission scanning electron Figure 2.
Composites with RGO films in (a) periodic array, (b) full coverage. microscopy
(SEM; S-4700, Hitachi, 15 kV, Tokyo, Japan). The crystal phase was identified by X-ray

2.5. Characterization and Measurement

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Materials 2018, 11, 1771 4 of 12

2.5. Characterization and Measurement

Materials
The 2018, 11, x FOR PEER
morphology were characterized using field emission scanning electron 4 of 12
REVIEW
of the samples
microscopy (SEM; S-4700, Hitachi, 15 kV, Tokyo, Japan). The crystal phase was identified by X-ray
diffraction
(XRD, D8 (XRD,D8 Avance,Karlsruhe,
Avance, Bruker, Bruker, Karlsruhe,
Germany)Germany) using
using Cu Kÿ (ÿ =Cu Kÿ Å)
1.54 (ÿ =radiation
1.54 Å) (40
radiation
kV, (40 diffraction
kV, 40 mA)
40 mA) in the
in the range
range of 5–90°
of 5–90ÿ withwith a step
a step scanscan of 0.01°
of 0.01ÿ perper step.
step. Raman
Raman spectra
spectra were
were acquired
acquired using a
using a He-Ne
Ne laser (RMS;laser (RMS; London,
Renishaw, Renishaw, London,
UK) UK) assource
as excitation excitation
(ÿ =source (ÿ =Rs532
532 nm). nm).RGO
of the Rs offilm
thewas
RGO He-
film was measured
measured using a four-probe
using a four-probe equipmentequipment (Voganruit
(Voganruit technology
technology co. LTD, co. LTD, Company,
Company, Beijing,
Beijing, China).
China). The electromagnetic
The electromagnetic measurement
measurement system
system used in used in this
this study study
was wasinshown
shown Figurein1d,
Figure 1d,was
which which
was mainlyof
composed composed of vector
vector network network
analyzer analyzer
(VNA, (VNA, Anritsu,
MS4644A, MS4644A, Anritsu, Kanagawa,
Kanagawa, Japan), mainly
Japan), waveguide
waveguide
chamber and chamber and support.
segmental segmentalThesupport. Theproperty
dielectric dielectric propertythe
including including
real andthe real andpart
imaginary imaginary
of
part of permittivity of specimens with a plane size of 22.86 mm ×10.16 mm for 8.2–12.4
permittivity of specimens with a plane size of 22.86 mm ×10.16 mm for 8.2–12.4 GHz (X-band) GHz (X-band)
and
and 15.79 mm × 7.9 mm for 12.4–18 GHz (Ku-band) was measured when VNA
15.79 mm × 7.9 mm for 12.4–18 GHz (Ku-band) was measured when VNA was equipped with the was equipped with
the waveguide
waveguide chamber
chamber as shown
as shown in Figure
in Figure 1e. 1e.
TheThe electromagnetic
electromagnetic RC RC of specimens
of specimens for Xforand
X and
Ku Ku
band
band was measured when VNA was equipped with the segmental support as shown in Figure 1f.
was measured when VNA was equipped with the segmental support as shown in Figure 1f.
Reflection from a pure metal plate with the same size as that of the fabricated composite
Reflection from a pure metal plate with the same size as that of the fabricated composite was used was used
for
for normalization.
normalization.

3. Results and Discussion

3.1. Structural Characterization

3.1. CharacterizationofofRGO
RGOFilms
Films

A
stacked
stacked
layer-by-layer
layer-by-layer
structure
structure
of of
thethe
RGO
RGO
film
film
with
with
thickness
thickness
under
under
1010
µmÿm
is is
evident
evident
from
from
the
A
cross-sectional
the andand
cross-sectional in-plane SEM
in-plane images
SEM shown
images in Figure
shown 3a,b,
in Figure respectively.
3a,b, respectively. The
The thickness
thicknessof of
the RGO
the RGO
film
tunedcanbybe
changing
tuned bythe
changing
volume the
of RGO
volume
suspension
of RGO suspension
during filtration.
duringThis
filtration.
lamellar
This
structure
lamellar film can be
structure
contributescontributes to theofabsorption
to the absorption of electromagnetic
electromagnetic waves that are waves thatvertical
emit in the are emit in the[22–24].
direction vertical direction
The
[22–24].
ultrathin
The films
ultrathin
are films
flexible
areas
flexible
evident
asfrom
evident
Figure
from
3c,
Figure
where3c,
they
where
are shown
they aretoshown
be bent
toand
be bent
rolled
around
and a pen.
rolled around a pen.

Figure 3.
Figure 3. (a)
(a) Cross-sectional
Cross-sectional SEM
SEM image;
image; (b)
(b) in-plane
in-plane SEM
SEM image
image and
and (c)
(c) flexibility
flexibility of
of the
the RGO
RGO film.
film.

Figure 4a
Figure 4a reveals
reveals the
the XRD
XRDspectra
spectraofofRGO-600,
RGO-600,RGO-800,
RGO-800,RGO-1000
RGO-1000andandRGO-RT
RGO-RTsamples.
samples.
InIn the
case
of RGO-600,
the RGO-800 and
case of RGO-600, RGO-1000,
RGO-800 only the graphite
and RGO-1000, crystalline
only the graphitepeak is observed
crystalline in is
peak the XRD
observed in the
spectra.
XRD The The
spectra. peakpeak
at 2ÿat=2ÿ26.5ÿ
= 26.5°corresponds to to
corresponds the
the(002)
(002)plane
planeofofgraphite
graphite layers with an
layers with aninter
inter-layer
spacing
of 0.334 nm [25,26]. For the as-filtrated RGO-RT, a peak around 23.1ÿ indicates a layer-to-layer
layer spacing of 0.334 nm [25,26]. For the as-filtrated RGO-RT, a peak around 23.1° indicates a layer
distancedistance
to-layer (d-spacing) of about of
(d-spacing) 0.385 nm,
about which
0.385 is due
nm, whichto is
thedue
existence of severalofoxygen
to the existence severalfunctional
oxygen
functional groups [27]. Structural characterizations of RGO films are further explored usingspectroscopy
groups [27]. Structural characterizations of RGO films are further explored using Raman Raman
where two peaks
spectroscopy at 1355
where cmÿ1atand
two peaks 1587
1355 cmÿ1
cmÿ1 andare obtained
1587 cmÿ1 are(Figure 4b), corresponding
obtained to the D and
(Figure 4b), corresponding
to GDbands,
the respectively.
and G bands, The peak
respectively. at 1587
The peak cmÿ1cmÿ1
at 1587 shows the Raman-active
shows the Raman-active E2gE2g
mode or or
mode thethe
GGband,
characterizing
band, the sp2
characterizing thehybridized C–C bonds
sp2 hybridized in RGO.
C–C bonds The DThe
in RGO. bandD at 1355
band at cmÿ1 originates
1355 cmÿ1 from the
originates from in-
plane vibration of sp2 carbon atoms, which reflects the disorder degree of the crystal structure [28,29].
the in-plane vibration of sp2 carbon atoms, which reflects the disorder degree of the crystal structure
Increased
[28,29]. annealing
Increased temperature
annealing can result
temperature in theinrecovery
can result of the
the recovery of sp2 configuration.
the sp2 According
configuration. to
three-stage
model from amorphous carbon state to nanocrystalline graphite state, the increase of ID/IG
According to three-stage model from amorphous carbon state to nanocrystalline graphite state, the from 0.95389
to 1.7097of
increase indicates the 0.95389
ID/IG from increasedtosp2 content
1.7097 [30,31].the increased sp2 content [30,31].
indicates
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Figure 4. (a)4.XRD
Figure and (b) (b)
(a) XRD Raman spectra ofofRGO films after different temperaturetreatments.
treatments.
Figure 4. (a) XRD and
and (b)Raman
Ramanspectra
spectra RGO
of RGOfilms afterafter
films different temperature
different temperature treatments.

For RGOForfilms
RGO films
treated treated
at different at different
temperatures, Rs temperatures,
was measured by aRs was measured
four-probe by RGO
method and For a four-probe
films treatedmethod
at differentand the
temperatures, Rs was measured by a four-probe method and results are listen in Table 1. It is evident that Rs decreases dramatically
with the
the results are increase of annealing
listen in Table 1. It is evident that Rs decreases dramatically with the increase of the results are listen in Table 1. It is evident
that Rs decreases dramatically with the increase of temperature. During the heating process from room temperature to 600 ÿC, the
deoxygenation
annealing temperature. During the heating process from room temperature to 600 °C, the annealing temperature. During the heating process
from room temperature to 600 °C, the reduction reaction is accompanied by the removal of most of the oxygen functional groups such as
deoxygenation
deoxygenation reduction reaction
reduction is accompanied
reaction is accompanied by the
by removal
the removalof most of the
of most of oxygen functional
the oxygen functional –OH,
–COOH, from the surface of graphene. Further increasing the temperature from 600 ÿC to
groups such as –OH, –COOH, from the surface of graphene. Further increasing the temperature from groups such as –OH, 1000from
–COOH, ÿC
the surface of graphene. Further increasing the temperature from results in a slight decrease in Rs due to the slow release of C–H groups
600 °Cand oxygen-containing
to 1000 °C results in agroups
slight decrease in Rs due to the slow release of C–H groups and oxygen 600 °C to 1000 °C results in a slight
decrease in Rs due to the slow release of C–H groups and oxygen between layers [32].
containing groups between layers [32]. containing
groups between layers [32].

TableTable 1. Sheet
1. Sheet Resistance
Resistance of RGO
of RGO Film
Film at at DifferentTemperature.
Different Temperature.
Table 1. Sheet Resistance of RGO Film at Different Temperature.
Temperature/ÿC
Temperature/°C RoomRoom Temperature
Temperature 600 800600
1000800 1000
Temperature/°C Room Temperature
600 800 1000 Sheet resistance/(ÿ/sq) 3100 ± 10 70 ± 3 40 ± 3 27 ± 3 Sheet resistance/(
/sq) 3100 ± 10 70 ± 3 40 ± 3 27 ± 3
Sheet resistance/(ÿ/sq) 3100 ± 10 70 ± 3 40 ± 3 27 ± 3

Based on the simulation results of CST, the composite is optimized to have as wide absorption Based on the simulation results of
CST,
havethe composite
as wide is optimized to have as wide absorption Based on the simulation results of CST, the composite is optimized to
absorption
band when Rs of RGO FSS films is 40 ÿ/sq. In other words, when RGO-800 films are applied as the band when Rs of RGO FSS films is 40
ÿ/sq.
filmsIn other
are words,
applied as when RGO-800 films are applied as the band when Rs of RGO FSS films is 40 ÿ/sq. In other words, when RGO-800
interlayer and arranged in a periodic pattern, the composites should exhibit excellent broadband interlayer and arranged in a periodic pattern,
the composites should exhibit excellent broadband the interlayer and arranged in a periodic pattern, the composites should exhibit excellent
broadband
microwave absorption. In this case, RGO-800 films are chosen as the FSS sandwiched by FR4 layers. microwave absorption. In this case,
RGO-800 films areby
FSS sandwiched chosen as the FSS sandwiched by FR4 layers. microwave absorption. In this case, RGO-800 films are chosen as the
FR4 layers.

3.2. Absorption Properties

3.2.Absorption
Absorption of the Composite
Properties with Sandwich Structure
3.2. Properties ofofthe
theComposite
Composite with
with Sandwich
Sandwich Structure
Structure The RC of the

composites
TheRC
RCcanofbe
theobtained according
composites canbebeto transmission
obtained line theory:
according
The of the composites can obtained according to to transmission
transmission line
line theory:
theory:

Zin-Z0Zin-Z0
Zin-Z0 |

(1) (1)
RC =RC
20 log10|
RC==2020 log10| (1)
| |

log10|Zin+Z0Zin+Z0
Zin+Z0

µr 2p
Zin= Z0 µr tan2h[j
p
2 pc ÿ µrÿr f d] µr (2)
Zin = Z0 µr
tanÿrh[j (2)
Zin = Z0ÿr tan h[jc ÿrfd] µr (2)
c ÿrfd]
ÿr
where, Z0 = (µ0/ÿ0) 1/2 is the characteristic impedance of free space, Zin is the normalized input
impedance of absorbing material, ÿr and µr are the relative complex permittivity and permeability,
where, Z0 = (µ0/ÿ0)1/2 is the characteristic impedance of free space, Zin is the normalized input where, Z0 = (µ0/ÿ0)1/2 is the characteristic
impedance
represents of free
the space, Zin is the normalized input respectively. f is the frequency, d is the thickness of absorbing material, and c
speed
impedance of absorbing material, ÿr and µr are the relative complex permittivity and permeability, impedance of absorbing material, ÿr and
µrµrare the relative
= 1. When complex permittivity and permeability, of light in free space. For non-magnetic dielectric substrates, the relative permeability
respectively. f is the frequency, d is the thickness of absorbing material, and c represents the speed of respectively. f is the frequency, d is
the thickness
absorbed andofthe
absorbing material, and c represents the speed of the RC is below ÿ10 dB, more than 90% electromagnetic energy is
corresponding
light in free space. For non-magnetic dielectric substrates, the relative permeability µr = 1. When the light in free space. For non-magnetic
dielectric substrates, the relative permeability µr = 1. When the frequency range is defined as the effective absorption bandwidth (EAB).
RC is below ÿ10 dB, more than 90% electromagnetic energy is absorbed and the corresponding RC is below ÿ10 dB, more than 90%
electromagnetic
laminate energy is absorbed and the corresponding The RC of the composites containing RGO-800 FSS films for different FR4
thicknesses,
frequency
frequency range is defined
range is defined as the effective
as the absorption bandwidth
effective (EAB).
is shown in Figure 5. It is evident that RC isabsorption
affected by bandwidth (EAB).
the thickness of the upper and lower FR4
TheTheRC RC
of the composites containing RGO-800 FSS films for different FR4 laminate thicknesses,
layer. RCmin gradually shifts towards the lower frequencies with increasingFR4
of the composites containing RGO-800 FSS films for different laminate
laminate thicknesses,
thickness.
is shown
shown in Figure 5. It is evident that RC is affected by the thickness of the upper and lower FR4 is
1.0 mm and d2 = 2.2 mm, the composite exhibits excellent microwave absorption performance,For d1 =
in Figure 5. It is evident that RC is affected by the thickness of the upper and lower FR4
layer. RCmin gradually shifts towards the lower frequencies with increasing laminate thickness. For d1
withRCmin
layer. EAB gradually
spanning shiftsthe entire
towards bandfrequencies
the lower from 8 to with18 GHz with
increasing anthickness.
laminate average ForRC
d1 of ÿ22.8 dB, as shown in
= 1.0 mmmm
=Figure
1.0 andand
d2 =d2 2.2 mm,mm, the the
composite exhibits excellent microwave absorption performance, withwith
5c. When d1 = 1.4 mm and d2 = 2.2 mm, the composite achieves RCmin of performance,
= 2.2 composite exhibits excellent microwave absorption ÿ46 dB with EAB of
EAB spanning the entire band from 8 to 18 GHz with an average RC of ÿ22.8 dB, as shown in Figure EAB spanning the entire band from 8
to 18 GHz with an average RC of ÿ22.8 dB, as shown in Figure 5c. When d1 = 1.4 mm and d2 = 2.2 mm, the composite achieves RCmin of
ÿ46 dB with EAB of 10 GHz. 5c. When d1 = 1.4 mm and d2 = 2.2 mm, the composite achieves RCmin of ÿ46 dB with EAB of 10 GHz.
Machine Translated by Google

Materials
Materials2018,
2018,11,
11,x1771
FOR PEER REVIEW 6 of 1212
6 of

Additionally, the composite with d1 = 1.4 mm and d2 = 1.8 mm in Figure 5c also has a wide EAB with
10GHz.
10 GHz. Additionally, the composite with d1 = 1.4 mm and d2 = 1.8 mm in Figure 5c also has a wide
EAB with 10 GHz.

Figure 5. Experimental results of RC of the composites with RGO-800 films in periodic array for
Figure 5. Experimental
for different results
thicknesses of theofFR4
RClaminates
of the composites withmm;
(a) d2 = 1.4 RGO-800
(b) d2 films
= 1.8inmm;
periodic
(c) d2array
= 2.2 mm;
different thicknesses of the FR4 laminates (a) d2 = 1.4 mm; (b) d2 = 1.8 mm; (c) d2 = 2.2 mm; (d) d2 = 2.6 (d) d2
= 2.6 mm.
mm.
To verify that RGO-800 FSS films play a very important role in absorbing microwave energy,
To verifywith
composites that full
RGO-800 FSS
coverage films play
between the aFR4
verylaminates
importantwere
role analyzed,
in absorbing
as microwave energy,
shown in Figure 6.
composites with full coverage between the FR4 laminates were analyzed, as shown in Figure
For d1 = 2.2 mm, d2 = 1.8 mm, the composite has the widest EAB of 5.9 GHz ranging from 10.9 6. For
GHz to
d1 = 2.2
16.8 GHzmm,
andd2RCmin
= 1.8 mm, the dB,
= ÿ20.1 composite hasinthe
as shown widest
Figure 6b.EAB of 5.9 GHz ranging from 10.9 GHz to 16.8
GHz and RCmin = ÿ20.1 dB, as shown in Figure 6b.
The composites with d1 = 1.0 mm and d2 = 2.2 mm in Figures 5c and 6c along with the composite
without RGO-800 are chosen for further analysis, as shown in Figure 7a. It can be observed that the
composite with RGO-800 FSS films covers the entire X and Ku band, whereas the composite with
RGO-800 film in full coverage has a much narrower EAB. In contrast, the composite without RGO-800
film has almost no microwave absorption ability establishing that the introduction of periodic RGO
films into a sandwich structure could effectively enhance their microwave absorption properties.
Figure 7b shows the simulation result of the composite with RGO-800 FSS films comparing with the
optimal experimental result (d1 = 1.0 mm, d2 = 2.2 mm). There is a similar tendency between the
simulated and experimental results. Although it is difficult to eliminate the difference between the
two results, it can be reduced by optimizing algorithm and refining database as the cases in other
studies [21–23].
Machine Translated by Google

Materials 2018, 11, 1771 7 of 12

Materials 2018, 11, x FOR PEER REVIEW 7 of 12

Figure
Experimental
6. Experimental
results of results
RC of the
of RC
composites
of the composites
with RGO-800
with RGO-800
films in fullfilms
coverage
in full coverage
for different
for Figure 6.
thicknesses
different of the FR4
thicknesses laminates
of the (a) d2(a)
FR4 laminates = 1.4
d2 =mm; (b) d2
1.4 mm; (b)=d2
1.8 mm;mm;
= 1.8 (c) (c)
d2 d2
= 2.2 mm;
= 2.2 (d)(d)d2d2==2.6
mm; 2.6mm.
8 of 12
Materials 2018, 11, x FOR PEER REVIEW
mm.

The composites with d1 = 1.0 mm and d2 = 2.2 mm in Figures 5c and 6c along with the composite without
RGO-800 are chosen for further analysis, as shown in Figure 7a. It can be observed that the composite with
RGO-800 FSS films covers the entire X and Ku band, whereas the composite with RGO-800 film in full coverage
has a much narrower EAB. In contrast, the composite without RGO 800 film has almost no microwave absorption
ability establishing that the introduction of periodic RGO films into a sandwich structure could effectively enhance
their microwave absorption properties. Figure 7b shows the simulation result of the composite with RGO-800
FSS films comparing with the optimal experimental result (d1 = 1.0 mm, d2 = 2.2 mm). There is a similar
tendency between the simulated and experimental results. Although it is difficult to eliminate the difference
between the two results, it can be reduced by optimizing algorithm and refining database as the cases in other
studies [21–23].

Figure 7. (a)
Figure 7. (a)RC
RCofofthe
thecomposite
composite with
with RGO-800
RGO-800 FSSFSS films,
films, RGO-800
RGO-800 in fullin full coverage
coverage and without
and without RGO-800,
respectively; (b) Comparison
RGO-800, respectively; of RC between
(b) Comparison numerical
of RC betweensimulation
numerical and experimental
simulation results
and experimental results for the
composite with RGO-800
for the composite FSS (d1FSS
with RGO-800 = 1.0
(d1mm, d2mm,
= 1.0 = 2.2d2mm).
= 2.2 mm).

3.3. Absorption Mechanism of the Composites

3.3. Absorption Mechanism of the Composites
On a macroscopic scale, the upper FR4 layer of the composite has a relatively smaller permittivity,
On a macroscopic scale, the upper FR4 layer of the composite has a relatively smaller which improves the
impedance matching and reduces the microwave reflection. Combining RGO FSS
permittivity, which improves the impedance matching and reduces the microwave reflection. with the sandwich
structure can bring about impedance matching and lead to enhanced microwave
Combining RGO FSS with the sandwich structure can bring about impedance matching and lead to absorbance
and bandwidth. Based on equivalent circuit model and transmission line theory, when
enhanced microwave absorbance and bandwidth. Based on equivalent circuit model and the thickness d of the
structure is set, the ideal Rs of the RGO FSS for perfect absorption is frequency
transmission line theory, when the thickness d of the structure is set, the ideal Rs of the RGO FSS for dependent.
For the composite (d1 = 1.0 mm, d2 = 2.2 mm) with RGO-800 FSS films, two resonant
perfect absorption is frequency dependent. For the composite (d1 = 1.0 mm, d2 = 2.2 mm) with RGO 800 FSS
films, two resonant peaks at 10.0 GHz and 14.7 GHz are excited. The electric field, magnetic field and power
loss density distributions for the composite at different frequencies have been performed by commercial CST, as
shown in Figure 8. As an electrically lossy material, the power loss distribution is similar to that of the electric
field at the two resonant peaks of 9.0 GHz and 14.8 GHz.
 On a macroscopic scale, the upper FR4 layer of the composite has a relatively smaller permittivity,
Machine Translated by Google
which improves the impedance matching and reduces the microwave reflection.
Combining RGO FSS with the sandwich structure can bring about impedance matching and lead to
enhanced microwave absorbance and bandwidth. Based on equivalent circuit model and transmission
11,
line 1771
theory,perfect
when the thickness d of the structure is set, the ideal Rs of the RGO FSS for Materials 2018, 8 of 12

absorption is frequency dependent. For the composite (d1 = 1.0 mm, d2 = 2.2 mm) with RGO 800 FSS
films, two resonant peaks at 10.0 GHz and 14.7 GHz are excited. The electric field, magnetic peaks at
10.0 GHzpower
field and and 14.7 lossGHz are distributions
density excited. The forelectric field, magnetic
the composite field and
at different power loss
frequencies density
have been distributions
for the composite at different frequencies have been performed by commercial
performed by commercial CST, as shown in Figure 8. As an electrically lossy material, the power CST,
loss as shown
distribution in Figure
is similar 8. of
to that Asthe
an electric
electrically
field lossy
at thematerial, the power
two resonant peaks loss
of 9.0distribution is similar
GHz and 14.8 to that of
GHz. the
electric field at the two resonant peaks of 9.0 GHz and 14.8 GHz. Due to electromagnetic
Due to electromagnetic coupling effects, there is strong microwave absorption between the adjacent coupling
effects,
unit there
cells is strong
at two microwave
resonant peaks as absorption
proved inbetween
Figure 8, thewhich
adjacent unit cells
is different at two
from theresonant peaks
case in full as
coverage
proved
situation.in Figure 8, which is different from the case in full coverage situation.

Figure 8.
Figure 8. The
The electric,
electric,magnetic
magneticfield
fieldand
andpower
powerloss
lossdensity
density distributions
distributions onon
thethe composite
composite at
at different
frequencies.
different frequencies.

On a microscopic scale, RGO films are composed of layered graphene sheets that are parallel to the
On a microscopic scale, RGO films are composed of layered graphene sheets that are parallel to
substrate, as is evident from the SEM image in Figure 3a. When the electromagnetic waves are incident
the substrate, as is evident from the SEM image in Figure 3a. When the electromagnetic waves are in
the vertical
incident direction,
in the thedirection,
vertical layered structure creates
the layered more barriers
structure createsleading to a higher
more barriers absorption
leading of
to a higher the
microwave energy
absorption of [24]. Unlike
the microwave traditional
energy [24]. FSS materials
Unlike such
traditional FSSasmaterials
carbon black
suchand metal, RGO
as carbon black
and inherently has superior properties. One the one hand (Figure 9), there are abundant
metal, RGO inherently has superior properties. One the one hand (Figure 9), there are abundantmicro-defects
in RGO
(higher
MaterialsD2018,
band11,
in xRaman
FOR PEERspectrum) as compared to traditional carbon materials, which act 9 of 12
REVIEW micro-defects in RGO (higher D band in Raman spectrum) as compared to traditional carbon as polarized centers
by accumulating dipoles in the alternating EM field and inducing polarization
materials, which act as polarized centers by accumulating dipoles in the alternating EM field and
loss [33–35].
inducing On the
polarization other
loss hand,
[33–35]. On due to the
the other multilayer
hand, structure
due to the multilayerand the increase
structure of conductivity
and the increase after
of conductivity
after
the annealing,
hopping RGO carriers
of charge can facilitate
throughtheconductive
hopping of paths,
chargewhich
carriers through
leads to conductive annealing, RGO can facilitate
considerable improvement
paths, which leads of conduction
to considerable loss
improvement [36,37]. loss [36,37].
of conduction

Figure
Figure9.
9.Schematic
Schematicfor
forabsorption
absorptionmechanism
mechanismof
ofthe
thesandwich-structured
sandwich-structuredcomposite
compositeininmicro
microscale.
scale.

Figure 10 summarizes the microwave absorption performance of the composites with multilayer
Figure 10 summarizes the microwave absorption performance of the composites with multilayer
structure in recent years. The sandwich structure combined with the FSS makes the proposed composite
structure in recent years. The sandwich structure combined with the FSS makes the proposed highly
competitive with respect to other composites with pure multilayer structure, which cannot
composite highly competitive with respect to other composites with pure multilayer structure, which cannot satisfy low
thickness and wide bandwidth conditions simultaneously [6,9,38–41]. Introducing FSS into the sandwich structure
can be an effective way to solve the above issue [10,42,43]. Li’s approach involved stencil printing of carbon black
nanoparticle ink mixed with multiwalled carbon nanotubes, which is complex and suffers from the problem involving
the dispersion of carbon
’
Machine Translated by Google

Materials 2018, 11, 1771 9 of 12

satisfy low thickness and wide bandwidth conditions simultaneously [6,9,38–41]. Introducing FSS
into the sandwich structure can be an effective way to solve the above issue [10,42,43]. Li’s approach
involved stencil printing of carbon black nanoparticle ink mixed with multiwalled carbon nanotubes,
which is complex and suffers from the problem involving the dispersion of carbon nanotubes [10].
A similar drawback has been observed with Lee’s approach where composites with RCmin of ÿ17 dB
were demonstrated [43]. Overall, the procedure proposed here is simple to implement and achieves a
wide absorption band of 10 GHz using a lower composite thickness of 3.2 mm and a high absorption
with RC Materials 2018of 11,
min, ÿ32x dB.
FOR PEER REVIEW 10 of 12

Figure 10. Effective absorption bandwidth (EAB) from 8–18 GHz versus thickness of typical
Figure 10. Effective absorption bandwidth (EAB) from 8-18 GHz versus thickness of typical sandwich
sandwich-structured composites published in open literature.
structured composites published in open literature.
4. Conclusions
4. Conclusions
In summary, the composite with RGO FSS films sandwiched between two dielectric FR4 layers
In summary,
was fabricated theacomposite
using with RGO
facile approach and FSS films of
the effect sandwiched
RGO FSS between twomicrowave
films on the dielectric FR4 layers
absorption
was fabricated using a facile approach and the effect of RGO FSS films on the microwave
properties of the composite was investigated. Through finite integration simulations, the composite absorption
properties
with RGO-800 of the
FSScomposite
films was was investigated.
found Through finite
to exhibit excellent integration
EM wave simulations,
absorption the composite
performance with the
thickness of 3.2 mm, a strong absorption with RCmin of ÿ32 dB and wide EAB from 8 to 18with
with RGO-800 FSS films was found to exhibit excellent EM wave absorption performance the
GHz,
thickness of 3.2 mm, a strong absorption with RCmin of ÿ32 dB and wide EAB
spanning the entire X and Ku band. Highest absorption was observed with RCmin of ÿ46 dB for a totalfrom 8 to 18 GHz,
spanning layer
dielectric the entire X andofKu
thickness 3.6band.
mm. Highest
Thus, it absorption was observed
was established with RCmin
that the composite of ÿ46
with dB for a total
the multi-scale
dielectric layer thickness of 3.6 mm. Thus, it was established that the composite
layered structure based on RGO films as FSS, possessed strong absorption and broad bandwidth with the multi-scale
layered structure based on RGO films as FSS, possessed strong absorption and
while maintain a low thickness. This work provides guidelines for the fabrication of ceramic matrixbroad bandwidth
while maintain a low thickness. This work provides guidelines for the fabrication of ceramic matrix composites with
microwave absorbing function.
composites with microwave absorbing function.
Author Contributions: Conceptualization, F.Y.; Data curation, F.Y. and C.S.; Formal analysis, Q.Z. and X.L.;
Funding acquisition, F.Y.,Conceptualization,
Author Contributions: L.C., X.Y. and L.Z.; Investigation,
F.Y.; M.H.F.Y. and C.S.; Formal analysis, Q.Z. and X.L.;
Data curation,
Funding: This research was funded by the National Natural M.H.
Funding acquisition, F.Y., L.C., X.Y. and L.Z.; Investigation, Science Foundation of China (51602258, 51372204,
and 51332004), Shaanxi Provincial Natural Science Foundation of China (2017JM5094), and the Innovation
Funding: This
Foundation research
for Doctor was funded
Dissertation ofby the NationalPolytechnical
Northwestern Natural Science Foundation
University of China (51602258, 51372204,
(CX201604).
and 51332004), Shaanxi Provincial Natural Science Foundation of China (2017JM5094), and the Innovation
Foundation for Doctor Dissertation of Northwestern Polytechnical University (CX201604).

Acknowledgments: The authors appreciate the Science and Technology on Thermostructural Composite
Materials Laboratory providing all technical supports in this paper.
Conflicts of Interest: The authors declare no conflict of interest.
Machine Translated by Google

Materials 2018, 11, 1771 10 of 12

Acknowledgments: The authors appreciate the Science and Technology on Thermostructural Composite Materials
Laboratory providing all technical supports in this paper.
Conflicts of Interest: The authors declare no conflict of interest.

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