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D. Geng, Y. Wang, J. An, J. He, D. Li, W. Liu and Z. Zhang, RSC Adv., 2015, DOI: 10.1039/C5RA06212H.

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Excellent microwave-absorption performances by matched

nanocapsules
Linwen Jiang,a Zhenhua Wang,*a Da Li,a Dianyu Geng,a Yu Wang,b Jing An,b Jun He,b Wei
Liua and Zhidong Zhanga

Abstract
The double-shelled Co/C/polyaniline (Co/C/PA) nanocomposites were prepared by
combing the arc-discharge process and in-situ chemical oxidative polymerization reaction.
The effects of PA shells on the magnetic properties of Co/C/PA nanocomposites were studied,
and the electromagnetic properties of Co/C/PA-paraffin composites were investigated in the
2-18 GHz frequency range. The reflection loss (RL) exceeding -10 dB is obtained in 9.916.4
GHz for the absorber thickness of 2.5 mm, which cover almost half of X-band (8-12 GHz)
and most of Ku-band (12-18 GHz). Moreover, some strong absorption peaks exceeding -40
dB can be observed in low frequency range (3.5-5.5 GHz). The excellent absorbing
performances show that the Co/C/PA nanocomposites have great prospects for application in
microwave-absorption field for their strong absorption and broad bandwidth.

1. Introduction
Microwave-absorption materials have many promising applications in military,
electronic

devices,

and

communication

instruments.

Exploiting

type

of

microwave-absorption material with strong absorption in a wide frequency range has been
attracting an increased attention.1-5 Currently, the research of nanocomposites, composed of a
magnetic core (Ni, FeNi, Co, etc.) and a dielectric shell (C, ZnO, polyaniline, etc.) in the
nanometer size, is very active in the microwave-absorption field due to their excellent
microwave-absorption performances. Some core-shell structured nanocomposites, including
a

Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang

110016, P. R. China. E-mail: zhwang@imr.ac.cn; Tel: +86-24-83978846

b

Division of Functional Material Research, Central Iron & Steel Research Institute, Beijing 100081, P. R. China

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magnetic-dielectric properties in double-shelled Co/C/polyaniline

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Ni/C,6 FeNi/C,7 Co/C,8 CoNi/C,9 Zn(Fe)/ZnO,10 Ni/polyaniline,11 are believed to be attractive

candidates for the new types of microwave-absorption materials. The excellent

the special core-shell structure. This core-shell structure can induce beneficial physical
effects on microwave absorption at an applied electromagnetic field, including reecting and
scattering inside materials,12-15 cooperative effects of dielectric properties and magnetic
properties,6,16 and multi-polarizations at core-shell interfaces.8,17
Recent interest has been expanded to the multi-shelled nanocomposites. It is expected
that the microwave-absorption properties of nanocomposites may obtain a great breakthrough
by adding more shells of different types due to the stronger physical effects of multi-shelled
structure. Some multi-shelled nanocomposites have been reported, such as double-shelled
FeCo/C/BaTiO3 nanocomposites,16 graphene/Fe3O4/SiO2/SnO2 nanocomposites.18 and Fe3O4
cores/double-shelled SnO2 nanocomposites,19 The research on multi-shelled nanocomposites
is becoming more and more active in the microwave-absorption field.
The choice of material types of cores and shells is very important for the enhancement
of

microwave-absorption

properties.

The

combining

of

magnetic-loss-type

and

dielectric-loss-type materials may generate a remarkable microwave-absorption performance

due to the balance of electromagnetic properties. Polyaline (PA) with good dielectric
properties has been studied on the microwave-absorption properties,20 and the single-shelled
Co/C nanocomposites with large saturation magnetization also have been investigated.8 In
this work, the unique double-shelled Co/C/PA nanocomposites were prepared by combining
the arc-discharge method and in-situ chemical oxidative polymerization method. The effects
of PA shells on the magnetic properties of Co/C/PA nanocomposites were investigated. The
electromagnetic properties of Co/C/PA-paraffin composites were investigated in the 2-18
GHz frequency range, and the excellent microwave-absorption performances were explained
by the proper magnetic-dielectric match set up by the special double-shelled structure.

2. Experimental section
2.1 Material Synthesis

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microwave-absorption performances of nanocomposites were reported to be associated with

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The single-shelled Co/C nanocomposites were prepared by an arc-discharge technique.

The detailed process is described as below: Co (99.98%) ingot was served as anode, and the

chamber (10 Pa) to serve as the source of plasma, and 20 mL C2H5OH was also introduced
into the evacuated chamber as the C resource. At the end of the arc-discharge process,
residual gases were pumped out. After being passivated in air for 24 h, the Co/C
nanocomposites were collected on the top of the chamber.
Subsequently, the double-shelled Co/C/PA nanocomposites were synthesized by the
in-situ chemical oxidative polymerization method. A typical preparation process is described
as below: the HCl aqueous solution was added to aniline monomer to obtain HCl-protonated
aniline. The Co/C nanocomposites of calculated amount were added to C6H8O7 solution
under ultrasonication for 30 min to obtain a uniform suspension. The well-dispersed Co/C
nanocomposites were mixed with the prepared HCl-protonated aniline monomer under
ultrasonication for 30 min. Then the APS (Ammonium persulphate, (NH4)2S2O8) was added
to the above solution as oxidant for polymerization reaction under vigorous mechanical
stirring. In this experiment, the molar ratio of aniline monomer, HCl and APS was retained at
1:1:1. The precipitated powders were centrifugated and washed with distilled water
repeatedly for five times, and finally dried in a drying cabinet at 40 C for 48 h.

2.2 Preparation of samples for the measurements of electromagnetic properties

The double-shelled Co/C/PA nanocomposites were mixed with paraffin uniformly and
then be pressed into a cylindrical-shaped compact of 7.00 mm outer diameter, 3.04 mm inner
diameter, and an approximate height of 2.00 mm for the electromagnetic parameter
measurements, wherein paraffin not only can agglomerate samples, but also can provide a
good passageway of microwave absorption due to its transparent properties. The mass
fraction of samples in paraffin matrix was set at 50 wt. %.

2.3 Material characterization

Phase analysis of the products was performed by powder X-ray diffraction (XRD) with
Cu K radiation at 50 kV and 300 mA. The scattering range (2) was set in 20o85o with a

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graphite needle was served as cathode. High purity argon was introduced into an evacuated

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scan rate of 4o/min-1. The size distribution, morphology and structures were investigated by
using a transmission electron microscope (TEM, JEOL 2010EX). The surface information of

line X-ray source. Magnetic properties of samples were measured using a vibrating sample
magnetometer (VSM). The variety of weight and thermal values of samples were investigated
by thermal gravimetric analysis (TGA) and differential thermal analysis (DTA) at ambient
pressure from 50oC to 800oC with a heating rate of 4oC/min. The electromagnetic parameters
of samples were determined in the frequency range of 2 to 18 GHz using an Agilent 8722ES
network vector analyzer with a transverse electromagnetic mode.

3. Results and discussion

In the arc-discharge process, Co atoms in the Co ingot and C atoms in C2H5OH
molecules obtained energy and escaped to the vacuum space by the sputtering of high-energy
Ar ions. The highly active Co and C atoms reassembled rapidly and nucleated through the
rapid energy exchange. After a series of thermodynamic process, the surfaces of Co were
covered by the light mass C. The formed Co/C nanocomposites with high speed were
stochastically diffused around the region of the plasma to all direction. When they entered
into a cool area, the speed of Co/C nanocomposites slowed down and finally deposited on the
wall of chamber. A schematic diagram of preparing Co/C nanocomposites is shown in Fig. 1a.
Covering of PA over the Co/C nanocomposites was carried out using in-situ chemical
oxidative polymerization reaction. The HCl as dopant was added into the aniline monomers
in order to obtain HCl-protonated aniline. During the polymerization reaction, the Co/C
nanocomposites were served as efficient nucleation centers of polymerization. The aniline
monomers were polymerized around the Co/C nanocomposites by the addition of APS
aqueous solution under vigorous mechanical stirring.21,22 Here, the APS as oxidant has
extremely strong oxidization ability which can participate in oxidation-reduction reaction
even at a very low concentration of aqueous solution. After the polymerization reaction, the
formed chained PA polymer covered over Co/C nanocomposites. A schematic diagram of
preparing Co/C/PA nanocomposites is shown in Fig. 1b.

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prepared samples was determined by X-ray photoelectron spectroscopy (XPS), with an Al K

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Fig. 1 Schematic diagrams of preparing (a) Co/C nanocomposites and (b) Co/C/PA
nanocomposites.

Fig. 2a shows TEM images of Co/C nanocomposites, which reveal clearly that they are
spherical in shape with diameters from 10 to 20 nm. The C shells are covered well over the
Co cores, and the shell thickness is about 3 nm, as shown in Fig. 2b. After the in-situ
oxidative polymerization reaction, the surfaces of Co/C nanocomposites were covered by PA.
Fig. 2c shows TEM images of as-prepared Co/C/PA nanocomposites. The shell thicknesses of
the Co/C/PA nanocomposites have an obvious rise as a result of cover of PA shells, as shown
in Fig. 2d. The inset in Fig. 2d shows that the Co/C/PA nanocomposites present
core-shell-shell structure. Fig. 2e depicts XRD patterns of as-prepared Co/C/PA, Co/C, C, PA.
Here, the C and PA were also prepared via arc-discharge method and in-situ oxidative
polymerization method, respectively. It can be observed that the strong sharp diffraction
peaks at 2 = 44.2, 51.5, and 75.9 in the XRD patterns of Co/C/PA are in good accord with
the (111), (200) and (220) planes of Co PDF [04-0836], respectively. The XRD patterns of
as-prepared C and PA reveal that both of them have crystalline structure. The broad
bread-shaped diffraction peak at 225 in the XRD pattern of C corresponds to the (0 0 2)
lattice plane of a graphite phase. The broad peak at 226 in the XRD pattern of PA

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corresponds to the repetition units of regular aniline monomers.23 However, the C and PA
components have not been detected in the XRD patterns of Co/C/PA, which may be due to

nanocomposites, it is also difficult to detect their XRD patterns because of breaking down of
the periodic boundary condition (translation symmetry) along radial direction.7 The average
size of Co cores is calculated from the broadening of the (111) diffraction peak by the
well-known Scherrer equation as follows.24
D=

0.89
cos

where D is crystallite size in nm, is the radiation wave length (0.15405 nm for Cu K), is
the corrected full width at half maximum, and is the diffraction angle. The average size of
the Co cores is calculated to be 18 nm, which is close with that of Co/C/PA nanocomposites.

Fig. 2 (a) TEM and (b) high-resolution TEM images of prepared Co/C nanocomposites, (c)
TEM and (d) high-resolution TEM of Co/C/PA nanocomposites, (e) XRD patterns of
Co/C/PA, Co/C, C, and PA.

XPS is a very effective and convenient technique to investigate the surface states of

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their low contents. Moreover, since the C and PA are located in the shells of the

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materials, which not only can present information about the atomic compositions, but also
can identify the type of bonds between atoms.25 Here, XPS was employed to identify the

Co/C/PA, Co/C and PA. Two strong peaks centered at 778.7 eV and 284.6 eV, corresponding
to the Co and C, can be observed from the XPS survey spectra of Co/C. The quantitative
results from XPS analysis reveal that the atomic percentages of Co and C in the surface are
11% and 89%, respectively. The major presence (89%) of C atoms in the surface shows that
the C atoms covered over the Co nanoparticles, which is accordance with the results of TEM
image. Three strong peaks centered at 283.9 eV, 398.5 eV and 530.6 eV, corresponding to the
C, N and O, are observed from the XPS survey spectra of Co/C/PA. The appearance of N
peaks confirms the formation of PA in the surface of the samples. The high-resolution C (1s)
core level spectra is displayed in Fig. 3b. The spectra are made of two components that can be
identified as follows: (1) a main peak at 284.6 eV (generated by photoelectrons emitted from
sp2-bond carbon atoms in graphite configuration); (2) a second peak centered at 285.4 eV
(from the photoelectron contribution of the sp3-bond carbon atoms).26 Fig. 3c represents the
N (1s) core level spectra which can be de-convoluted into four peaks. The binding energy
centered at 396.6, 398.3, 399.5 and 400.8 eV can be assigned to quinoid [=N-], benzenoid
amine [-NH-], cationic nitrogen atoms (=NH+) and protonated amine units (-NH+) in PA,
respectively.27 Furthermore, the positively charged nitrogen (=NH+) is associated with the
cationic nitrogen atoms. The peak at binding energy of 400.8 eV assigned to protonated
amine units (-NH+) is ascribed to the stronger electron localization associated with poor
conjugation at sp3 bonded sites.28 A relatively weak peak centered at 776.8 eV, corresponding
to Co (2p), is observed in the XPS survey spectra of Co/C/PA. The quantitative results from
XPS analysis reveal that the atomic percentage of Co is 0.9%, far lower than 11% of Co in
Co/C. As a result of the high surface sensitivity (less than 10 nm in depth) of XPS, the
decrease of Co content in the surface shows that the shell thickness of Co nanoparticles has
been increased. This indicates again that the PA has covered over the nanoparticles. Fig. 3d
shows the C (1s) core level spectra in Co/C/PA. The C (1s) peak could be de-convoluted into
four peaks with binding energies centered at 283.9 eV, 284.7 eV, 285.9 and 287.4 eV
corresponding to C-H, C-C, C-N and C=C species, respectively.27 One can observe that O

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surface information of the prepared samples. Fig. 3a displays the XPS survey spectrum of

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atoms exist in the surface of Co/C/PA nanocomposites. The presence of the O atoms may be
ascribed to the remnants of reactants with O-element in PA during the in-situ chemical

shown in Fig. 3a. It can be observed that the similar O-peak also exists in the survey spectra,
and the peak intensity is close with that of Co/C/PA. Therefore, it is concluded that the
presence of O atoms originates from the remnants of reactants with O-element.

Fig. 3 (a) XPS survey spectra of synthesized Co/C/PA, Co/C and PA, (b) deconvolution
spectra of C (1s) of Co/C, deconvolution spectra of (c) N (1s) and (d) C (1s) of Co/C/PA.

The TGA-DTA plots of Co/C and Co/C/PA nanocomposites are shown in Fig. 4. The
TGA-DTA plots of Co/C nanocomposites display three stages: in the first stage (50240 oC),
the weight of Co/C nanocomposites nearly has no variety. In general, the metal nanoparticles
are easy to transform spontaneously into metal oxides in room temperature as the size
decreases from micron to nanometer, thus have an obvious weight increase. Here, the
unchanged weight shows that the Co/C noanocapsules have not been oxidized even at 240 oC

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polymerization. To prove it, the XPS spectra of single-component PA were investigated, as

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since protective C shells prevent the Co cores from oxidation. The result indicates that the Co
cores are well coated by C shells, which is in good agreement with the TEM results. The

shells, which is similar with that of Ni/C nanocomposites (250280 oC).29 The strong
exothermal peak at about 250 oC can be attributed to the strong burning of C shells. The Co
cores are oxidized quickly after the burning of protective C shells, thus an obvious weight
increase is observed in the TGA curve. In the third stage (270800 oC), the weight and
thermal values only have slight change as a result of much weaker oxidative behaviors. It can
be observed that a strong exothermal peak of Co/C/PA nanocomposites locates at about 310
o

C. This temperature is higher than that (250 oC) of Co/C nanocomposites, which can be

ascribed to the higher burning temperature of PA shells. The inner C shells have not been
burned before the outer PA shells start burning. The weight increase of Co/C/PA
nanocomposites is slow as the temperature increases, which is an integrated result of the
weight decrease induced by the burning of C/PA and the weight increase induced by the
oxidation of Co cores.

Fig. 4 TGA-DTA plots of Co/C nanocomposites and Co/C/PA nanocomposites.

The magnetic properties of both Co/C and Co/C/PA nanocomposites are measured in order
to investigate the effects of PA shells on the magnetic properties. The M-H curves at 300 K of
Co/C/PA are shown in Fig. 5a, wherein the saturate magnetization (Ms), remanent

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second stage (240270 oC) may be associated with oxidative behaviors of the Co cores and C

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magnetization (Mr), and coercive field (Hc) are 97 emu/g, 15 emu/g, and 280 Oe, respectively.
The Ms is relatively lower than that of Co/C (110 emu/g), and is only about 58% that of bulk

magnetic properties are strongly dependent on the particle size as well as the crystalline
structure and the chemical bonding at the surface. The magnetic properties may be affected
by a combination of magnetization mechanisms related closely to several anisotropies. The
coating of PA on the Co/C nanocomposites will likely affect the contributions of surface,
shape, and interface anisotropies to the net anisotropy.30 (2) The decrease of content of
magnetic matters (Co) weakens the magnetic properties of total materials as a result of the
introduction of PA. It is noteworthy that the additive PA has diamagnetic properties, as shown
in the inset 2 of Fig. 5. However, the diamagnetic properties of PA are quite smaller, only
reaching -0.11 emu/g at an applied field of 20 kOe, thus negligible.

Fig. 5 M-H curves of Co/C/PA and Co/C nanocomposites at 300 K. Inset 1: low field part of
M-H curves. Inset 2: M-H curve of PA at 300 K. Inset 3: the parameters of magnetic
properties at 300 K.

Fig. 6a shows the frequency dependence of the real parts () and imaginary parts () of
relative permittivity of the Co/C/PA-paraffin composites. It can be found that the values of
and declined from 8 to 5 and from 3.5 to 1, respectively, with a slight fluctuation in 218
GHz. The large values are attributed to the lags of polarization between the core/shell/shell
interfaces, as shown in Ni/C,6 FeCo/C/BaTiO3,16 FeCo/C.31 The is mainly associated with
the amount of polarization occurring in the material, and is related to the dissipation of

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Co. The relatively lower Ms in Co/C/PA may be due to the following reasons: (1) the

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energy. The performance of relative permittivity depends on ionic, electronic, orientational,

and space charge polarization.32 Of these polarization mechanisms, space charge polarization

with increasing frequency may be attributed to the decrease in interfacial polarization.33 In a

heterogeneous system, the accumulation of space charges at the interface of two media will
lead to interfacial polarization and is known as MaxwellWagner polarization.34 Here, plenty
of heterogeneous interfaces in double-shelled Co/C/PA nanocomposites contribute to the
interfacial polarization.
Conventionally, the permittivity can be represented by the Debye dipolar relaxation
expression,11

= +

= + ,
1 + 2

where f is the microwave frequency, is the relaxation time, s and is the stationary and
optical dielectric constant, respectively. From the equation, the results below can be deduced:

= +
,
1 + 2
2
=
.
1 + 2
It can be found that the is a function of /f, viz. = +

. Thus, if the

dielectric loss is only a consequence of Debye dipolar relaxation, the plot of (f) versus
(f)/f would be linear. Fig. 6b shows the plots of versus /f of Co/C/PA-parafn composite
samples. Here, it presents approximate four beelines, suggesting that four Debye dipolar
relaxation processes may occur in the Co/C/PA nanocomposites. Each beeline corresponds to
a Debye dipolar relaxation process.8 The four Debye dipolar relaxation processes may mainly
result from the electron displacement polarization, the interfacial polarizations at Co/C, C/PA
and PA/air interfaces, respectively. According to the different slopes of four beelines, we can
obtain the following results: 1=7.810-11 s, 2=2.610-10 s, 3=6.210-10 s, 4=1.510-9 s. In
general, the building time of electric relaxation process is about in the range of 10-2-10-9s.
Here, the relatively short time of relaxation processes may be attributed to the weak applied
field.
The real part () and the imaginary part () of relative permeability of the

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(interfacial polarization) is more frequency-dependent. The observed decrease in and

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Co/C/PA-paraffin composite as a function of frequency in 218 GHz are shown in Fig. 6c.
The values exhibit a nearly linear decrease from 1.4 to 0.8 in the 218 GHz frequency

GHz, 9.1 GHz and 13.6 GHz, respectively. These multi-resonance peaks of can be due to
the exchange mode resonance, which may be associated with the small size effect, the
surface effect and spin wave excitations, etc.29 Zhang et al. reported the relation of versus
frequency of single-shelled Co/C nanocomposites, wherein the resonance peaks present at
about 6 GHz and 12 GHz.8 The different resonance peaks of of the Co/C nanocomposites
and Co/C/PA nanocomposites may be due to the additional PA shell. Moreover, the resonance
frequency is dependent on the particles radius, lattice defects and interior stress resulting
from the special double-shelled structure, which can bring a great increase in the effective
anisotropy field and further lead to the resonance frequency appearing at a different
frequency.30,35 The microwave-absorption performances of the Co/C/PA-paraffin composites
depend on their magnetic and dielectric loss. Fig. 6d shows the frequency dependence of the
dielectric loss factor tan () (viz. /) and magnetic loss factor tan () (viz. /). The
dielectric loss factor tan() exhibits the fluctuation behaviors from 0.24 to 0.45 in the 218
GHz range, which can be ascribed to the relaxation process.36,37 The magnetic loss factor
tan() varies from 0.06 to 0.24, and exhibits three broad peaks at about 5.0 GHz, 9.1 GHz
and 13.8 GHz, respectively. Magnetic loss factor tan () is a significant parameter for
magnetic loss. In general, the contributors to magnetic loss include magnetic hysteresis,
domain-wall displacement, and eddy current and natural resonance. Here, the natural
resonance loss may be the main contributor to the magnetic loss due to the weak applied
electromagnetic field.6 It is expected that the natural resonance will result in strong magnetic
loss abilities, implying enhanced microwave absorption during gigahertz frequency range.

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range. Meanwhile, as the frequency is varied, values exhibit three broad peaks at about 4.9

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Fig. 6 The frequency dependence of (a) and of the Co/C/PA-paraffin composites. (b) the
plots of versus / f of Co/C/PA-paraffin composites. The frequency dependence of (c) ,
, and (d) tan (), tan () of the Co/C/PA-paraffin composites.

To further reveal the microwave-absorption properties, the reflection loss (RL) of

Co/C/PA-paraffin composites is calculated using the relative complex permeability and
permittivity at a given frequency and thickness layer according to the transmission-line
theory by means of the following expressions:38,39
Zin=Z0 (r/r)1/2tanh[ j(2fd/c) (rr)1/2],
RL=20log| (Zin-Z0)/(Zin+Z0) |,
where f is the frequency of microwave, d is the thickness of absorber, c is the velocity of light,
Z0 is the impedance of air, and Z is the input impedance of absorber.
Fig. 7a shows the relationship between the calculated RL values and the frequency for
the Co/C/PA-paraffin composites in 218 GHz. In general, the thickness of absorber,
absorption bandwidth, and absorption intensity are used to evaluate the absorbers in

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engineering applications.40 It can be seen that the Co/C/PA nanocomposites present excellent
absorption performances due to the high absorption intensity and wide absorption bandwidth

given thickness of 2.5 mm, which cover almost half of X-band (8-12 GHz) and most of
Ku-band (12-18 GHz). The RL exceeding -10 dB corresponds to 90% attenuation of the
microwave absorption, which is believed to be the valuable bandwidth in engineering
applications.24 Some strong absorption peaks exceeding -40 dB are located in 3.5-5.5 GHz for
the given thicknesses range from 5 to 7 mm. The excellent absorbing performances show that
the Co/C/PA nanocomposites have great prospects for application in microwave absorption
for its strong absorption and broad bandwidth in low frequency range. The excellent
microwave-absorption performances can be explained by the following facts. Firstly, the
double-interfaces are advantageous for microwave absorption due to the multi-interfacial
polarizations.41 Secondly, the core-shell interfaces can provide more active sites for reflection
and scattering of microwave. The microwave will be reflected and absorbed repeatedly inside
the nanocomposites, and is hard to escape from the nanocomposites before being absorbed
and transferred to heat.15 Ling et al. reported that the microcellular foaming method can
enhance the microwave absorption since the interface of microscale air bubbles in the foams
could attenuate the microwave by reecting and scattering between the cell wall and
nanollers.14 To explain clearly the effects of core-shell interfaces on the microwave
absorption, a physical model of reflection and scattering of microwave in double-shelled
Co/C/PA nanocomposites is shown in Fig. 7b. Thirdly, the void space at the interfaces can
effectively interrupt the spread of electromagnetic wave and generate dissipation due to the
existing impendence difference and enhanced the microwave absorption properties.18

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at different thicknesses. The RL exceeding -10 dB is obtained in the 9.916.4 GHz for a

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Fig. 7 (a) Relationship between the calculated RL values and the frequency for the
Co/C/PA-paraffin composites in the 218 GHz frequency range. (b) Physical model of
reflection and scattering of microwave in double-shelled Co/C/PA nanocomposites.

The physical properties of materials are associated greatly with the constituent structures.
A good constituent structure may generate some beneficial physical effects on the
microwave-absorption performances of materials,42,43 e.g., multi-polarizations at interfaces,44
multi-reflections inside materials,15 cooperative effects of dielectric-magnetic properties.45
These beneficial effects may lead to the enhancement of microwave-absorption properties. In
the case of Co/C/PA nanocomposites, the excellent microwave-absorption performances may
be associated with the particular double-shelled structures. To prove the conclusion, the
microwave-absorption properties of the mixture of single-shelled Co/C and PA are
investigated. The electromagnetic parameters of the mixture of single-shelled Co/C and PA as
a dependence of frequency are shown in Fig. 8a. It can be found that the values of and
declined from 9.3 to 5.6 and from 7.0 to 2.4, respectively, in the 2-18 GHz frequency range.

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Meanwhile, the values of declined from 1.40 to 0.87, and the values of exhibit an
approximate constant (0.23) in 2-9 GHz and then decline from 0.23-0.11 in 9-18 GHz. One

with that of double-shelled Co/C/PA, while the permittivity of the mixture of single-shelled
Co/C and PA is higher than that of double-shelled Co/C/PA. Herein, the higher permittivity
probably results from the following reason: the Co/C and PA are separated from each other in
the mixture of single-shelled Co/C and PA, while Co/C and PA are connected tightly by
core-shell interfaces in double-shelled Co/C/PA nanocomposites. In other words, the
conductive matters (include Co/C and PA) in the mixture has a more dispersed state in
comparison with those in double-shelled Co/C/PA nanocomposites, resulting in the formation
of a qualitatively more conductive network.

Fig. 8 (a) Electromagnetic parameters and (b) RL as a dependence of frequency in 218 GHz
for the mixture of single-shelled Co/C and PA.

The RL as a dependence of frequency of the mixture of single-shelled Co/C and PA is

shown in Fig. 8b. It can be observed that the maximum RL reaches -23.3 dB at 17.2 GHz
with 2 mm thickness layer. With increasing the thickness layer, the RL peak value exhibits a
slow decline, and the absorption peak shifts to lower frequency range. When the thickness
layer reaches a maximum 7 mm, the RL peak value is reduced to -12.8 dB. Obviously, the
absorption performances of the mixture of single-shelled Co/C and PA are much weaker than
those of double-shelled Co/C/PA nanocomposites, especially in low frequency range. The
results indicate that the double-shelled structure is more advantageous in obtaining good
microwave-absorption performances in contrast with the single-shelled structure. In general,

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can observe that the permeability of the mixture of single-shelled Co/C and PA is very close

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higher

permittivity

usually

leads

to

higher

dielectric

loss

and

obtains

better

microwave-absorption properties. However, in this work, the mixture of single-shelled Co/C

comparison with the double-shelled Co/C/PA nanocomposites. It may be attributed to the

mismatched dielectric-magnetic properties. The excellent microwave-absorptions result from
the efficient complementarities between the permittivity and permeability in materials. Either
only the magnetic loss or only the dielectric loss may induce a weak microwave-absorption
property due to the imbalance of the dielectric-magnetic match.6 Zhang et al. reported that the
excellent microwave-absorption performances of Fe/C nanocomposites result from a good
dielectric-magnetic match between the dielectric C shells and magnetic Fe cores by the
particular core-shelled microstructures.45 In the case of double-shelled Co/C/PA
nanocomposites, a similar dielectric-magnetic match also may be set up by the particular
double-shelled

microstructures,

resulting

in

the

excellent

microwave-absorption

performances. The core-shell-structural nanocomposites with dielectric shells and magnetic

cores may become attractive candidates in the microwave-absorption field for their special
magnetic-dielectric match.

4. Conclusions
The double-shelled Co/C/PA nanocomposites were prepared by combing the
arc-discharge process and the in-situ chemical oxidative polymerization reaction. The results
of XRD, TEM, XPS and TGA-DTA show that both the C and PA were covered over the Co
cores. The M-H curves at 300 K of Co/C/PA nanocomposites show that the saturate
magnetization (Ms), remanent magnetization (Mr), and coercive field (Hc) are 97 emu/g, 15
emu/g, and 280 Oe, respectively. The RL exceeding -10 dB is obtained in a wide frequency
range in the 2-7 mm thickness range. Moreover, some strong absorption peaks exceeding -40
dB can be observed in low frequency range (3.5-5.5 GHz). The results show that the Co/C/PA
nanocomposites have great prospects for application in microwave-absorption field for its
strong absorption and broad bandwidth. By the contrastive experiments, it indicates that the

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and PA with higher permittivity exhibits weaker microwave-absorption properties, in

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double-shelled structure is more advantageous in obtaining good microwave-absorption

Acknowledgements
This research project has been supported by the National Basic Research Program
No.2012CB933103 of China, Ministry of Science and Technology China, and the National
Nature

Science

Foundation

of

China

No.51102244,

51171185

and

51371055,

and International S&T Cooperation Program of China No. 2012DFA51300.

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