Journal of Physics and Chemistry of Solids 73 (2012) 12681273

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Journal of Physics and Chemistry of Solids

journal homepage: www.elsevier.com/locate/jpcs

Synthesis and microwave absorbing properties of FeNi alloy incorporated

ordered mesoporous carbonsilica nanocomposite
Guoxian Li, Yunxia Guo 1, Xin Sun, Tao Wang, Jianhua Zhou, Jianping He n
College of Material Science and Technology, Nanjing University of Aeronautics and Astronautics, Mailbox 1006, 29 Yudao Street, Nanjing 210016, P.R. China

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 14 June 2011
Received in revised form
30 May 2012
Accepted 17 June 2012
Available online 26 June 2012

Ordered mesoporous carbonsilica/FeNi nanocomposite were prepared by a solgel method and

following sintering process. The electromagnetic parameters were measured in the 0.518 GHz range.
Compared with ordered mesoporous carbonsilica composite, the permittivity of ordered mesoporous
carbonsilica/FeNi nanocomposite decreases, while the permeability almost remains unchanged. The
optimal reection loss of ordered mesoporous carbonsilica/FeNi nanocomposite can reach  45.6 dB at
11.1 GHz for a layer thickness of 3.0 mm. The enhanced microwave absorption of the mesoporous
carbonsilica/FeNi nanocomposite is due to better balance between the complex permittivity and
permeability, geometrical effect, as well as multiple reections by the ordered mesoporous structure.
& 2012 Elsevier Ltd. All rights reserved.

Keywords:
A. Nanostructures
A. Alloys
C. X-ray diffraction
D. Magnetic properties

1. Introduction
With the drastically increasing problems of the electromagnetic
interference and military defense, considerable attention has been
focusing on the novel electromagnetic wave absorbing materials
with lightweight and strong absorption over a broad frequency
spectrum [14]. Generically, the microwave absorption properties
are determined by the electromagnetic properties such as permittivity (e), permeability (m), electromagnetic impedance matching,
layer thickness of the absorber and the microstructure of the
absorber [5,6]. According to the dispersion characteristic of the
complex permittivity and permeability, microwave absorption
materials can be divided into two types: magnetic materials and
dielectric materials, which are relevant to magnetic loss and
dielectric loss, respectively [7,8]. Carbon-based materials are kind
of dielectric materials which have long been explored as possible
electromagnetic shielding and microwave absorbing materials
[912]. However, the poor magnetic permeability of the carbonbased materials makes the mismatch of impedance and limits their
use as microwave absorbing material [13,14]. Two strategies have
been carried out to solve this problem. One is to introduce
vacancies or pores in the carbon-based materials, as it has been
reported that porous structure modication is an effective way to
reduce the complex relative dielectric permittivity, which endow
the materials better impedance matching property [1517]. On the
other hand, the magnetic permeability of carbon-based materials
can be enhanced by compounding with magnetic particles. Based
n

Corresponding author. Tel.: 86 25 52112900; fax: 86 25 5211 2626.

E-mail addresses: lgx_nuaa@sina.com (G.X. Li), ynxia@nuaa.edu.cn (Y.X. Guo),
sunxin52199@163.com (X. Sun), wangtao0729@nuaa.edu.cn (T. Wang),
huajian0921@yahoo.com.cn (J.H. Zhou), jianph@nuaa.edu.cn (J.P. He).
1
Joint rst author.
0022-3697/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jpcs.2012.06.013

on the above strategies, ordered mesoporous composites become

notably attractive as the candidate novel electromagnetic wave
absorbers because of its unique structures, tunable ingredients and
very low densities. Liu et al. successfully fabricated ordered
mesoporous carbon and fused silica composite, and its elaborate
nanostructure contributes the excellent electromagnetic interference shielding efciency [18]. In our previous studies, we have
found that ordered mesoporous carbonalumina composite could
be used as a promising lightweight electromagnetic wave absorber
[19]. However; the lack of magnetism limits their application.
Metal particles of Fe and some Fe-based alloys are kind of
magnetic materials and have been widely investigated as electromagnetic wave absorbers [2023]. Ferromagnetic alloys possess high
saturation magnetization and good electromagnetic wave absorption
performance due to their higher Snoeks limitation frequency. We
have reported a facile synthesis of Mesoporous carbonSiO2Fe
nanocomposites earlier, and discussed their electromagnetic wave
absorption properties [24]. Liu et al. [25] found that the electromagnetic wave absorption property of (Fe, Ni)/C nanocapsules are better
than that of Ni/C or Fe/C nanocapsules, because they can take
advantages of both the nickel and iron. That inspires us to introduce
FeNi alloy into the ordered mesoporous carbon system and further
investigate the possibility of the ordered mesoporous carbon nanocomposite used as electromagnetic wave absorber.

2. Experimental
2.1. Preparation
FeNi alloy incorporated ordered mesoporous carbonsilica
nanocomposites were synthesized using a solvent-evaporation

G. Li et al. / Journal of Physics and Chemistry of Solids 73 (2012) 12681273

induced self-assembly method. In a typical synthesis, 1.0 g F127

(Mw12 600, PEO106PPO70PEO106) was dissolved into 10.0 g
ethanol with vigorous stirring for 1 h at 40 1C to obtain a clear
solution. Then 0.66 mmol FeCl3 d6H2O and 0.33 mmol
NiCl2d6H2O were added to the solution. After stirring at 40 1C
for another 1 h, 1.04 g TEOS (tetraethyl orthosilicate) and 0.5 mL
furfuryl alcohol were poured in succession. After stirring for 2 h, a
homogeneous solution was obtained. The solution was transferred into dishes to evaporate ethanol under room temperature
and then thermopolymerized in an oven at 80 1C for 24 h. The
carbonization was carried out in a tubular furnace at 350 1C for
5 h and 700 1C for 2 h under N2 atmosphere using a heating rate
of 1 1Cdmin  1. The resulting nanocomposites are denoted as
CSFeNi. For comparison, the pure carbonsilica nanocomposite
CS was prepared by the same process without metal chloride.

2.2. Characterization
The samples were characterized by transmission electron
microscopy (TEM, FEI Technai G2 and JEM 2100), and X-ray
powder diffraction (XRD, Bruker D8 Advance diffractometer with
Cu KR source). Nitrogen adsorptiondesorption isotherms were
measured at 77 K using a Micromeritics ASAP 2010 system. The
magnetization of the sample CSFeNi was measured by a vibrating sample magnetometer (VSM) integrated in a physical property measurement system (PPMS-9, Quantum Design) up to
10,000 Oe at 300 K. The permittivity and permeability of samples
with 40 wt% prepared powder in a parafn matrix were measured
in the 218 GHz range by using a vector network analyzer
(Agilent E8363A).

1269

3. Results and discussion

The small and wide angle XRD patterns of nanocomposite CSFeNi
are shown in Fig. 1(a) and (b) respectively. The presence of the
diffraction peak at pseudo-small angles suggests that this sample may
consist of a highly regular or ordered structure. The identication of
this mesoporous structure will be discussed later with the assistance
of TEM analysis. There are three prominent sharp diffraction peaks in
Fig. 1(b), which are associated with the (111), (200), and (220) planes
of FeNi3 (JCPDS:38-0419). The broad peak at about 2y 251 in
Fig. 1(b) can be identied as the diffraction of amorphous carbon.
The small peaks (at about 2y 351, 371, 621) marked in Fig. 1(b) may
come from the unreduced NiFe2O4.
Fig. 1(c) shows N2 sorption isotherm of CSFeNi. The curve
exhibits representative type IV isotherms with H2 type hysteresis
loop. Fig. 1(d) shows a narrow pore size distribution centered at
3.9 nm which imply uniform pore size. The BET surface area and pore
volume of CSFeNi are as high as 493 m2 g  1 and 0.45 cm3 g  1.
Fig. 2 reveals a detailed structural characterization of CSFeNi
by TEM. It shows large-area highly ordered stripe-like image and
mesoporous channels are highly arranged and parallel to each
other in the [110] direction, indicating a large region of ordered
mesopores in CSFeNi. FeNi alloy particles are dispersed in the
carbonsilica frameworks. There are some collapses in the image,
which may be resulted from the quick removal of the surfactant
in the carbonization. The TEM image agrees with the result from
the small angle XRD pattern. Additionally, the presence of both Fe
and Ni was qualitatively conrmed by energy dispersive X-ray
(EDX) spectrometric analysis.
The magnetic property of CSFeNi at room temperature was
characterized using a vibrating sample magnetometer (VSM).

Fig. 1. (a)small angle XRD patterns of nanocomposite CSFeNi; (b) wide angle XRD patterns of nanocomposite CSFeNi; (c) N2 adsorptiondesorption isotherms curve of
CSFeNi; (d) pore diameter distribution of CSFeNi.

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G. Li et al. / Journal of Physics and Chemistry of Solids 73 (2012) 12681273

Fig. 2. TEM images of CSFeNi. The inset is the corresponding typical EDX
spectrum.

Fig. 4. Frequency dependences of complex permittivity(a) and permeability(b) of

CS and CSFeNi. In measurement, a 40 wt % sample and 60 wt % epoxy resin
were used.

Fig. 3. Magnetization curve of CSFeNi.

As shown in Fig. 3, the magnetization hysteresis loop is a S-like

curve and the maximum saturation magnetization value reaches
2.45 emu/g. Furthermore, the magnetic remanence of the sample
is 0.035 emu/g, nearly zero. This indicate that there is almost no
remaining magnetization when the applied magnetic eld is
removed, suggesting that CS-FeNi exhibits a superparamagnetic
behavior.
The complex permittivity and permeability were measured by
a network analyzer on the basis of transmission/reection coaxial
line method [26], and the results are shown in Fig.4. For CS and
CSFeNi, with increasing frequency, the e0 values decreased from
12.7 and 8.6 to 6.0 and 5.0 in the 0.518 GHz range, respectively.
The e00 of CSFeNi are almost constant with less variation
throughout the whole frequency range (e00 E1.5). The e00 value
of CS has a slight increase from 1.5 to 3.5. Obviously, when FeNi is
introduced in the nanocomposite, both e0 and e00 are smaller to
that of FeNi free sample. Presence of NiFe2O4 phase may contribute to the decrease of e0 and e00 .[27] Fig.4(b) reveals that the

permeability of CS and CSFeNi are almost the same with little

diversity in the high frequency. The possible causes may be that
the content of FeNi added was controlled in a relative low level,
for the purpose of preserving the ordered mesoporous structure,
which play an important role in dissipating energy. Furthermore,
it was noted that negative m00 values were observed in some
conditions as indicated in Fig. 4(b). Similar phenomenon was also
found in some studies for various composites. In some cases, Lee
[28] and Chiu [29] believe that the negative permeability is
meaningless in physics but indicated these materials may have
potential as left-handed materials. In other cases, a negative m00
value denotes that magnetic energy is radiated out from the
absorber [17,30,31]. According to the Maxwell equations, the
motion of charges in an electromagnetic eld will produce an ac
electric eld, and as a result induces a magnetic eld. The permeability and permittivity are coupled in this situation. In our work, a
coupling is found in the permittivity and permeability. Hereinafter,
we can observe the phenomenon of a maximum e00 =e0 and a
minimum m00 =m0 at the same frequencies in Fig.5. So, it is reasonable
that the electric property of the nanocomposites should take responsibility for the phenomenon of negative m00 .
The tangent of dielectric and magnetic loss of the CSFeNi/parafn
composite is calculated as tande e00 =e0 and tandm m00 =m0 , respectively. Fig. 5 shows the dielectric and the magnetic factor loss of
CSFeNi. The electromagnetic wave absorption of the CSFeNi
composite results mainly from dielectric loss rather than magnetic

G. Li et al. / Journal of Physics and Chemistry of Solids 73 (2012) 12681273

Fig. 5. Frequency dependence of the dielectric loss and magnetic loss of CSFeNi.

Fig. 6. Values of m00 m0 2 f

1

versus frequency for CSFeNi.

loss because the value of tande is much higher than that of tandm . The
dielectric loss mainly comes from polarization and interfacial polarization. Eddy current loss and natural resonance are two major
reasons for magnetic loss at microwave band. If the magnetic loss
1
results from eddy current loss, the values of m00 m0 2 f
should be
constant when frequency is varied [32]. Fig. 6 represents the values of
m00 m0 2 f 1 versus frequency, it can be seen that the values of
m00 m0 2 f 1 uctuate with the increasing of frequency. Therefore,
the main magnetic loss for CSFeNi could be natural resonance.
To investigate the microwave absorption properties, the theoretical reection loss (RL) were calculated from the complex
permeability and permittivity at various sample thicknesses with
the following equations [33]:

r
Z in Z 0

mr
2pf d p
tanh j
mr er
c
er

absorption, which is considered as an adequate microwave

absorption [34].
As shown in Fig. 7(a) and (b), the introduction of FeNi into
mesoporous carbon leads to enhanced absorption intensity and
broadened bandwidth. The sample CS shows a maximum reection loss of only  13.4 dB at 5.9 GHz for an absorber thickness of
6.0 mm, while CSFeNi shows a maximum reection loss of
 45.6 dB at 11.1 GHz for a layer of thickness 3.0 mm. For the
sample CS, the RL values exceeding 10 dB are reached in the
range of 9.111.4 GHz for an absorber thickness of 2.5 mm. The
effective absorption bandwidth (lower than 10 dB) is 5.6 GHz
for CSFeNi, as the layer thickness is 2.5 mm. The optimal RL of
CSFeNi is 28 dB for an absorber thickness of 2.0 mm, which is
much lower than previously reported Fe incorporated mesoporous carbonsilica nanocomposite [24].
The combination of carbon-based materials and magnetic
components has been widely studied as electromagnetic wave
absorption material. Table 1 shows electromagnetic wave absorption properties of some similar reports. It can be seen that the RL
below 10 dB of this work are outstanding with abroad absorption frequency range. The minimum RL reaches 48.2 dB when
the thickness is 2.5 mm.
To achieve low reection loss values, a basic prerequisite that
effectively couple the incident microwave into the material while
minimum reection must be satised. That is to say, the complex
permittivity should be equal to complex permeability:

e0 m0

e00 m00

Though the introduction of FeNi into mesoporous carbon

results in little change for complex permeability, the matching
between the complex permittivity and permeability becomes
more effectively. Compared with permeability, the permittivity
of CS is so large that it is difcult to gain impedance match, which
means most of the incident microwave cannot transmit into
interior. Thus, the microwave absorption of CS is weak. However,
in CSFeNi, the reduction of complex permittivity brings about
proper impedance match. Then the electromagnetic wave can
easily transmit into the absorber. The incident microwaves
undergo an energy dissipation process, while the mesostructures
of absorbers can cause multiple reections and led to sufcient
absorption.
Besides the better impedance match and the mesostructure,
geometrical effect plays an important role in microwave
absorption, which means that when the thickness of absorber
satises the quarter-wavelength (l/4) condition [3537]:
d

nlm
n 1,3,5:::
4

c
q
9er mr 9

lm
fm



 Z Z 0 

R 20 log in
Z in Z 0 

1

2

where f is the frequency of the electromagnetic wave, d is the

thickness of the absorber, c is the velocity of light, Z0 is the
impedance of air and Zin is the input impedance of the absorber.
Fig. 5 shows the frequency dependence of the RL for the samples.
The RL value of 10 dB is corresponding to the 90% microwave

1271

where the incident and reected waves in the absorber are out of
phase 1801, the reected waves in the air-absorber interface will
be totally canceled. In the above equation, d and fm are the
matching thickness and peak frequency, er and mr are the complex
permittivity and permeability at fm, and c is the velocity of light.
The dc calculated through Eq. (5) (n 1) and the ds simulated by
Eq. (1) for each composite are shown in Fig. 7(c) and (d). In these
gures, the simulated results ds agree well with the calculated
values dc. It validates that the excellent microwave absorbing
ability is related to geometrical effect.

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G. Li et al. / Journal of Physics and Chemistry of Solids 73 (2012) 12681273

Fig. 7. Frequency dependence of RL for CS(a) and CSFeNi(b); dependence of l/4 thickness on frequency for CS(c) and CSFeNi(d).

Table 1
Electromagnetic wave absorption properties of some similar reports. Here, RLmin
and fmin are the minimum reection value and its corresponding frequency value,
respectively. f10 is frequency bands in which the reections RL is all below
 10 dB.

matching between the complex permittivity and permeability,

multiple absorption originated from the mesostructure, and the
geometrical effect.

Specimen

RLmin(dB)

fmin(GHz)

f10 (GHz)

Thickness(mm)

Ref.

Acknowledgments

FeNiCNTs
FeCoGNFs
FeNi/C
NiFeCNFs
FeCo/CF
CSFeNi

 9.9
 30.6
 4.3
 20
 48.2
 42.0

13.6
7.4
3.5
10
10.8
13.7

y
6.3  8.1
y
8.3  12
10  12
11.3  17.0

2
2
2
2.4
1.7
2.5

[38]
[39]
[40]
[41]
[42]
This work

This work was supported by Natural Science Foundation(Grant

no. 50871053) and Aeronautical Science Foundation of China
(Grant no. 2007ZF52061).

4. Conclusions
In summary, by introducing metal constituent FeNi alloy into
highly ordered mesoporous CSiO2 nanocomposite, an effective
microwave absorber CSFeNi is obtained. Compared with the
metal free composite, the complex permittivity of the CSFeNi
composite is reduced, and the permeability is almost unchanged,
resulting in a broader effective absorption bandwidth and lower
RL. The CSFeNi nanocomposites exhibits a maximum reection
loss of 45.6 dB at 11.1 GHz for a layer of thickness 3.0 mm and
the bandwidth lower than 10 dB is as large as 5.6 GHz when the
layer thickness is 2.5 mm. This material is promising as a lightweight, broad bandwidth, and strong absorption absorber. The
excellent absorbing property can be attributing to the better

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