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Controllable synthesis, characterization and microwave absorption properties of magnetic

Ni1−x Cox P alloy nanoparticles attached on carbon nanotubes

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2008 J. Phys. D: Appl. Phys. 41 125303

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IOP PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS
J. Phys. D: Appl. Phys. 41 (2008) 125303 (7pp) doi:10.1088/0022-3727/41/12/125303

Controllable synthesis, characterization

and microwave absorption properties of
magnetic Ni1−xCoxP alloy nanoparticles
attached on carbon nanotubes
Yongjie Li, Cunzhen Zhu and Chunming Wang
Department of Chemistry, Lanzhou University, Lanzhou 730000, People’s Republic of China
E-mail: wangcm@lzu.edu.cn

Received 29 February 2008, in final form 21 April 2008

Published 29 May 2008
Online at stacks.iop.org/JPhysD/41/125303

Abstract
Ni1−x Cox alloy nanoparticles (x = 0.25, 0.50, 0.75), with diameters in the range 8–18 nm were
uniformly attached on the surface of multi-walled carbon nanotubes (MWNTs) by electroless
plating, and were characterized by transmission electron microscopy, energy-dispersive x-ray
spectrometry, x-ray diffraction analysis, vibrating sample magnetometry and vector network
analysis. Magnetization measurement indicates that both coercivities and saturation
magnetizations decreased linearly with increasing Ni concentration in Ni–Co–P deposits. The
complex permittivities of MWNT–olefin matrix composites also decreased linearly with
increasing Ni concentration while the complex permeabilities increased slightly, which were
measured in the range 2–18 GHz. The microwave absorbing properties enhanced with
increasing Co concentration and a maximum reflection loss of −26.84 dB was obtained at a
frequency of 7.75 GHz when the matching thickness was 2.5 mm and x = 0.75.

1. Introduction An alternative approach is coating support media of low

In recent years, the problem of electromagnetic interference
(EMI) has attracted considerable attention due to the explosive
growth in the application of electronic devices such as mobile
phones, local area networks, personal computers and radar
systems [1–3, 12]. EMI can cause severe interruption in
electronically controlled systems. Furthermore, overexposure
to microwave energy can be potentially harmful to biological
systems [4]. Amongst effects that have been reported
were structural rearrangement of protein due to nonthermal
microwave effects [5], increase in heart-beat rate [6], inducing
deoxyribonucleic acid (DNA) strand breaks in rat brain cells
[7], weakening of immune responses [8] and the possibility
of cancer [9]. To overcome the electromagnetic interference
problems, electromagnetic wave absorbing materials with the
capability of absorbing unwanted electromagnetic signals are
suggested [3] and are therefore very attractive. Conventional
absorbing materials such as ferrites and metallic materials
have been studied widely [3, 4, 10–14]. Although presenting
good absorption properties these materials are too heavy.
density with polymer or metallic materials [15, 16]. A
recent development in absorber technology is to produce
absorbers that are thin, flexible and strong. Carbon nanotubes
(CNTs) are very suitable as supporting media for this purpose
because of their low density, good thermal and chemical
stabilization.
CNTs are attracting increasing scientific and technological
interest with their novel properties and potential applications
[17]. The study of metal-coated CNTs is now becoming a
promising and challenging area of research owing to their
unique applications such as nanoelectronic devices [18],
support media in heterogeneous catalysis [19, 20], fuel cells
[21, 22], magnetic recording [23] and microwave absorbers
[16]. As is well known, there have been various approaches
for depositing metallic nanoparticles such as Ni [24,25], Fe–Ni
[26], Fe–Co [27], Cu [25], Pd [28–30], Pt [29, 31], Ag [29, 31]
and Au [29, 31] on the surface of CNTs by electrochemical
deposition [24], electroless plating [25], wet chemistry [26,
27], chemical evaporation deposition [28], solid-state reaction
[29], supercritical carbon dioxide deposition [30] and chemical

0022-3727/08/125303+07$30.00 1 © 2008 IOP Publishing Ltd Printed in the UK

J. Phys. D: Appl. Phys. 41 (2008) 125303
Table 1. Bath composition and operating conditions for electroless
nickel–cobalt coating.
Chemical reagent Concentration
Nickel sulfate, hexahydrate 0.05–0.15 mol l−1
Cobalt sulfate, heptahydrate 0.05–0.15 mol l−1
Sodium citrate 40 g l−1
Ammonium sulfate 40 g l−1
Sodium hypophosphite, monohydrate 15 g l−1
Operating conditions
pH (adjusted using NaOH) 9.03–9.05
Bath temperature 80 ◦ C
decoration [31]. As for bimetallic systems or alloys, Ni–Co
alloys are interesting for their remarkable magnetic properties
and a slight variation in the composition of the Ni–Co alloy can
cause substantial changes in the coercivities and microwave
absorbing properties. Therefore, the control of composition is
often a key element in optimizing the magnetic properties in
a magnetic material. Since there are no literature reports on
Ni–Co alloy nanoparticles attached on CNTs, we are interested
in the preparation of Ni–Co alloy nanoparticles attached on
CNTs with a controllable composition. The main objectives
of this work are to prepare Ni1−x Cox alloy nanoparticles
(x = 0.25, 0.50, 0.75) attached on the surface of CNTs by
electroless plating, to characterize the coated CNTs and to
investigate the magnetic, microwave dielectric and absorptive
properties of the prepared samples.
2. Experimental
The multi-walled carbon nanotubes (MWNTs) purchased from
Shenzhen Nanotech Port Co. Ltd (China) have an outer
diameter in the range 40–60 nm (with lengths of up to a
few micrometres). The procedure employed for preparing
Ni1−x Cox alloy nanoparticles attached on CNTs is as follows.
In a typical synthesis, MWNTs (100 mg) were treated with
boiling HNO3 (68% 50 ml) for 5 h, washed with distilled water
and then fully dispersed in a solution of 10 g l−1 SnCl2 for
60 min with continuous stirring at room temperature. After
washing with distilled water, the Sn2+ -sensitized nanotubes
were further activated in an aqueous solution of 0.25 g l−1
PdCl2 for another 150 min with continuous stirring at a
temperature of 40–50 ◦ C. The activated nanotubes were
washed with distilled water and then introduced into an
electroless-plating bath. The composition of the plating
solution and the reaction conditions are given in table 1. By
varying the molar ratio of the nickel and cobalt salts in the
solution with atomic ratios of Ni : Co = 3 : 1, 1 : 1 and 1 : 3,
respectively, Ni1−x Cox alloys were prepared.
Phase analysis of the coated CNTs was carried out by
a x-ray diffraction analyzer ((XRD) Rigaku D/max-2400
Cu K-α radiation, λ = 0.1541 nm) in the 2θ range from 20◦
to 80◦ . The morphologies and composition of coated CNTs
were characterized using a transmission electron microscope
((TEM) JEM-1200EX) and an energy-dispersive x-ray (EDX)
spectrometer attached on a scanning electron microscope
((SEM) JSM-5600LV/KEVEX Sigma). The static magnetic
property of coated CNTs was measured at room temperature
2
Y Li et al
Figure 1. XRD patterns of the Ni1−x Cox P alloy nanoparticles
attached on CNTs: (a) x = 0.25; (b) x = 0.50; (c) x = 0.75.
using a vibrating sample magnetometer ((VSM) Lakeshore
7304). The sample, containing 25 wt% Ni–Co–P–CNT
particles that were mixed with olefin by heating up, was
made into a toroidal-shaped sample with an outer diameter of
7.0 mm and an inner diameter of 3.0 mm for the microwave
measurement. The complex permeability and permittivity
of the composite were investigated using a vector network
analyzer (Agilent E8363B) in the frequency range 2–18 GHz.
The reflection losses were calculated using the measured
complex permittivity and permeability.
3. Results and discussion
3.1. XRD characterization
Figure 1 shows the XRD patterns of the heat-treated samples
at 500 ◦ C for 3 h, which displays the presence of the
crystal structure of Ni1−x Cox (x = 0.25, 0.50 0.75) alloy
nanoparticles. As seen, when x = 0.25 and 0.50 the XRD
spectra in figures 1(a) and (b) show that the peaks at 2θ values
of 37.4◦ , 43.4◦ , 62.9◦ and 75.3◦ correspond to the crystal planes
of (1 1 2), (4 1 1), (0 0 4) and (4 0 4) of crystalline Ni1−x Cox
alloy (JCPDS75-1328), respectively. It is clear that the peak
at the 2θ value of 26.3◦ is caused by the CNTs. However, as
seen from figure 1(c), when x = 0.75 the peaks at 2θ values of
31.2◦ , 44.6◦ , 59.1◦ and 64.9◦ correspond to the crystal planes
of (3 1 3), (2 2 1), (1 3 0) and (8 0 2), respectively, agreeing well
with standard cards (JCPDS75-1329 and JCPDS76-2283). It is
evident that the amorphous nature of the deposits still remains
when the temperature of the heat treatment is below 300 ◦ C
according to [32]. After the heat treatment at 300 ◦ C for 1 h,
the XRD pattern reveals the presence of fcc nickel, bct nickel
phosphide (Ni3 P) and hexagonal Ni5 P2 phases. It can be seen
that the Ni5 P2 phase disappeared, but a tetragonal Ni12 P5 phase
was formed after annealing at 400 ◦ C for 1 h. Finally, when
being annealed at 480 ◦ C, the Ni12 P5 phase vanishes and the
Ni phase and the Ni3 P phase increase strongly. It is also clear
that the effect of mole ratios CoSO4 /(CoSO4 + NiSO4 ) on
the phase transformation behaviour of electroless Ni–Co–P
deposits is trivial [32]. Although Huang et al only discussed
J. Phys. D: Appl. Phys. 41 (2008) 125303
Figure 2. TEM images of the Ni1−x Cox P alloy on CNTs at different
atom ratios of (a) x = 0.25; (b) x = 0.50; (c) x = 0.75.
the crystallization process of specimen Ni65.8 Co19.6 P15.6 after
heating at the temperatures of 260, 300, 420 and 480 ◦ C for 1 h,
the phase transformation processes of different compositions
of Ni–Co–P alloy particles are similar to each other in the
range 250–435 ◦ C. Therefore, Ni–Co–P ternary alloy deposits
attached on MWNTs transformed into different crystal planes
but similar mixture crystallizations of α-Co, Ni and Ni3 P in this
paper. Although the Ni1−x Cox alloy only comprises a small
portion of the samples, its peaks are much stronger and sharper
than those of CNTs, revealing the high crystalline structure of
the nanoparticles. The average sizes of the Ni1−x Cox alloy
nanoparticles which were calculated by using the Debye–
Scherrer formula [33] based on the full-width at half-maximum
(FWHM) of the (1 1 2) diffraction peak are 8.18 nm, 8.53 nm,
18.39 nm when x = 0.25, 0.50, 0.75, respectively. The 2θ of
the (1 1 2) diffraction peak are 37.18◦ , 37.44◦ , 36.65◦ , and the
FWHM are 1.08◦ , 1.04◦ , 0.518◦ when x = 0.25, 0.50, 0.75,
respectively. The results indicated that the alloy sizes decrease
with the increase in nickel concentration, which is caused by
the fact that the Co atom radius (1.25 Å) is bigger than the Ni
atom radius (1.24 Å).
3.2. TEM images and EDX analysis
Figure 2 shows the TEM images of Ni1−x Cox (x = 0.25,
0.50, 0.75) alloy nanoparticles attached on MWNTs. It
3
Y Li et al
can be seen that the Ni1−x Cox alloy nanoparticles are in
the form of irregular dots and are dispersed disorderly and
unsystematically on the outer sidewall of the CNTs. And
it can also be seen that Ni1−x Cox alloy nanoparticles could
be obtained in the inner sidewall of the CNTs. These entire
phenomena could be explained as follows. The MWNTs
have ultra-small size, high chemical stability and large surface
area and have no autocatalytic capability. Thus, only the
sensitized and activated position on CNTs can be nucleated
and subsequently plated. The Pd-activation procedure in
the pretreatment step of CNTs assured the elimination of
the passive condition of the surfaces, making them suitable
for electroless plating due to the presence of chemically
deposited Pd nuclei that initiate nickel and cobalt deposition.
However, the activation process of the nanotube surface does
not produce a uniform distribution of palladium compared
with the large surface to be plated. This is because MWNTs
were subjected to oxidation pretreatment using HNO3 solution
[34], so as to remove impurities and generate sufficient
numbers of functional groups, such as –OH, –COOH and
–C=O, on the surfaces. These surface functional groups
have stronger attraction forces towards metal ions than bare
CNT surfaces and some even have ion exchange capabilities,
such as carboxylic acid groups. Therefore, they are believed
to work as metal-anchoring sites in order to facilitate metal
nuclei formation and metal deposition. In fact, this process
is somewhat similar to electroless deposition that requires
some imperfect sites on the substrate surfaces to anchor and
hold the reduced metals. Caturla et al [35] also found a
very irregular distribution of palladium after activation of
polycrystalline graphite with Sn/Pd, with large areas of the
surface not covered by palladium. Therefore, Ni1−x Cox
alloy nanoparticles could not be obtained perfectly uniform
on the outer surface of CNTs. In addition, owing to the
capillary function, Ni1−x Cox alloy nanoparticles can also
be encapsulated in the cavities. The average values of the
nanoparticles’ size measured from TEM images were 9.0 nm,
10.0 nm, 20.0 nm for x = 0.25, 0.50, 0.75, respectively. With
the increase in nickel concentration , the size of nanoparticles
decreases. This trend is consistent with the trend of the
changes in the size that were calculated from the Debye–
Scherrer formula, but the alloy size measured from the TEM
image is slight larger than that calculated from the Debye–
Scherrer formula under the same molar ratio of nickel to
cobalt. The possible reasons for this discrepancy include the
contributions of microstrains to line broadening [36] and the
differences between volume-weighted averaging in XRD and
number-weighted averaging for TEM. These results indicate
that the size of Ni–Co alloy nanoparticles could be controlled
by adjusting the ratio of nickel to cobalt in the mixed solution of
sulfates, and these CNTs are efficient templates in the synthesis
of nanoscale metal alloy nanoparticles.
The chemical composition of the Ni1−x Cox alloy
nanoparticles on the CNTs was analysed using the energy-
dispersive x-ray spectrometer attached to the scanning electron
microscope. The EDX spectrum of an individual nanoparticle
shows nickel, cobalt, phosphorus and carbon. Figure 3 is
shown as an example. It is clear that carbon is caused
J. Phys. D: Appl. Phys. 41 (2008) 125303
Figure 3. The EDX spectrum of the Ni0.75 Co0.25 alloy on CNTs.
by MWNTs. The EDX quantitative microanalysis shows
the following: Ni (73.35 at%) and Co (20.16 at.%) in
Ni0.75 Co0.25 ; Ni (42.72 at%), Co (43.93 at%) in Ni0.50 Co0.50 ;
Ni (32.18 at%) and Co (55.94 at%) in Ni0.25 Co0.75 . In addition,
autocatalytic nickel–cobalt deposition was preformed using
sodium hypophosphite as the reducing agent, giving electroless
nickel–cobalt deposits along with a simultaneous deposition
of phosphorus from the electroless bath. Therefore, the
electroless nickel–cobalt deposit was a Ni–Co–P ternary
alloy, as confirmed by the EDX examination. Thus, the
phosphorus content in Ni1−x Cox P alloys is 6.49 at%, 13.36 at%
and 11.88 at% when x = 0.25, 0.50 and 0.75, respectively.
It was noted that the composition of the Ni1−x Cox alloys
attached on the surface of CNTs formed from their mixed
sulfate solution was close to but different from the original
composition of sulfates. The reasons can be explained
as follows: for electroless Ni–Co–P plating, the oxidizing
and reducing reactions and their standard Gibbs free energy
changes [37] can be represented as below:
H2 PO− − −
2 + H2 O = H2 PO3 + 2H + 2e ,
+
G◦ = −96.5 kJ,
(1)
2H2 PO−
2
+ −
+ 4H + 2e = 2P + 4H2 O, ◦
G = +48.3 kJ,
(2)
Ni2+ + 2e− = Ni, G◦ = +54.0kJ, (3)
Co2+ + 2e− = Co, G◦ = +48.3 kJ. (4)
From the value of G◦ for each reaction, it is clear that Ni,
Co and P can all be reduced by sodium hypophosphite and the
trend of reduction for Ni is larger than Co. Additionally, the
catalytic activity of Ni for the reaction of (1) is better than that
of Co [38]. Therefore, the concentration of Ni in a Ni–Co–P
ternary alloy is always larger than Co.
3.3. Magnetic measurements
The magnetic properties of CNTs impregnated with Ni–Co
deposits were investigated at room temperature using a
4
Y Li et al
Figure 4. Hysteresis loops of the Ni1−x Cox P-CNT nanoparticles
measured at room temperature.
Table 2. Magnetization data for Ni1−x Cox on CNTs at room
temperature.
Samples (Ni1−x Cox ) Mr /Ms Hc (Oe) Ms (emu g−1 )
x = 0.25 0.36 319.75 14.29
x = 0.50 0.29 368.34 16.67
x = 0.75 0.22 369.91 29.32
vibrating sample magnetometer with an applied field of
−10 000 Oe
H
10 000 Oe. Figure 4 shows the
hysteresis loops of the samples with Ni0.75 Co0.25 , Ni0.50 Co0.50
and Ni0.25 Co0.75 alloys attached on CNTs, which are the
typical loops of a soft magnet. Coercivity and saturation
magnetization values for all samples are listed in table 2.
The coercivity of Ni–Co alloy nanoparticles decreased with
increasing Ni content; this trend can be well correlated with
the size of the Ni1−x Cox alloy nanoparticles, i.e. the size
of nanoparticles decreased with increasing Ni content. The
behaviour is in good agreement with the theoretical predictions
of the random-anisotropy model (RAM) [26]. On the other
hand, the coercivity of the Ni-containing particle is lower than
that of the Ni-free particle because of the random distribution
of the particles [26]. It is noted that the differences in the
coercivity of Ni1−x Cox alloy nanoparticles are small when
x = 0.5 and 0.75.
The dependence of the saturation magnetization of the
Ni1−x Cox alloys at room temperature on Co concentrations
is shown in table 2. The saturation magnetization values
of the Ni1−x Cox alloy nanoparticles are 14.29 emu g−1 ,
16.67 emu g−1 and 29.32 emu g−1 when x = 0.25, 0.50 and
0.75, respectively. It is noted that a comparison of the
magnetic characteristics of electroless Ni–Co–P deposits of
this study reveals that the saturation magnetization increased
with increasing Co content of the deposits. This can be mainly
attributed to the cobalt atom’s substitution of the nickel atom in
the deposits and the fact that the nickel atom has a much smaller
magnetic moment than the cobalt atom. The Bohr magnetons
(MB ) of Co atom and Ni atom are 1.7 and 0.6, respectively.
Therefore, the magnetic moment of cobalt is better than that
of nickel. The P atom is nonmagnetic. The Co content of
the Ni0.25 Co0.75 layer is the largest; therefore, the Ni0.25 Co0.75
J. Phys. D: Appl. Phys. 41 (2008) 125303
Figure 5. Frequency dependence of the complex relative dielectric
permittivity for the Ni1−x Cox P alloy nanoparticles attached on
CNTs: (a) x = 0.25; (b) x = 0.50; (c) x = 0.75.
coating possesses better magnetism than the Ni0.75 Co0.25 and
Ni0.50 Co0.50 coatings. Rivero et al [39] reported a linear
increase in the magnetic moment with the increase in the cobalt
content for electrodeposited Ni–Co–P amorphous ribbons and
Matsubara [40] also reported an increase in the saturation
magnetization of electroless Ni–Co–P deposits with increased
cobalt content.
3.4. Microwave and absorption properties
Figure 5 illustrates the real and imaginary parts of the
complex relative dielectric permittivity versus frequency for
the prepared powder–olefin composites. As shown in figure 5
the powder–olefin composites exhibit a slightly decreased
real part εr of the complex relative dielectric permittivity
except for a little variation that was observed at around
14 GHz. The average values of the real part εr of the
complex relative dielectric permittivity of Ni1−x Cox alloy
nanoparticles attached on CNTs are increased regularly when
the x values increased from 0.25 to 0.75. The reason for the
difference in the complex relative dielectric permittivity of
the three samples may be the different composition contents
of the plated Ni–Co–P layers. The electrical resistivities at
25 ◦ C of Ni and Co are as follows: Ni—6.84 × 10−8  m;
Co—6.64 × 10−8  m; thus, the electrical conductivity of
cobalt is better than nickel, and their electrical conductivities
are all higher than phosphorus, which is nonconductive. It
can be seen from the EDX analysis that the concentration of
metals in Ni1−x Cox alloy nanoparticles increases along with
the increased x values. Therefore, the increased average values
of the real part εr of the complex relative dielectric permittivity
of Ni1−x Cox alloy nanoparticles could be attributed to better
metallic behaviour of cobalt and nickel atoms than the
phosphorus atom. However, the real part values of the complex
relative dielectric permittivity are comparatively smaller than
those observed for the metal powder or fibre composites
as reported in the literature [41–43]. The lower real part
value of complex relative dielectric permittivity is of great
advantage for striking a balance between permeability and
permittivity, thus decreasing the reflection coefficient of the
absorber compared with other metal magnetic materials for
microwave absorbing application. Generally the permittivity
5
Y Li et al
Figure 6. Frequency dependence of the complex relative magnetic
permeability for the Ni1−x Cox P alloy nanoparticles attached on
CNTs: (a) x = 0.25; (b) x = 0.50; (c) x = 0.75.
originates from orientation polarization, atomic polarization
and electronic polarization. Normally, the resonance that
originates from vacancy or pores usually dominates in the
low frequency regions, provided that there exist space charges
in the materials. High frequency resonances are attributed
to atomic and electronic polarizations [44]. The values of
the complex relative dielectric permittivity of metal or oxide
particles are usually constant in the microwave frequency
range or decrease with increasing frequency [42–46]. The
most probable mechanism of resonance in this frequency
range is electronic or ionic polarization, because the high
dielectric constant and the dielectric loss of ferroelectric
materials in the microwave frequency region was explained
by domain wall polarization or dynamics of polar clusters,
and electronic displacement (optical polarization) and ionic
displacement (infrared polarization) have contribution to the
dielectric constant that is too small: εr ≈ 10 in most ionic
crystals [47]. The imaginary part εr of the complex relative
dielectric permittivity in figure 5 is almost constant between
3 and 13 GHz, but increases slightly for frequencies below 3
and above 13 GHz. The dielectric loss in the samples can be
described as being due to the contributions from both the dc
conductivity and the ac conductivity or ion jump and dipole
relaxation based on the expression [3, 4]
εr = [σdc /(ωε0 ) + εac

], (5)
where σdc is the dc conductivity, ω is the angular frequency,

ε0 is the permittivity of free space and εac is the ac loss
contribution at high frequencies. The expression shows that
dc conduction loss is inversely proportional to the frequency,
hence, the reason for the increase in εr for the materials with
a decrease in frequency in the low-frequency regime. Similar
behaviour has also been observed for LiZn ferrites [4].
The frequency dependence of the complex relative
magnetic permeability for Ni1−x Cox alloy nanoparticles is
shown in figure 6. One feature of the data is that the values of
the real part µ of the complex relative magnetic permeability
for the three samples are close to each other and all decrease
slightly with increasing frequency except for a little variation
around the frequency of 14 GHz. The three samples show
an almost constant imaginary part µ of the complex relative
J. Phys. D: Appl. Phys. 41 (2008) 125303
Figure 7. Frequency dependence of the reflection loss for the
Ni1−x Cox P alloy nanoparticles attached on CNTs at the thickness of
2.5 mm: (a) x = 0.25; (b) x = 0.50; (c) x = 0.75.
magnetic permeability in the frequency range 2–18 GHz. This
is most likely caused by the intrinsically small magnetic loss
tangent (tan δM ) of the MWNTs used in this study.
The normalized input impedance Zin of a single metal-
backed microwave-absorbing layer is given by [48]

 √ 
µr 2πf d µr εr
Zin = tanh j , (6)
εr c
where µr and εr are the relative complex permeability and
permittivity, respectively, of the composite medium, c is the
velocity of electromagnetic waves in free space, f is the
frequency of microwaves and d is the thickness of the absorber.
The reflection loss is related to Zin by [48]
 
 Zin − 1 
RL = 20 lg  . (7)
Zin + 1 
Thus, the surface reflectance of an absorber is a function of
six characteristic parameters, namely, µr , µr , εr , εr , f and
d. Figure 7 shows the calculated reflection loss as a function
of the frequency for Ni1−x Cox alloy nanoparticles plated on
CNTs at a matching thickness of 2.5 mm. When the x value
is up to 0.75, the peak value reaches the maximum value
of −26.84 dB corresponding to the frequency of 7.75 GHz.
Additionally when x values are 0.25 and 0.50, the peak values
are −9.83 dB and 11.28 dB corresponding to the frequencies
of 11.49 GHz and 9.98 GHz, respectively. It is clear that
the position of the strongest reflectivity peak is shifted to
a lower frequency with increasing Co content, which may
result from the different compositions of the powders. It
can also be concluded that the difference in the microwave
absorption properties of the Ni1−x Cox alloy nanoparticles
can be attributed to the different cobalt content in the plated
Ni–Co–P layers. Generally, microwave absorption properties
of microwave absorbing materials are determined by the
dielectric and magnetic losses, and for magnetic microwave
absorbers, the magnetic loss is the main microwave loss tunnel.
The Bohr magnetons (MB ) of the Co atom and the Ni atom
are 1.7 and 0.6, respectively. So, the magnetic moment of
cobalt is better than nickel. The P atom is nonmagnetic. The
6
Y Li et al
powder with better magnetism results in a larger microwave
loss. The Co content of the Ni0.25 Co0.75 layer is the largest,
and the Ni0.25 Co0.75 coating possesses better magnetism than
the Ni0.75 Co0.25 and Ni0.50 Co0.50 coatings. Therefore, the
reflection loss is enhanced along with the increased x values in
Ni1−x Cox P ternary alloys. Additionally, from the permittivity
and permeability data shown in figures 5 and 6, it seems that
the dielectric loss shows a significant change compared with
magnetic loss for these three samples. However, according to
expressions (6) and (7), it can be seen that the combinations of
both µr and εr determine the reflection loss. Thus, the primary
variation of reflection loss with frequency can be considered
to be the integrated result of dielectric loss and magnetic
loss. Compared with conventional ferrites of high density, the
density of these magnetic CNTs is very low and CNT-based
substances have good mechanical property;therefore, this is
an effective way of reducing the weight of absorbing materials
in the Ku-band. In short, the prepared samples exhibit good
absorption performance in the 2–18 GHz frequency band and
appear to be potential microwave-absorbing materials. Further
study is in progress to adjust the permeability and permittivity
to improve the absorbing properties and expand the absorbing
bandwidth.
4. Conclusions
In summary, Ni1−x Cox alloy nanoparticles (x = 0.25, 0.50,
0.75) attached on the surface of MWNTs were prepared
by electroless plating with a controllable composition.
The characterization techniques show that Ni–Co alloy
nanoparticles are transformed into the crystal structure after
heat treatment and are in the form of irregular dots and
dispersed disorderly and unsystematically in the cavities or
attached on the external surface of CNTs. The magnetic
measurement shows that both coercivity and the saturation
magnetization decrease with increasing Ni concentration. In
addition, along with increasing Co concentration, the position
of the reflectivity peak moves to a lower frequency and a
maximum reflection loss of −26.84 dB was obtained at the
frequency of 7.75 GHz when the matching thickness was
2.5 mm and x = 0.75. The results evidently demonstrate
that electroless plating is a promising method of fabricating
Ni–Co alloy nanoparticles coated on CNTs for applications in
suppression of electromagnetic wave interference.
Acknowledgment
This work was supported by the National Natural Science
Foundation of China (grant no. 20577017).
References
[1] Lim K M, Kim M C, Lee K A and Park C G 2003 IEEE Trans.
Magn. 39 1836
[2] Sugimoto S et al 1998 Mater. Trans. 39 1080
[3] Yusoff A N, Abdullah M H, Ahmad S H, Jusoh S F,
Mansor A A and Hamid S A A 2002 J. Appl. Phys. 92 876
[4] Yusoff A N and Abdullah M H 2004 J. Magn. Magn. Mater.
269 271
J. Phys. D: Appl. Phys. 41 (2008) 125303
[5] Porcelli M, Cacciapuoti G, Fusco S, Massa R, d’Ambrosio G,
Bertoldo C, De Rosa M and Zappia V 1997 FEBS Lett.
402 102
[6] Jauchem J R, Ryan K L and Frei M R 2000
Bioelectromagnetics 21 159
[7] Lai H and Singh N P 1997 Bioelectromagnetics 18 446
[8] Veyret B, Bouthet C, Deschaux P, de Seze R, Geffard M,
Joussot-Dubien J, le Diraison M, Moreau J M and
Caristan A 1991 Bioelectromagnetics 12 47
[9] Ritcher E, Berman T, Ben-Michael E, Laster R and Westin J B
2000 Int. J. Occup. Environ. Health 6 187
[10] Meshram M R, Agrawal N K, Sinha B and Misra P S 2004
J. Magn. Magn. Mater. 271 207
[11] Shen G, Xu Z and Li Y 2006 J. Magn. Magn. Mater. 301 325
[12] Liu J R, Itoh M and Machida K 2003 Appl. Phys. Lett. 83 4017
[13] Miura K, Masuda M, Itoh M, Horiikawa T and Machida K
2006 J. Alloys Compounds 408–412 1391
[14] Zhang B, Lu G, Feng Y, Xiong J and Lu H 2006 J. Magn.
Magn. Mater. 299 205
[15] Fan Z J, Luo G H, Zhang Z F, Zhou L and Wei F 2006 Mater.
Sci. Eng. B—Solid State Mater. Adv. Technol. 132 85
[16] Ch. Che R, Peng L M, Duan X F, Chen Q and Liang X L 2004
Adv. Mater. 16 401
[17] Robert F 1998 Science 281 940
[18] Dai H J, Wong E W and Lieber C M 1996 Science 272 523
[19] Coq B, Planeix J M and Brotons V 1998 Appl. Catal. A—Gen.
173 175
[20] Liu Z J, Xu Z D, Yuan Z Y, Lu D Y, Chen W X and Zhou W Z
2001 Catal. Lett. 72 203
[21] Steigerwalt E S, Deluga G A and Lukehart C M 2002 J. Phys.
Chem. B 106 760
[22] Che G, Lakshmi B B, Martin C R and Fisher E R 1999
Langmuir 15 750
[23] Liu Z J, Xu Z D, Yuan Z Y, Chen W X, Zhou W Z and
Peng L M 2003 Mater. Lett. 57 1339
[24] Xu Q, Zhang L and Zhu J 2003 J. Phys. Chem. B 107 8294
[25] Ang L M, Andy Hor T S, Xu G Q, Tung C H, Zhao S P and
Wang J L S 2000 Carbon 38 363
[26] Wu H Q, Cao Y J, Yuan P S, Xu H Y and Wei X W 2005
Chem. Phys. Lett. 406 148
[27] Wu H Q, Yuan P S, Xu H Y, Xu D M, Geng B Y and Wei X W
2006 J. Mater. Sci. 41 6889
Y Li et al
[28] Kong J, Chapline M G and Dai H 2001 Adv. Mater. 13 1384
[29] Xue B, Chen P, Hong Q, Liu J and Tan K L 2001 J. Mater.
Chem. 11 2378
[30] Ye X R, Lin Y H and Wai C M 2003 Chem. Commun. 5 642
[31] Satishkumar B C, Vogl E M, Govindaraj A and Rao C N R
1996 J. Phys. D: Appl. Phys. 29 3173
[32] Huang Y, Shi K, Liao Z J, Wang Y L, Wang L and Zhu F 2007
Mater. Lett. 61 1742
[33] Wu H Q, Shao M W, Gu J S and Wei X W 2004 Mater. Lett.
58 2166
[34] Chien C C and Jeng K T 2006 Mater. Chem. Phys. 99 80
[35] Caturla F, Molina F, Moline-Sabio M and
Rodriguez-Reinoso F 1995 J. Electrochem. Soc.
142 4084
[36] Fenineche N E, Hamzaoui R and El Kedim O 2003 Mater.
Lett. 57 4165
[37] Glenn O M and Juan B H 1990 Electroless Plating:
Fundamentals, Applications (Orlando, FL: American
Electroplaters and Surface Finishers Society)
[38] Chiang H H and Shen W 2001 The Fundamentals and
Practice of Electroless Plating (Beijing: National Defense
Industry Publisher)
[39] Rivero G, Multigner M, Garcia J M, Crespo P and Hernando A
1998 J. Magn. Magn. Mater. 177–181 119
[40] Matsubara H and Yamada A 1994 J. Electrochem. Soc.
141 2386
[41] Wu M Z, He H H, Zhao Z S and Yao X 2000 J. Phys. D: Appl.
Phys. 33 2927
[42] Wu M Z, He H H, Zhao Z S and Yao X 2000 J. Phys. D: Appl.
Phys. 33 2398
[43] Chen P, Wu R X, Zhao T E, Yang F and Xiao J Q 2005 J. Phys.
D: Appl. Phys. 38 2302
[44] Verma A, Saxena A K and Dube D C 2003 J. Magn. Magn.
Mater. 263 228
[45] Matsumoto M and Miyata Y 1997 IEEE Trans. Magn.
33 4459
[46] Wu M Z, Yao X, Zhai J W and Zhang L Y 2001 Meas. Sci.
Technol. 12 1932
[47] Kim S S, Yoon Y C and Kim K H 2003 J. Electroceram.
10 95
[48] Kim S S, Jo S B, Gueon K I, Choi K K, Kim J M and
Churn K S 1991 IEEE Trans. Magn. 27 5462