APPLIED PHYSICS LETTERS 90, 011108 共2007兲

Doping effect of multiwall carbon nanotubes on the microwave

electromagnetic properties of NiCoZn spinel ferrites
Mangui Hana兲 and Longjiang Deng
State Key Laboratory of Electronic Thin Films and Integrated Devices, University of Electronic Science
and Technology of China, Chengdu 610054, China
共Received 13 October 2006; accepted 2 December 2006; published online 3 January 2007兲
NiCoZn ferrites have been found exhibiting two well separated resonance peaks. One is due to
domain wall movement at 1.76 GHz. One is due to spin rotation at 6.80 GHz. With increasing the
content of multiwall carbon nanotubes 共MWCNTs兲 in the NiCoZn ferrite/MWCNT/wax hybrid
composites, both resonance peaks are maintained, but their peak positions are found dependent on
the MWCNT content. The damping factor for spin rotation is found decreasing as the content of
MWCNT in composites increases. The dielectric loss of hybrid composites is also found
significantly increased by increasing the content of MWCNT. The doping effects of MWCNT are
thought due to the interaction between the ferrite and MWCNT. The microwave permeability of
pure MWCNT has also been investigated, and it is believed due to the residual nanosized Ni
particles. © 2007 American Institute of Physics. 关DOI: 10.1063/1.2429020兴

Since the discovery of carbon nanotubes 共CNTs兲 in 1991
by Iijima,1 the intensive investigations on CNT have shown
that CNT has a series of unique mechanical, electrical, mag-
netic, optical, and thermal properties.2–6 Multiwall carbon
nanotube 共MWCNT兲/epoxy resin composites are considered
good candidate materials for microwave applications due to
its large dielectric loss, such as antireflection, electromag-
netic interference shielding, or microwave absorbing.7,8 A
measurable induced magnetic moment has been observed
when CNTs are contacting with magnetic materials, espe-
cially with half metal magnetic materials, for instance,
Fe3O4. The induced magnetic moment was believed due to
the spin polarized charge transfer between CNTs and mag-
netic material.9,10 Except for this induced magnetism, there
are always some nanosized residual magnetic metals 共Fe or
Ni兲 left on CNT during the CNT manufacture process, and
enable the CNT to exhibit a weak ferromagnetism. A mag-
netoresistance effect also has been found in CNTs.11 As we
know, electromagnetic wave absorbers work by dissipating
electromagnetic energy into heat via magnetic and dielectric
losses. Spinel ferrites are one of the frequently used electro-
magnetic wave absorbing materials, but they suffer from the
lower spin rotation resonance compared with other ferrites,
such as hexagonal ferrites. In this letter, we report the doping
effect of MWCNT on the resonance frequencies of NiCoZn
spinel ferrites.
共Ni0.4Co0.24Zn0.36兲Fe2O4 ferrites with average particle
size of 2 – 3 ␮m have been synthesized by sintering the oxide
mixtures of Fe2O3, NiO, ZnO, and Co2O3 at 1250 ° C for
2 h. The crystal structure of prepared ferrite checked by
x-ray diffraction shows a typical spinel structure. MWCNTs
have been prepared by chemical vapor deposition using Ni as
the main catalyst. The average length of MWCNT is about
50 ␮m. The outer diameter of MWCNT is about 10– 30 nm.
The purity of MWCNT has been checked by energy disper-
sive x-ray 共EDX兲 measurement. Three composites of
NiCoZn ferrite and MWCNT have been prepared by adjust-
ing the MWCNT contents: Sample 0 contains 0 wt %
a兲
Electronic mail: mangui@gmail.com
MWCNT, sample 1 contains 5.2 wt % MWCNT, smple 2
contains 10.4 wt % MWCNT, and sample 3 contains
15.6 wt % MWCNT. In each composite sample for micro-
wave measurements, the weight of wax added for binding is
16 wt %. The ferrite, MWCNT, and wax are carefully mixed
to ensure that the samples are homogenous and isotropic.
The shape of samples for microwave measurements on an
Agilent 8720 vector network analyzer is toroidal with the
inner diameter of 3 mm and the outer diameter of 7 mm. The
frequency range selected for microwave measurements is
0.5– 14 GHz. The microwave permeability 共␮ = ␮⬘ − j␮⬙兲 of
pure MWCNT also has been measured.
The EDX measurement shows that the impurities of
MWCNT include Ni 共0.5 wt % 兲, Al 共0.1 wt % 兲, and O
共5.5 wt % 兲. Ni, Al, and O in MWCNT are residual sub-
stances due to the MWCNT fabrication process. As shown in
Fig. 1共a兲, two peaks are found in the spectrum of ␮⬙-f for
sample 0 共NiCoZn ferrite/wax composite兲. For these two
peaks, one is at 1.76 GHz and the other one is at 6.80 GHz.
It is well accepted that there are two mechanisms responsible
for the permeability dispersion of power ferrites: domain
wall motion and spin rotation. The resonance frequency of
domain wall motion 共i. e., f dw兲 is lower than the one for the
spin rotation 共i. e., f r兲. The permeability dispersion curve of
MWCNT is shown as the inset in Fig. 1共d兲. The observed
permeability of MWCNT is believed due to the residual
nanosized Ni particles on MWCNT. For samples 1, 2, and 3,
the magnetic materials contributing to the permeability spec-
trum shape include ferrite and Ni. For such hybrid magnetic
composites containing two ferromagnetic substances, the dis-
persion curve is extremely difficult to be expressed by super-
posing the magnetic spectrum of each magnetic material.
Similar situation has been reported in permalloy-NiZn ferrite
hybrid composite materials by Kasagi et al.12 Also, if the
permeability dispersion curve is badly distorted, the disper-
sion curve would be very difficult to be fitted by assuming it
comprises two component spectra: one is for domain wall
movement; one is for spin resonance, for instance, the per-
meability spectra in Fig. 1共d兲.

0003-6951/2007/90共1兲/011108/3/$23.00 90, 011108-1 © 2007 American Institute of Physics

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 011108-2 M. Han and L. Deng
FIG. 1. Microwave permeability spectra of NiCoZn ferrite/MWCNT/wax
hybrid composites, “dw” denotes the domain wall component. “spin” de-
notes the spin rotation component. ␮⬙ 共max兲 denotes the maximum value of
␮⬙ found on the experimental curve. 共a兲 is for sample 0 containing 0 wt %
MWCNT. 共b兲 is for sample 1 containing 5.2 wt % MWCNT. 共c兲 is for
sample 2 containing 10.4 wt % MWCNT. 共d兲 is for sample 3 containing
15.6 wt % MWCNT. The inset in 共c兲 denotes the ␮-f spectrum for
MWCNT/wax composite.
Based on the spectrum shape, we learn that the spectra in
Fig. 1 are the relaxation type because no negative ␮⬘ values
have been observed. Therefore, the resonances at lower fre-
quencies in Figs. 1共a兲–1共c兲 are due to the domain wall move-
ment mechanism. The resonances at higher frequencies are
due to the spin rotation mechanism. In Fig. 1共a兲, f dw and f s
are 1.76, and 6.80 GHz, respectively for sample 0. In
Fig. 1共b兲, f dw and f s are 1.28, and 8.03 GHz for sample 1.
In Fig. 1共c兲, f dw and f s are 1.98, and 11.08 GHz for sample 2.
Clearly, the doping effect of MWCNT on the resonance fre-
quency of spin rotation is much significant than that of do-
main wall movement. For the domain wall resonance with a
relaxation-type spectrum, the real and imaginary parts of per-
meability can be expressed by Debye’s dispersion law,13
1 Secondly, we calculate the ␮⬘-f curves by using the obtained
⬘ = 1 + ␹d0
␮dw , 共1兲
关1 − 共f/f dw兲2兴
f/f dw
⬙ = ␹d0
␮dw , 共2兲
关1 − 共f/f dw兲2兴
where ␹d0 is the static susceptibility for domain wall move-
ment. The resonance frequency f dw above can be expressed
by physical parameters as13 f dw = 共9␲␴wall␳兲 / 共8a␮20M s2兲,
where ␴wall is the density of domain wall energy, a is the
average distance of impurities in a ferrite particle which im-
pede the domain wall movements, ␳ is the electric resistivity
of ferrite, and M s is the saturation magnetization. In our case,
the ferrites in different composite samples are same. Hence,
␴wall can be considered as a constant. The particle size of
ferrites is about 2 – 3 ␮m. Multidomains can exist in each
ferrite particle, so the parameter a can be assumed as a con-
stant. Then, as shown in this equation, f dw is dependent on ␳
and M s. It is well known that MWCNT is a substance with
very low resistivity and weak ferromagnetism. Doped with
MWCNT, both ␳ and M s of ferrite-wax composite will drop.
Qualitively speaking, for sample 1, we can conjure that the
drop in ␳ is stronger than the drop in M s, hence f dw is lower
than the one for sample 0. For sample 2, the effect of the
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Appl. Phys. Lett. 90, 011108 共2007兲
TABLE I. Fitting parameters for permeability dispersion curves. f dw 共exp兲
and f s 共exp兲 denote the frequencies at which the ␮⬙ values on experimental
curves reach maximum for domain wall motion component and spin rotation
component, respectively. f s 共max兲 is the calculated value, please see its
definition in the text. f dw, f s, ␹d0, ␹s0, and ␣ are the fitting parameters.
Domain wall motion Spin rotation
f dw f dw 共exp兲 fs f s 共exp兲 f s 共max兲
Samples 共GHz兲 共GHz兲 ␹d0 共GHz兲 共GHz兲 共GHz兲 ␹s0 ␣
No. 0 1.57 1.76 1.49 9.42 6.80 6.39 1.167 1.083
No. 1 1.20 1.28 1.26 10.73 8.03 8.12 1.411 0.863
No. 2 1.63 1.98 1.83 11.37 11.08 10.20 0.881 0.493
drop in M s is stronger than the drop in ␳, then f dw is higher
than samples 0 and 1.
As for the spin resonance frequency f s, it depends on14
f s = 共␥ / 2␲兲 HA, where ␥ is the gyromagnetic ratio and HA is
the effective magnetic anisotropic field. In our case, the per-
meability spectrum due to the spin rotation mechanism is a
relaxation type. Accordingly it can be expressed as15
␹s0␻s2关共␻s2 − ␻2兲 + ␻2␣2兴
␮s⬘ = 1 + , 共3兲
关␻s2 − ␻2共1 + ␣2兲兴2 + 4␻2␻s2␣2
␹s0␻s␻␣关␻s2 + ␻2共1 + ␣2兲兴
␮s⬙ = , 共4兲
关␻s2 − ␻2共1 + ␣2兲兴2 + 4␻2␻s2␣2
where ␹s0 is the static susceptibility for spin rotation, ␻s is
the angular resonance frequency, ␣ is the damping factor for
spin rotation, and ␻ is the angular frequency of alternating
magnetic field.
Fitting the experimental curves in Fig. 1 with combined
equations for ␮⬘-f 关Eqs. 共1兲⫹共3兲兴 and ␮⬙-f 关Eqs. 共2兲⫹共4兲兴 is
found extremely difficult. Therefore, we have separately fit-
ted the peaks for spin rotation component 共designated as
“spin”兲 and domain wall component 共designated as “dw”兲 in
the spectra: Firstly, we fit each peaks in the ␮⬙-f curves.
fitting parameters and corresponding ␮⬘ expressions
关Eqs. 共1兲 or 共3兲兴. The fitting results are shown in
Figs. 1共a兲–1共c兲. The fitting parameters are listed in Table I.
f s共exp兲 is the frequency at which the ␮⬙ value of the spin
rotation component reaches a maximum value on the experi-
mental curve. f dw共exp兲 has a similar definition for the do-
main wall component on the experimental curve. As shown
clearly in Table I, the damping factor ␣ of spin rotation
mechanism is monotonously decreased with the increase of
the MWCNT contents in the composites. For spin rotation
resonance, the maximum frequency f s共max兲, which is de-
fined as the frequency at which ␮⬙ reaches a maximum
value, can be derived from Eq. 共4兲 as15 f s共max兲 = f s / 冑␣2 + 1.
With the obtained fitting parameters, the calculated f s共max兲
values are also listed in Table I. The small difference be-
tween the experimental f s共exp兲 values and the fitted f s共max兲
values indicate that our fitting method makes sense.
Tsutaoka reported that in ferrite/resin composites, both
f dw and f s increased with the decrease of the volume fraction
of Ni–Zn ferrites.15 They ascribed this to the gap parameter
共␦ / D兲 in ferrite composites. According to their theory, a
sphere ferrite particle 共or a particle cluster兲 with a diameter
of D is supposed to be enclosed by a layer of nonmagnetic
 011108-3 M. Han and L. Deng
FIG. 2. Microwave dielectric properties of NiCoZn ferrite/MWCNT/wax
composites. The inset in 共b兲 is the dependence of dielectric loss on the
different MWCNT loadings.
substance, such as epoxy resin. The thickness of nonmag-
netic layer is ␦ / 2. f dw and f r can be expressed, respectively
as f dw = f B-dw共1 + ␹B-dw共␦ / D兲兲1/2 and f s = f B-s共1 + ␹B-s共␦ / D兲兲,
where ␹B-dw 共f B-dw兲 and ␹B-s 共f B-s兲 are the static susceptibility
共resonance frequency兲 of bulk ferrite for domain wall motion
and spin rotation mechanisms, respectively. As the concen-
tration of nonmagnetic material increases 共i.e., the concen-
tration of magnetic material decreases兲, the ␦ / D value in-
creases. It is clear that both f dw and f s increase with the
decrease of ferrite content. However, in our case, the f dw
value is not monotonously increased with the decrease of the
ferrite content 共83, 78, and 72.9 wt % for samples 0, 1, and
2, respectively兲. For instance, f dw in sample 1 is lower than
those in samples 0 and 2, see Table I. Furthermore, we also
found that with more MWCNT 共15.6 wt % 兲 added in the
composite studied 共sample 3兲, the dispersion curve has been
seriously distorted, as shown in Fig. 1共d兲, where an addi-
tional peak appears. In Fig. 1共d兲, since the point A in the
inset and the A⬘ point have same frequency; therefore we
believe that the peak A⬘ is due to the effect of MWCNT. The
other two peaks are due to the spin rotation component
共f s共max兲 = 7.06 GHz兲 and domain wall component
共f dw共max兲 = 0.85 GHz兲. Compared with sample 2 in
Fig. 1共c兲, both f dw共max兲 and f s共max兲 in Fig. 1共d兲 have
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Appl. Phys. Lett. 90, 011108 共2007兲
shifted toward lower frequencies. Therefore, from the per-
spective of MWCNT doping effect on resonance frequency,
the appropriate doping range is 0 – 10.4 wt %. In addition,
the permeability behaviors of the MWCNT/NiCoZn ferrites/
wax hybrid composites are different from the one reported
by Tsutaoka15 Such an unusual behavior is believed due to
the interactions between the MWCNTs and the NiCoZn fer-
rite particles. Interactions maybe occur between the residual
nanosized Ni particles in MWCNT and NiCoZn ferrite par-
ticles, or between the MWCNT and NiCoZn particles. Fur-
ther investigation will be conducted in the future. The varia-
tion of permeability peak shapes also indirectly manifests the
existence of such an interaction.
The permittivity spectra for NiCoZn/MWCNT/wax hy-
brid composites are shown in Fig. 2. For sample without
MWCNT 共sample 0兲, the ␧ values are almost constant within
the measurement frequency range: ␧⬘ is about 5 and ␧⬙ is
about 0, showing a typical feature of ferrite in gigahertz
range. With increasing the MWCNT contents in composites
共samples 1–3兲, both ␧⬘ and ␧⬙ increase in the measurement
frequency range, and both are gradually decreased with in-
creasing frequency. Especially, for sample 2 and 3, there is a
clear inverse proportion relationship between ␧⬙ and fre-
quency. This is a typical feature of a conducting media and
shows that with more MWCNT added into the studied com-
posite, it will become a conducting composite due to the high
conductivity of MWCNT. At lower frequency range of
0.5– 6 GHz, both samples 2 and 3 show a significant dielec-
tric loss, please see the ␧⬙ / ␧⬘ values in the inset in Fig. 2共b兲.
In summary, for NiCoZn ferrite/MWCNT/wax hybrid
composites, f dw and f s are found dependent on the contents
of MWCNT, especially for the spin rotation resonance fre-
quency f s. From the perspective of increasing resonance fre-
quency, the suitable doping range is 0 – 10.4 wt %. An in-
creased dielectric loss also can be obtained. Employed as an
electromagnetic wave absorber, the reported results in this
letter offer us an alternative to adjust its working frequency
range and dielectric loss.
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