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magnetic properties are controlled by both the demagnetizing eld and domain wall motion in the
ferrite phase. However, in the composites above fc, the magnetic particles are completely coalescent
with each other, thus the magnetic behaviors are closely dependent on the anisotropic eld of the
ferrite phase. The magnetic properties of the NZFO/BTO ceramic composite synchronously exhibit a
critical behavior at the percolation threshold.
Introduction
Multi-functional materials are important members of the
materials family because of their excellent performance and
potential applications in advanced electronic devices such as
magnetic nano-oscillators, printed circuit boards, passive
lters, electromagnetic sensors etc. in modern technologies.16
Due to the scarcity of single-phased multi-functional materials
in nature, articial composite materials such as ferromagnetic/
ferroelectric composites, have attracted much interest owing to
their combinational characteristics of electrical and magnetic
responses under external elds.711 Since they are expected to
improve the functionality of future electronic devices, especially
where both controllable dielectric and magnetic properties are
needed, it is of fundamental interest and practical signicance
to develop such high-property composite materials.
As revealed by many pioneering researches, the percolation
eect could appear in several composites with one of the
constituent phases being conductive, substantially inuencing
the dielectric properties of these composites.1215 In percolative
composites, the permittivity will present an abnormally giant
and nonlinear increase with the volume fraction of the
conductive phase approaching the percolation threshold fc,
which is theoretically predicted to be only 0.16 for threedimensional systems.16 However, subsequent investigations
pointed out that the value of fc is closely associated with the
Experimental
xNi0.5Zn0.5Fe2O4/(1 x)BaTiO3 composite ceramics with the
molar fraction of NZFO ferrite x varying from 0 to 1 were
prepared by a solgel in situ method through the following
steps. AR-grade acetic acid (CH3COOH), barium acetate
(Ba(CH3COO)2), nickel acetate (Ni(CH3COO)2$4H2O), iron
nitrate (Fe(NO3)3$9H2O), zinc nitrate (Zn(CH3COO)2$4H2O),
tetrabutyl titanate (Ti(OC4H9)4) and ethylene glycol monomethyl ether (CH3OCH2CH2OH) were used as raw materials to
prepare the sol precursor. The obtained sol was dried at 120 C
in an oven for 3648 h. During the heating process, the sol
changed into a gel and further transformed into composite
powder, which was ground in an agate mortar to obtain a ner
state for subsequent treatment. In order to remove the residual
organic solvent thoroughly, the composite powder was presintered at 750 C for 1.5 h. Aerward, it was added 5% PVA,
pressed into toroidal rings under a non-axial pressure of 200
MPa, and sintered in air at 1310 C for 12 h and then at 1320 C
for 20 min. The step-sintering process will enhance the calcination of the NZFO/BTO composite, ensuring the constituent
phases to grow in a saturated state. The sintering process was
controlled precisely to avoid possible occurrence of big pores at
high temperature. The sample rings average 20 mm in outer
diameter, 10 mm in inner diameter and 12 mm in height. The
surfaces were polished with abrasive paper before XRD testing
and SEM observation. A detailed description of the preparation
procedures of solgel in situ derived NZFO/BTO composite can
be found in ref. 28.
The constituent phases were identied by a RIGAKUD/MAXC type X-ray diractometer (XRD, Cu Ka target) produced in
Tokyo, Japan. The wavelength of the X-ray source is 0.1540562
nm, and the step width is 0.02 with a scanning speed of 4 per
minute between 10 and 80 . The morphology and microstructure were observed by a SIRION-type eld emitting
6326 | J. Mater. Chem. C, 2013, 1, 63256334
Paper
scanning electron microscope (SEM) produced by Japan FEI
Corporation. The permeability spectra were measured by an
Agilent 16451B precision impedance analyzer (Palo Alto, CA)
within the frequency range of 100 kHz to 110 MHz. The
magnetic hysteresis loops and zero-eld cooled (ZFC)-eld
cooled (FC) curves were measured by a Vibrating Sample
Magnetometer (VSM) and a Physical Property Measurement
System (PPMS-9T) produced by Quantum Design Cooperation
(USA).
Paper
Fig. 3
EDS mapping results on samples x 0.3, x 0.6 and x 0.9. The white areas represent the distribution of constituent phases.
Paper
Fig. 4 (a) The frequency dependence of the eective permeability of as-prepared NZFO/BTO composite with various volume fractions of NZFO ferrite fNZFO; (b) plots of
the initial permeability as a function of fNZFO. The inset shows the change of the grain size of NZFO particles. (c) Three-dimensional diagrams depicting the formation of
percolation paths and the change of topological structure with increasing fNZFO as described in the text.
(2)
Paper
cd
ud
Ks
1i
(3)
(4)
u
us
Kd ud 2
u2 ibu
(5)
(6)
2
us u2
ud 2 u2 b2 u2
m00
Ks uus
Kd ud bu
2
2
us 2 u2
ud u2 b2 u2
2
(7)
(8)
Kd 3pMs2D/4g
(9)
and
Spin rotation
fNZFO
Ks
us ( 10 )
Kd
ud ( 107)
b ( 107)
0.447
0.548
0.829
0.916
1.0
4.09
6.20
34.82
52.76
89.47
13.80
11.90
8.31
7.11
6.45
1.24
1.51
17.93
33.86
68.21
3.12
2.85
2.11
1.75
1.71
3.84
2.66
2.63
2.45
2.45
Paper
permeability component contributed by domain wall motion in
the composite below fc is much smaller than that contributed by
spin rotation. Therefore, domain wall motion is an important
factor governing the behavior of eective permeability below fc,
but such governability gets seriously undermined above the
percolation point when the mobility of domain walls becomes
quite easy through the percolation networks. Consequently, the
magnetic susceptibilities of the composite are typically dierent
before and aer the transition point of the topological microstructure, during which the shielding eect on the response of
magnetic moments and the pinning eect on domain wall
motion compete with each other in controlling the value of
permeability. At low NZFO content, the ferrites are surrounded
by a non-magnetic phase, and the permeability is primarily
determined by domain wall motion and the demagnetizing
eld, whereas at high content when the ferrite particles form
percolation networks, the inuence of the two factors becomes
much smaller.
The magnetic hysteresis loops of as-prepared NZFO/BTO
composites with dierent fNZFO measured at room temperature
are shown in Fig. 6. The arrow denotes the increased volume
fraction of NZFO ferrite. The details near zero magnetic eld are
shown as insets in Fig. 6(a), and the variation of saturation
magnetization (Ms) and coercivity (Hc) as a function of fNZFO are
summarized in Fig. 6(b). All the samples are saturated in
magnetization under an externally applied eld of 6 kOe,
exhibiting novel so magnetic properties that could be sensitively tuned by external magnetic eld. It is clearly illustrated in
Fig. 6(b) that the saturation magnetization Ms increases almost
linearly with increasing fNZFO, from 15.0 emu g1 at fNZFO
0.342, 72.8 emu g1 at fNZFO 0.916 to 76.6 emu g1 at fNZFO
1.0. The saturation magnetization is insensitive to microstructure because it is determined by the total amount of magnetic
moments in the system. However, the coercivity shows an
interesting behavior which is completely dierent from that of
saturation magnetization. As plotted in Fig. 6(b), it increases
slightly at rst, then decreases dramatically until it reaches an
impressively low value of 0.788 Oe near the percolation
threshold. Aerward, it increases with increasing fNZFO, and
nally approaches a stable value of about 6 Oe. This behavior is
a reection of its intrinsic structure-sensitive feature in
response to the change of NZFO content in the composite.
In this context, the composition dependence of coercivity
could be divided into three regions over the whole volume
fraction range. In region I, where fNZFO is far below the percolation threshold, the magnetic NZFO islands are uniformly
dispersed in a non-magnetic matrix, being separated by BTO
clusters. In such situation, the spin rotation is signicantly
blocked by the demagnetizing eld exerted on the ferrite phase,
and the domain wall motion is seriously pinned by the
surrounding BTO phase. Hence, the coercivity of the composite
might be relatively large and controlled mainly by shielding of
spin rotation and pinning of domain wall motion in this region.
In region III, where fNZFO is much higher than the percolation threshold, the NZFO particles fully contact with each other
and tend to act as a single ferrite cluster with a small quantity of
non-magnetic BTO islands dispersed among them. The
Paper
Fig. 6 Magnetic hysteresis loops measured at room temperature: (a) dierent volume fraction of NZFO ferrite. The insets show the details of the loops near zero
magnetic eld. (b) The variation of saturation magnetization and coercivity as a function of fNZFO.
Paper
Fig. 7 Magnetic hysteresis loops of as-prepared NZFO/BTO composite with (a) fNZFO 0.447; (c) fNZFO 0.916; (e) fNZFO 0.645 measured between 2 and 300 K. The
plots of saturation magnetization and coercivity as a function of temperature are shown in (b), (d) and (f), respectively.
been observed. For the system above fc as shown in Fig. 7(d), the
coercivity increases with increasing temperature from about
3.5 Oe at 2 K to 78 Oe at 300 K. As discussed, the dominant
factor controlling the magnetic response in this case is the
anisotropy eld of the ferrite phase, so the coercivity behavior is
evidence of increased anisotropy with rising temperature in the
composite. A similar dependence has also been reported within
the same temperature range.41 For the system below fc, the
coercivity decreases with decreasing temperature from 78 Oe at
300 K to about 1 Oe at 70 K and then increases sharply to about
15 Oe at 2 K as shown in Fig. 7(b). Its blocking temperature Tb,
shown in Fig. 8, also appears near 70 K. The blocking temperature can be dened as the temperature at which thermal
activation begins to exceed the energy barrier created by
anisotropy and a broad maximum of magnetization in ZFC
process may occur around it. Below this temperature, the spins
are locked randomly in all possible directions and this state is
usually accompanied with restrained magnetization.42 Since the
coercivity is controlled by domain wall motion and spin rotation
for the NZFO/BTO composite below fc, if the temperature is low
enough below Tb, the spins will be seriously locked and the
coercivity may increase with decreasing temperature due to a
strong eective blocking eect on spin rotation and the domain
wall motion. Obviously, the increment of the coercivity with
Fig. 8 ZFCFC curves of the NZFO/BTO composite with fNZFO 0.447, fNZFO
0.645 and fNZFO 0.916 measured between 2 and 300 K under an applied
magnetic eld of 200 Oe.
Paper
decreasing temperature below Tb conrms the essential role of
domain wall motion. When the temperature increases up to the
blocking temperature, the domain walls will be unblocked
completely and the coercivity will reach the smallest value of
only 1 Oe. Nevertheless with further increase in temperature,
the anisotropy eld increases gradually and plays a overwhelming role in controlling coercivity, thus the coercivity
increases with rising temperature from its smallest value
around 70 K to 78 Oe at 300 K as shown in Fig. 7(b).
Comparatively, the experimental results of fNZFO 0.645 (critical region) shown in Fig. 7(e) and (f) reveals that the behavior of
coercivity resembles the system below fc (it is dicult to locate
the precise position of fc, thus the measured sample may lie
only below or above the critical point), however, from the ZFC
FC curves in Fig. 8, we can see that the magnetization of fNZFO
0.645 is the largest, corresponding to its smallest coercivity
value of only 0.788 Oe. Likewise, the magnetization of fNZFO
0.447 is the smallest as it has the largest coercivity (8.03 Oe). A
smaller coercivity usually implies an easier magnetization of the
sample under external magnetic eld, therefore, these results
are in good agreement with the experimental data shown in
Fig. 6(b), providing solid evidence for the existence of a
magnetism threshold in the NZFO/BTO composite.
In a word, the presented experimental evidence reveals that
there does exist a magnetism threshold in the NZFO/BTO
composite. At the percolation point, the functional properties
synchronously exhibit a critical behavior following the transition of topological structure. Below the percolation threshold,
the magnetic response is mainly correlated with inhibited spin
rotation and pinned domain wall motion, whereas above the
percolation threshold, it is signicantly inuenced by the
anisotropy eld of the ferrite phase. The percolation threshold
controls the transition of magnetic behavior in the percolative
magnetic/non-magnetic composite.
Conclusions
The NZFO/BTO ceramic composites were successfully prepared
through a modied sintering process by a solgel in situ
method. The composition dependence of the magnetic properties reveals that a transition of topological microstructure
appears at the percolation threshold fc 0.55. The matrix
changes from a non-magnetic BTO phase to a magnetic NZFO
phase near the percolation point, resulting in a critical behavior
of magnetic responses. The static spin susceptibility and
domain wall motion contribute directly to the eective permeability of the composite, but the behavior of magnetic susceptibility is typically dierent below and above the threshold. The
demagnetizing eld imposed on spin rotation and the pinning
of non-magnetic phase on domain walls cooperatively control
the susceptibility of the composite below fc 0.55. The
anisotropy eld of the ferrite phase plays an important role in
determining the values of the eective permeability and the
coercivity of the composite above fc 0.55. The ndings may be
of interest and importance for establishing a clear physical
picture of percolative composites and may be useful to improve
the performance of related multifunctional devices.
Acknowledgements
This work was supported by the Natural Science Foundation of
China under grant no. 51272230 and no. 50872120, Zhejiang
Provincial Natural Science Foundation (Grant no. Z4110040)
and the National Key Scientic and Technological Project of
China (Grant no. 2009CB623302).
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