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Ceramics International 41 (2015) 1225312257

www.elsevier.com/locate/ceramint

Sintering, microstructure and magnetic properties of low temperature

co-red NiCuZn ferrites with Nb2O5 and MoO3 additions
Yazhou Wanga, Hongqing Zhoua,n, Hongqing Qia, Luchao Rena, Zhiming Xub, Zhenxing Yuec
a

College of Materials Science and Engineering, Nanjing University of Technology, Nanjing 210009, PR China
b
Jiangsu Huaxing Electronic Co., Ltd., Changzhou 213234, PR China
c
College of Materials Science and Engineering, Tsinghua University, Beijing 100084, PR China
Received 22 May 2015; received in revised form 9 June 2015; accepted 10 June 2015
Available online 18 June 2015

Abstract
Sintering behavior and magnetic properties of NiCuZn ferrites with different amount of Nb2O5 and MoO3 additions were investigated. It was
found that Nb2O5 and MoO3 additives could improve densication and promote uniform grain growth. The appropriate Nb2O5 and MoO3
additions not only efciently increase the initial permeability (i) and saturation ux density (Bs), but also noticeably reduce the remanent ux
density (Br) and coercive led strength (Hc) of the NiCuZn ferrites sintered at 925 1C. By contrast, the NiCuZn ferrites with 0.2 wt% Nb2O5 and
0.3 wt% MoO3 additions showed excellent magnetic properties: i 1097.88 at 100 kHz, Bs 160.81 mT, Br 63.55 mT and Hc 26.6 A  m-1.
& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: C. Magnetic properties; D. Ferrite; Low temperature sintering; Microstructure

1. Introduction
A tendency of downsizing electronic components began in
1990s. Concurrently, progress also occurred in surface-mount
technology and efforts have been made to accomplish high density
incorporation of ferrite inductors into a printed circuit board. This
has, as a result, allowed various types of multilayer ferrite chip
inductors (MLCI) to meet the demands from relevant elds [1].
The key materials of multilayer chip inductors are NiCuZn ferrites
which have gained popularity in the eld of microelectronic
devices for low sintering temperature and excellent magnetic
properties, such as high permeability, environmental stability and
high electrical resistivity [2,3]. In addition, Ag is used as the
electrode material that matches perfectly with MLCIs. In order to
be co-red ferrite materials with Ag electrode and inhibit the
interfacial reactions between NiCuZn ferrites and Ag electrode
simultaneously, several methods have been developed to reduce
sintering temperature of the ceramics under the melting point of Ag
electrode, such as ux, ion exchange, ne powder and chemical
n

Corresponding author. Tel./fax: 86 25 86639976.

E-mail address: [email protected] (H. Zhou).

http://dx.doi.org/10.1016/j.ceramint.2015.06.048
0272-8842/& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

processing [35]. By contrast, ux is lower in cost and easier to

process than that of the others due to liquid phase formation or
grain growth promotion [5,6]. Some typical uxes such as B2O3,
Bi2O3, MoO3 and glass [79] were introduced into NiCuZn ferrites
to lower sintering temperature and promote magnetic properties.
Nb2O5 and MoO3 have been reported as efcient sintering aids
among various additives. Rao et al. [10] reported that Nb2O5
additive led to high permeability of NiZn ferrites. Su et al. [11]
found that MoO3 additive was conducive to promote densication
and improve magnetic properties. However, effects of Nb2O5 and
MoO3 mixed additives on NiCuZn ferrites have rarely been dealt
with in the literature. Therefore, different proportions of Nb2O5 and
MoO3 mixture were added into NiCuZn ferrites as sintering ux
and effects of additives on densication, microstructure and
magnetic properties were investigated systematically and discussed
in greater detail in this study.
2. Experimental procedures
A NiCuZn ferrite with composition of (Ni0.15Cu0.2Zn0.65O)1.02(Fe2O3)0.98 was prepared by the conventional solid
state reaction technique. The raw materials of NiO, CuO, ZnO

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Y. Wang et al. / Ceramics International 41 (2015) 1225312257

and Fe2O3 with purities higher than 99 wt% were chosen as

initial materials and weighed according to the formula. After
being wet mixed uniformly in a ball mill and dried, the
powders were calcined at 800 1C for 4 h in the air. The
calcined powders were then added by various proportion of
Nb2O5 and MoO3 additives and remilled for 8 h. The mixtures
were granulated with PVA (10 wt%) and pressed into circular
ring shape for sintering study and further research.
The bulk density was measured by the traditional Archimede's method. Scanning electron microscope (SEM JSM6500) was applied to observe the fracture surface microstructures of the sintered samples. The permeability and Q-factor
spectra were measured at room temperature by Agilent 4294A
impedance analyzer with the frequency range from 1 kHz to
15 MHz. The temperature dependence of the permeability was
obtained at a constant frequency (100 kHz) within the temperature range from 20 to 100 1C. The hysteresis graph was
measured using IWATSU SY-8216 B-H analyzer.

3. Results and discussion

3.1. Sintered densities of the NiCuZn ferrites
The bulk densities of NiCuZn ferrite samples with various
amounts of Nb2O5 and MoO3 additives are shown in Fig. 1. In
general, the variation of three curves basically exhibits a same
tendency and densities vary greatly with the increase of MoO3
additive. For example, the density containing 0.2 wt% Nb2O5
additive increases from 4.68 to 5.03 with MoO3 content rising
from 0 to 0.3 wt%, then decreases to 4.81 as the MoO3 content
goes up to 0.7 wt%. This indicates that small amount of MoO3
additions dramatically improve sinterability of the green compacts.
Density values of the second doping point (0.3 wt% MoO3) in
three curves are high enough and reach their peaks for water
absorptions of these samples are less than 1.1%. The melting point
of MoO3 addition is 795 1C, therefore, a lower temperature
densication is attributed to the formation of liquid phase, thus
reducing the activation energy and promoting the grain growth [2].

Fig. 1. Bulk densities of the ferrites as a function of MoO3 content sintered at

925 1C.

Furthermore, molybdenum cations with high electronic valence

entered into the grain boundary region and metallic ion vacancies
in the grain boundary region increased to balance the electric
charges. As a result, the movement speed of grain boundary has
been increased [12]. Thus, grain growth has been promoted and
bulk density has been increased. It reported that an appropriate
Nb2O5 additive could make grains grow small and uniformly [13],
then the grains grew more uniformly in later further growth when
MoO3 additive added. However, excess Nb2O5 additive results in
much smaller grains and the later reaction need more MoO3
additive to improve the densication. The specimens containing
0.3 wt% Nb2O5 possess lowest density and relatively low densication, which will perform against magnetic properties. For this
purpose, the samples doped with 0.1 wt% and 0.2 wt% Nb2O5
respectively have been focused in the following research.

3.2. Microstructural obseravation

The fracture surfaces of the sintered specimens at 925 1C are
examined to research the variation of densication and grain
size. The SEM images of NiCuZn samples with or without
additions are illustrated in Fig. 2. The effects of Nb2O5 and
MoO3 additions on the ferrites are exerted not only by
improvement of sinterability and reduction of porosity, but
also by uniformity of grains growth. According to Fig. 2a,
NiCuZn sample without any additives reveals more porous. As
0.1 wt% Nb2O5 and 0.1 wt% MoO3 are mixed and added into
NiCuZn sample (Fig. 2b), crystal grains get smaller and more
uniform, then grains grow bigger and porosities decline with
the content of MoO3 additive increases to 0.3 wt% (Fig. 2c).
Nb2O5 can make grains grow smaller and uniformly and MoO3
can further promote growth of these small grains, which causes
the variations of grain size as shown in Fig. 2ac. However, as
the concentration of MoO3 additive continues increasing
(0.7 wt%), the samples present much larger average grain
sizes that even exceed 5 mm. In this case, some abnormal
grains emerge and microstructure turns to non-uniform in
Fig. 2d. This leads to inhomogeneous grains and intragranular
pores, and then causes the reduction of density compared with
Fig. 2c, which is well coincident with the results in Fig. 1. The
typical illustration is showed in Fig. 2e, which corresponding
samples are doped with 0.2 wt% Nb2O5 and 0.3 wt% MoO3
additives respectively, the result shows that NiCuZn ferrite
grains grow more uniformly and slightly bigger than that in
Fig. 2c. It indicates that 0.2 wt% Nb2O5 additive can optimize
the balance between Nb2O5 and MoO3, leading to grains grow
bigger and more uniformly when 0.3 wt% MoO3 additive
added. Nb and Mo are two metallic elements at the same
period of two adjacent subgroup in the periodic table of
chemical elements. Therefore, its ion radius is similar in size,
respectively, Nb5 0.064 nm and Mo6 0.059 nm. The force
of grain boundaries which inhibits them to coalesce the
particles with each other is rather weak. As a result, Nb5
and Mo6 can enter into mutual crystal lattices, forming a
more uniform grains growth and a better intergranular
morphology.

Y. Wang et al. / Ceramics International 41 (2015) 1225312257

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Fig. 2. SEM micrographs of the ferrites with different amounts of Nb2O5 and MoO3 additives sintered at 925 1C: (a) pure, (b) 0.1 wt% Nb2O5 and 0.1 wt% MoO3,
(c) 0.1 wt% Nb2O5 and 0.3 wt% MoO3, (d) 0.1 wt% Nb2O5 and 0.7 wt% MoO3, (e) 0.2 wt% Nb2O5 and 0.3 wt% MoO3.

3.3. Magnetic properties

Fig. 3 shows the frequency dependent real permeability of the
samples with different amount of Nb2O5 and MoO3 additives. The
result reveals that small content of Nb2O5 and MoO3 additives
remarkably improve the permeability of NiCuZn ferrites. It was
found that permeability values do not change linearly with the
rising amount of additives and initial permeability value of the
ferrites with 0.2 wt% Nb2O5 goes up rstly from 570.99 to
1097.88 as MoO3 concentration increases from 0 to 0.3 wt%, then

drops to 533.62 for the composition with 0.9 wt% MoO3. In

addition, the maximum value of permeability moves to lower
frequency region with the mounting MoO3 content from 0 to
0.3 wt%, i.e., the resonance frequency decreases, which follows
Snoek's law [14]. When MoO3 content in NiCuZn ferrites keeps at
a same horizontal line, the values of permeability increase with the
rising content of Nb2O5 additive due to grains grow more
uniformly.
It is universally accepted that various intrinsic and extrinsic
factors such as saturation magnetization (Ms), crystal magnetic

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Y. Wang et al. / Ceramics International 41 (2015) 1225312257

Fig. 3. Permeability spectra of samples with different amount of Nb2O5 and

MoO3 additives.

Fig. 4. Q-factor spectra of samples with different amount of Nb2O5 and MoO3
additives.

anisotropy (K1), magnetostriction constant (), the grains size,

porosity, purity, particle shape, particle distribution and
chemical activity greatly affect the magnetic properties of
polycrystalline ferrites. The signicant increase of permeability
within MoO3 concentration range from 0 to 0.3 wt% may be
attributed to the decrease of magnetostriction constant induced
by molybdenum ions. Molybdenum ions emerage in the grain
boundary region, these cations will balance the electric charges
and increase the movement speed of grain boundary. Therefore, promoting grains growth (Fig. 2c) [15]. However, nonuniform microstructure (inhomogeneous grains and intragranular pores) was found as the MoO3 additive continues to
increase (Fig. 2d), thus the motion of domain wall was
inhibited and permeability was affected by it. Moreover, a
more Nb2O5 additives (0.2 wt%) make grains grow more
uniformly (Fig. 2e), which promotes the sintering of NiCuZn
ferrites and improves permeability values to a certain extent
compared with that in Fig. 2c.
The variation of Q-factor versus frequency is shown in
Fig. 4. Q-factor is a common measurement of performance and
represents inductance to loss ratio. Compared with Figs. 3 and
4, the latter variation trend is different from that of the former.
A small amount of Nb2O5 can increase the Q-factor in a minor
range. The Q-factor decreases in value as the percentage
composition of MoO3 addition increases from 0.1 to 0.3, then
increases gradually until the percentage concentration reaches
0.5. The Q-factor values of NiCuZn ferrite samples containing
0.1 wt% Nb2O5 and 0.2 wt% Nb2O5 show a same tendency
with the rising content of MoO3 additive. The more MoO3
added, the larger Q-factor maximum values obtained. With an
increasing molybdenum ions, a more molybdenum ions substitution occurs in tetrahedral sites and a more iron ions move
to octahedral sites, which leads to the increase of spinel
displacements and oxygen vacancies. These substitution and
oxygen vacancies can be a transport path of grains and may be
a promotion of grain growth further [8]. However, the second
doping point (0.3 wt% MoO3) is an exception, on which
permeability maximizes in value. The reasons for the

phenomenon are not clear. In general, core loss can be divided

into three parts, i.e., eddy current loss, hysteresis loss and
residual loss. Eddy current losses are signicantly determined
by electrical resistivity of material at high frequencies. MoO3
is an efcient sintering aid, it can act as an electrostatic trap by
pinning the movement of electrons at some cations. Thus, the
resistivity of the grains has been increased. A larger resistivity
of the grains may be one of the reasons for the rising of Qfactor values. When the content of Nb2O5 additive rises from
0.1 wt% to 0.2 wt%, Q-factor values increase slightly, it may
due to a more Nb2O5 additives make grains grow more
uniformly and smaller. This will be conducive to the promotion of grains growth when later a more MoO3 additive added.
Therefore, improvements of the densication and Q-factor
values of the specimens are reasonable (Fig. 2e).
As is shown in Fig. 5, the permeability as a function of
temperature with different amount of Nb2O5 and MoO3
additives is measured at the constant frequency of 100 kHz.
It was observed that the permeability changes slightly and then
falls abruptly as temperature increases. The Curie temperature
(Tc), or called magnetic transition temperature, can be identied as the temperature at which the permeability falls sharply.
It is well known that the ferromagnetic substance transforms to
a paramagnetic substance at Tc. It can be concluded that the
variations of Nb2O5 content do not basically affect the
variation of Tc values. Tc values of the ferrite samples
containing a same Nb2O5 content increase slowly with the
increasing content of MoO3 additives and the values go up
gradually from 60 to 80 1C as the concentration of MoO3
increases from 0.1 to 0.7 wt%. A small quantity of Mo ions
may be incorporated into the lattice of ferrite and the number
of strong magnetic ions begins to increase in both A and B
sites, which increases the strength of exchange interactions,
thereby strengthening the Curie temperature in the system.
Table 1 presents some important parameters of the NiCuZn
ferrites with various amount of Nb2O5 and MoO3 additives sintered
at 925 1C. Small amount of Nb2O5 and MoO3 additives not only
can efciently increase i and Bs, but also obviously reduce Br and

Y. Wang et al. / Ceramics International 41 (2015) 1225312257

12257

0.3 wt% MoO3 added in NiCuZn ferrites possess optimum

magnetic properties: i 1097.88 at 100 kHz, Bs 160.81 mT,
Br 63.55 mT and Hc 26.6 A m  1.
Acknowledgments
This work is partly supported by Program for Changjiang
Scholars and Innovative Research Team in University (PCSIRT)
under Grant no. IRT114; A Project funded by the Priority
Academic Program Development of Jiangsu Higher Education
Institutions (PAPD) (Grant no. IRT1146); A Project funded by the
Natural Science Foundation of the Jiangsu Higher Education
Institutions under Grant no. 13KJB430016. A Project funded by
Natural Science Foundation of the Jiangsu province under Grant
no. BK20141460.
Fig. 5. Temperature dependence of permeability of the ferrites with different
amount of Nb2O5 and MoO3 additives.

Table 1
Some important parameters of the NiCuZn ferrites with various amount of
Nb2O5 and MoO3 additives sintered at 925 1C.
Nb2O5 (wt%)

MoO3 (wt%)

i (100 kHz)

Bs (mT)

Br (mT)

Hc (A/m)

0
0.1
0.1
0.1
0.1
0.2
0.2
0.2
0.2

0
0.1
0.3
0.5
0.7
0.1
0.3
0.5
0.7

412.93
580.35
1032.76
757.38
654.59
679.50
1097.88
767.13
668.31

114.34
139.12
155.26
149.63
147.18
151.39
160.81
149.57
146.24

80.22
73.09
62.51
33.49
30.68
70.64
63.55
34.21
28.12

50.62
37.04
21.13
20.10
22.43
34.04
26.6
20.22
20.37

Hc. The NiCuZn ferrites could be suitable for low-temperature-red

ferrite materials with higher i, Bs and lower Br, Hc. In summary,
the NiCuZn ferrites with a composition of 0.2 wt% Nb2O5 and
0.3 wt% MoO3 additive demonstrates excellent magnetic properties: i 1097.88 at 100 kHz, Bs 160.81 mT, Br 63.55 mT and
Hc 26.6 A m  1.
4. Conclusions
In this study, the effects of Nb2O5 and MoO3 additives on
sintering behavior, microstructure and magnetic properties of
NiCuZn ferrites were investigated. It was found that Nb2O5
and MoO3 additives could dramatically enhance the densication of samples based on uniformity of grains and promotion
of grains growth. A appropriate addition of mixed Nb2O5 and
MoO3 not only can signicantly increase the initial permeability (i) and saturation ux density (Bs), but also can
markedly reduce the remanent ux density (Br) and coercive
eld strength (Hc) of the NiCuZn ferrites sintered at 925 1C,
which offers the NiCuZn ferrites suitable for low temperature
sintered ferrite materials. By contrast, 0.2 wt% Nb2O5 and

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