International Journal of Inorganic Materials 3 (2001) 11891192

Liquid phase sintering of NiCuZn ferrite and its magnetic properties

Yuh-Ruey Wang*, Sea-Fue Wang
Department of Materials and Minerals Resources Engineering National Taipei University of Technology, 1, Sec. 3, Chung-Hsiao E. Rd., Taipei,
Taiwan

Abstract
The influence of glass additives on the densification, microstructural evolution and magnetic properties of NiCuZn ferrites were
investigated. Two glass systems including PbO?SiO 2 and PbO?B 2 O 3 were used to reduce the sintering temperature of a NiCuZn ferrite.
The PbO?SiO 2 glass system was shown to be an effective additive to obstruct the grain boundary movement and prevent the abnormal
grain growth. In addition, it significantly lowers the sintering temperature of the ferrite. Ferrites sintered with PbO?SiO 2 have higher
resistivity, higher Q and higher Hc compared with those of PbO?B 2 O 3 systems. These results also indicated that the ratio of modifier to
glass-former did not significantly change the densification behavior, microstructural evolution and magnetic properties of the NiCuZn
ferrite. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Soft ferrite; Liquid phase sintering; Magnetic properties

1. Introduction
The surface mounting devices, such as multilayer chip
beads or inductors, have been developing rapidly for
electronic applications. Among available materials, polycrystalline ferrites have been used widely because of their
high permeability in the RF frequency region, high electrical resistivity, and environmental stability [1]. Ag is
suggested as an internal electrode for multilayer ferrites
due to its high conductivity that provides the components
with a higher quality factor, Q. Also, the Ag paste has
much lower cost compared with that of the Ag / Pd paste.
Therefore, the ferrite is required to sinter at temperatures
below 9508C. There has been a growing interest in NiCuZn
ferrites for the applications of producing the multilayertype chips mainly because these oxides can be sintered at
relatively low temperatures with a wide range of composition [2]. In addition, NiCuZn ferrites have better
properties at high frequencies than MnZn ferrite and lower
densification temperatures than NiZn ferrites.
Several approaches were attempted to reduce the sintering temperature, including (a) the reduction of the particle
size of the ferrite [3], (b) the incorporation of dopants into
the ferrite lattice [4], and (c) the usage of sintering
additives which change the sintering mechanism (liquid
phase sintering) [2,5]. Among them, the use of sintering
additives was found to be an effective method in practical
*Corresponding author.

applications. Typical fluxes used for liquid phase sintering

for NiCuZn ferrites include V2 O 5 , Na 2 O, PbO, Bi 2 O 3 , and
3NiO?V2 O 5 [5,6]. In order to investigate the influence of
the glass additives on the densification, microstructural
evolution and magnetic properties of NiCuZn ferrites,
different ratios of the modifier / glass-former for PbO?SiO 2
and PbO?B 2 O 3 were used as sintering aids for a commercial NiCuZn ferrite. Effects of the flux systems on the
densification behavior of the powders were investigated
through sintering studies. Electrical resistivity and magnetic properties such as permeability, quality factor and
hysteresis loop of the sintered parts were measured and
analyzed.

2. Experimental procedure
A NiCuZn ferrite (Ni / Cu / Zn50.38:0.12:0.50) prepared
from the solid state reaction was used during this study.
The powders have a particle size of 0.73 mm from SEM
micrographs and surface area of 7.60 m 2 g 21 using BET
method. The 2PbO?SiO 2 , 5PbO?SiO 2 , 2PbO?B 2 O 3 , and
5PbO?B 2 O 3 glasses were prepared by mixing stoichiometric amounts of PbO and SiO 2 or B 2 O 3 (Fisher Scientific, reagent grade) for 24 h in a vibratory mill. After
drying, these powders were transferred to a Pt crucible,
reacted at 8508C, and quenched. The powder was then
dry-milled and sieved though a 325 mesh screen.
(Ni 0.38 Cu 0.12 Zn 0.50 )Fe 2 O 4 powders were mixed with 3

1466-6049 / 01 / $ see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S1466-6049( 01 )00123-4

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wt% of 2PbO?SiO 2 , 5PbO?SiO 2 , 2PbO?B 2 O 3 , and 5PbO?

B 2 O 3 , respectively, methyl alcohol and an iron ball ([55
mm) media, using a ball mill for 2 h. The slurries were
then dried in a 1508C oven for 24 h. Then the as-obtained
powders were mixed with 3.5 wt% of a 15% PVA solution
and then pelletized into toroid- and disc-shapes using an
uniaxial pressure of 5 tons cm 22 . The samples were then
heat treated at 5508C for 2 h to eliminate the PVA,
followed by sintering at temperatures between 850 and
10508C for 2 h (heating rate5108C min 21 ). Densities of
specimens were measured by employing the liquid displacement method. Microstructure of sintered surfaces
were investigated using a scanning electron microscopy
(Joel JSM-T330A) at 20 kV. For the magnetic properties,
initial permeability ( m ) and quality factor (Q) were
measured using a HP4194 impedance analyzer at a frequency of 1 MHz on toroid-shape samples. BH curve is
performed using a magnetic hystersis loop tracer
(Yokagawa 3257) at a voltage of 20 V.

3. Results and discussion

The sintered densities of (Ni 0.38 Cu 0.12 Zn 0.50 )Fe 2 O 4
powders with 3 wt% of 2PbO?SiO 2 , 3 wt% of 5PbO?SiO 2 ,
3 wt% of 2PbO?B 2 O 3 , or 3 wt% of 5PbO?B 2 O 3 sintered
at temperatures ranging from 850 to 10508C are shown in
Fig. 1. For pure (Ni 0.38 Cu 0.12 Zn 0.50 )Fe 2 O 4 powders, it
requires sintering temperature of 12508C in order to
achieve the density of 5.00 g cm 23 (97.2% theoretical
density). Powders with PbO?SiO 2 , or PbO?B 2 O 3 additives
significantly reduce their sintering temperature down to
10008C. The lower sintering temperatures are due to the
liquid phase formation during sintering. Results in Fig. 1
also showed that the ratio of modifier / glass-former (i.e.
PbO:SiO 2 , or PbO:B 2 O 3 ratio) did not significantly modify

Fig. 2. Initial permeability ( m1 ) at 1 MHz for ferrite with various fluxes

sintered at the temperatures ranging from 850 to 10508C.

the densification behavior of NiCuZn ferrite. The microstructure study indicates that an uniform microstructure
with a grain size ranging from 1 to 2 mm was observed for
NiCuZn ferrites sintered with 2PbO?SiO 2 or 5PbO?SiO 2
glasses. However, for ferrites sintered with 2PbO?B 2 O 3 , or
5PbO?B 2 O 3 , the microstructures showed a rapid grain
growth for a limited number of grains up to (15 mm)
much larger than the average grain size population (of the
order of 1.5 mm). It seems that PbO?SiO 2 glass is an
effective additive to obstruct the grain boundary motion
and prevent the exaggerated grain growth.
Figs. 2 and 3 depict the initial permeability ( mi ) and
quality factors (Q) at 1 MHz for ferrite sintered with
various fluxes at the temperatures ranging from 850 to
10508C. The results revealed that the initial permeability
increases with the sintering temperature for all cases. It

Fig. 1. Densification curves for the (Ni 0.38 Cu 0.12 Zn 0.50 )Fe 2 O 4 powder sintered with different flux systems.

Y.-R. Wang, S.-F. Wang / International Journal of Inorganic Materials 3 (2001) 1189 1192

1191

Fig. 3. Quality factor (Q 1 ) at 1 MHz for ferrite with various fluxes sintered at the temperatures ranging from 850 to 10508C.

seems that neither the PbO:SiO 2 nor the PbO:B 2 O 3 ratio

significantly impacted on the permeability of NiCuZn
ferrite. The increase in initial permeability is closely
correlated to the densification and grain size of the
ceramics. Ferrites with higher density and larger average
grain size possess a higher initial permeability. An increase
in the density of ceramics not only results in the reduction
of demagnetizing field due to the presence of pores but
also raises the spin rotational contribution, which in turn
increases
the
permeability
[7].
For
a
pure
(Ni 0.38 Cu 0.12 Zn 0.50 )Fe 2 O 4 material sintered at 12508C for
2 h, the initial permeability is 387 and the quality factor is
6.3 with an average grain size of 30 mm. Deducting
from the effects of densification and grain size, the dilution
of the initial permeability by the presence of fluxes is
apparent. Also, the permeability could be diluted by the
continuous second phases along the grain boundary [8].
As revealed in Fig. 3, the dependence of quality factor
on the sintering temperature behaved differently from that
of the permeability shown in Fig. 2. It appears that quality
factors of the ceramics are not coincident with the sintered
density values. The quality factor reduced significantly as
the sintered density raised. This is probably due to the
reduction of DC resistivity with sintering temperatures.
Among the flux systems; the ferrites sintered with 2PbO?
SiO 2 have the best quality factor, as indicated in Fig. 3.

This may be due to the low reactivity nature of PbO?SiO 2

glass and the consequent fine grain size of the sintered
ferrite.
Table 1 presents the magnetic parameters from hysteresis loops obtained at 258C for ferrites sintered with
PbO?SiO 2 and PbO?B 2 O 3 flux systems at 10008C. A
decreasing tendency of coercivity (Hc ) and remanence (Br )
are observed for the samples with larger grains. It could be
explained by the corresponding facility to domain wall
motions. Also, a larger saturation flux density (Bs ) is
observed for ferrites with an increasing average grain size,
which is due to the presence of a multidomain grain
structure and hence the increase in the number of dipoles
per unit volume.

4. Summary
The PbO?SiO 2 glass system is an effective additive to
obstruct the grain boundary movement and can prevent the
exaggerated grain growth for (Ni 0.38 Cu 0.12 Zn 0.50 )Fe 2 O 4
ferrite. It reduces the sintering temperature of the ferrite
and results in ceramics of high Q and larger Hc . The
results also showed that the ratio of modifier to glassformer (i.e. PbO:SiO 2 , or PbO:B 2 O 3 ratio) did not sig-

Table 1
Magnetic parameters obtained from hysteresis loops for ferrites sintered with various flux systems at 10008C
Sample

Sintering
temperature

Density
(g cm 23 )

Br (G)

Bs (G)

Hc (Oe)

3 wt% 2PbO?SiO 2
3 wt% 5PbO?SiO 2
3 wt% 2PbO?B 2 O 3
3 wt% 5PbO?B 2 O 3
Pure ferrite

10008C / 2 h
10008C / 2 h
10008C / 2 h
10008C / 2 h
12508C / 2 h

5.04
5.04
5.06
4.99
4.94

3049
2957
2706
2807
2060

3675
3635
3680
3696
4241

2.79
3.17
1.79
1.96
0.41

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Y.-R. Wang, S.-F. Wang / International Journal of Inorganic Materials 3 (2001) 1189 1192

nificantly change the densification behavior, microstructural evolution and magnetic properties of NiCuZn ferrite.

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