J. Murbe,
J. Topfer
University of Applied Sciences Jena, Dept. SciTec, Carl-Zeiss-Promenade 2, 07745 Jena, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 27 April 2011
Received in revised form
23 August 2011
Available online 1 September 2011
We have studied sub-stoichiometric NiCuZn ferrites with iron deciency (i.e., o 50mol% Fe2O3) of
composition Ni0.20Cu0.20Zn0.60 zFe2 zO4 (z/2) with 0 r z r 0.06. The temperature of maximum shrinkage rate is shifted from T 1000 1C for z 0 towards lower temperatures down to T 900 1C for a substoichiometric ferrite with z 0.02. Dense samples are obtained after ring at 900 1C for z 40 only. Substoichiometric compositions (z 40) do not form single-phase spinel ferrites after sintering at 900 1C,
but rather represent mixtures of CuO and a stoichiometric ferrite with slightly modied composition.
The formation of small amounts of CuO at grain boundaries is demonstrated by XRD and SEM. The
permeability is increased from m 80 for stoichiometric ferrites (z 0) to m 660 for z 0.02. The
formation of CuO during sintering of sub-stoichiometric ferrites supports densication and is a
prerequisite for low temperature ring of multilayer inductors. Addition of 1 wt% Bi2O3 as liquid phase
sintering aid is required to provide sufcient densication of the stoichiometric ferrite (z 0) at 900 1C.
Addition of 0.37 wt% Bi2O3 to a sub-stoichiometric ferrite (z 0.02) results in dense samples after ring
at 900 1C; however, the microstructure formation is dominated by heterogeneous grain growth.
& 2011 Elsevier B.V. All rights reserved.
Keywords:
Soft ferrite
Low temperature sintering
Permeability
Sub-stoichiometry
1. Introduction
NiCuZn ferrites are standard materials for multilayer inductors
because of their low sintering temperature and good performance
up to MHz frequencies [13]. The temperature for co-ring the
multilayer component is restricted to about 900 1C because of the
melting point of silver used as metallization material. Consequently,
the choice of a proper ferrite composition and optimum processing
route is crucial for the fabrication of devices. The positive effect of Cu
on lowering the sintering temperature of NiZn ferrites has been
known for years [4]. However, papers reporting on correlations
among NiCuZn ferrite composition, sintering behavior and magnetic properties are scarce [59]. Moreover, a common feature of
typical low-ring ferrite compositions seems to be a small deciency of iron oxide, i.e. less than 50mol% Fe2O3 is used in the
starting mixture of oxides. Such compositions are referred to as substoichiometric here. Their composition typically translates into a
spinel formula with less than two Fe per formula unit, e.g.
Ni0.20Cu0.20Zn0.62Fe1.98O3.99, compared to stoichiometric ferrites
with 50mol% Fe2O3 and two Fe per formula unit MeFe2O4. The
effect of sub-stoichiometry through iron deciency has been investigated earlier. It was shown that sub-stoichiometry enhances
densication [9,10]. Precipitation of Cu at grain boundaries of a
0304-8853/$ - see front matter & 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2011.08.040
2. Experimental
Ferrite powders of composition Ni0.20Cu0.20Zn0.60 zFe2 zO4 (z/2)
with 0rzr0.06 were prepared by the standard ceramic route.
a-Fe2O3 (TKS Germany, HP grade) with a specic surface S4.3 m2/g;
NiO (Inco, Black Nickel Oxide, Grade F) with S 70 m2/g; CuO.
(Merck, Germany) with S4.6 m2/g and ZnO (Harzsiegel Heubach,
Germany, standard grade) with S4.5 m2/g were used as starting
materials. The oxides were wet mixed for 12 h in a polyethylene
container. After drying the powder was calcined at 750 1C for 2 h and
subsequently milled in a planetary ball mill using zirconia grinding
media. Bi2O3 was added during ne-milling. The powders were
compacted using polyvinyl-alcohol as a binder to give pellets for
sintering studies or toroids for permeability measurements.
J. M
urbe, J. T
opfer / Journal of Magnetism and Magnetic Materials 324 (2012) 578583
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Fig. 1. Shrinkage (a) and shrinkage rate (b) of Ni0.20Cu0.20Zn0.60 zFe2 zO4 (z/2)
with 0r zr 0.06.
Fig. 2. Density vs. z of Ni0.20Cu0.20Zn0.60 zFe2 zO4 (z/2) with 0r z r0.06 sintered
at 900 1C for 2 h.
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J. M
urbe, J. T
opfer / Journal of Magnetism and Magnetic Materials 324 (2012) 578583
Fig. 3. XRD patterns of ferrites sintered at 900 1C for 2 h with z 0 and 0.06.
Fig. 5. Permeability vs. frequency for Ni0.20Cu0.20Zn0.60 zFe2 zO4 (z/2) with
0r zr 0.06, inset: permeability at 1 MHz vs. z.
J. M
urbe, J. T
opfer / Journal of Magnetism and Magnetic Materials 324 (2012) 578583
Fig. 6. Permeability vs. temperature for Ni0.20Cu0.20Zn0.60 zFe2 zO4 (z/2) ferrites.
581
identical Bi2O3 concentrations (Fig. 7b). The shrinkage rate displays a change from a broad peak for Bi2O3-free samples to a
series of sharp rate peaks for samples containing bismuth oxide,
which is interpreted as signature of the dominance of liquid phase
sintering in the latter case. For stoichiometric Ni0.20Cu0.20Zn0.60Fe2O4 (z0) the shrinkage rate peak is shifted subsequently down
to lower temperatures and reaches 900 1C for a sample with
addition of 1 wt% Bi2O3 (Fig. 7a). For the sub-stoichiometric ferrite
with z 0.02 signicantly lower Bi2O3 concentrations are sufcient to shift the maximum shrinkage rate to 900 1C (Fig. 7b). This
effect is supported by the fact that the temperature of the
maximum shrinkage rate of the sub-stoichiometric ferrite with
z0.02 appears at lower temperatures compared to z 0 already
for samples without Bi2O3 additive. Closer inspection of the
shrinkage rates of stoichiometric ferrites (z 0) reveals that the
maximum shrinkage rate peak is shifted from 990 to 900 1C for
0.375 and 1 wt% Bi2O3, respectively (Fig. 7a). A second, smaller
peak is also systematically shifted from 1055 1C to 965 1C for
0.375 and 1 wt% Bi2O3, respectively. In the case of sub-stoichiometric samples (z 0.02) a similar shift of the two shrinkage rate
peaks is found (Fig. 7b); however, an additional third peak at
around 840 1C signals the formation of a liquid phase and
subsequent rearrangement of particles. Liquid phase sintering
might be triggered by the formation of an eutectic in the system
Bi2O3CuONiOZnOFe2O3. Formation of eutectics at as low as
740 and 770 1C has been reported in the pseudo-binary ZnO
Bi2O3 and CuOBi2O3 systems, respectively [21,22]. Since this
shrinkage rate peak at 840 1C does not occur in the shrinkage rate
curves of stoichiometric ferrites with Bi2O3 additive (Fig. 7a),
melting of Bi2O3 (825 1C) is an unlikely reason for the appearance
of this peak in the case of sub-stoichiometric ferrites (Fig. 7b).
This observation suggests that the process of liquid phase formation includes CuO, which appears as an impurity phase during
ring of sub-stoichiometric ferrites. However, the observed series
of several shrinkage rate peaks is a signature of the underlying
liquid phase sintering, i.e. liquid formation, rearrangement and
solution-precipitation processes.
The density of powder compacts sintered at 900 1C for 2 h as a
function of the Bi2O3 additive concentration is shown in Fig. 8.
Stoichiometric ferrites exhibit little densication only; samples with
addition of 0.5 wt% Bi2O3 show a low density of about 4.3 g/cm3
Fig. 8. Density of Ni0.20Cu0.20Zn0.60Fe2.00O4.00 (z 0) and Ni0.20Cu0.20Zn0.62Fe1.98O3.99 (z 0.02) sintered for 2 h at 900 1C as a function of bismuth oxide
concentration.
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J. M
urbe, J. T
opfer / Journal of Magnetism and Magnetic Materials 324 (2012) 578583
4. Conclusions
The sintering behavior and permeability of sub-stoichiometric Ni
CuZn ferrites of the iron-decient series Ni0.20Cu0.20Zn0.60 zFe2 z
O4 (z/2) (0rzr0.06) was investigated. It is shown that, compared to
stoichiometric ferrites (z0), sub-stoichiometric ferrites exhibit specic shrinkage behavior, microstructure and permeability:
(z 0)
and
Fig. 10. SEM micrographs of ferrites with z 0 (a) and z 0.02 (b) sintered for 2 h at 900 1C with addition of 1 wt% Bi2O3.
J. M
urbe, J. T
opfer / Journal of Magnetism and Magnetic Materials 324 (2012) 578583
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