Temperature Dependence of Core Loss in Cobalt Substituted Ni-Zn-Cu Ferrites

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Temperature Dependence Of Core Loss In Cobalt Substituted Ni-Zn-Cu

Ferrites
A. Lucas 1,2, R. Lebourgeois 1, F. Mazaleyrat 2, E. Labour 2,3
1. THALES R&T, Campus Polytechnique, 1 av. Augustin Fresnel, 91767 Palaiseau,
France
2. SATIE, ENS de Cachan, 61 av. du Prsident Wilson, 94235 Cachan, France
3. LGEP SUPELEC, Plateau de Moulon, 11 rue Joliot-Curie, 91192 Gif Sur Yvette

Abstract : The temperature dependence of core loss in cobalt substituted Ni-Zn-Cu


ferrites was investigated. Co2+ ions are known to lead to a compensation of the magnetocrystalline anisotropy in Ni-Zn ferrites, at a temperature depending on the cobalt content
and the Ni / Zn ratio. We observed similar behaviour in Ni-Zn-Cu and it was found that
the core loss goes through a minimum around this magneto-crystalline anisotropy
compensation. Moreover, the anisotropy induced by the cobalt allowed a strong decrease
of core loss, a ferrite having a core loss of 350 mW/cm3 at 80C was then developed
(measured at 1.5 MHz and 25 mT). This result represents an improvement of a factor 4
compared to the state of art Ni-Zn ferrites.

Keywords : NiZnCu ferrites, cobalt substitution, core loss versus temperature, permeability

1 Introduction
Nickel-zinc-copper ferrites are essential materials because of their high permeability in MHz
range. Moreover, their low sintering temperature makes them suitable for the realization of
integrated components in power electronics. As for nickel-zinc ferrites, cobalt substitution is an
efficient technique to decrease the permeability [1] and the magnetic losses of nickel-zinc-copper
ferrites [2]. The effect of cobalt is to allow the pinning of the domain wall by inducing a magnetic
anisotropy [3]. The consequence is a decrease of tan at high frequency [4] and also an
improvement of core loss [2]. The aim of this paper is to study the effect of cobalt substitution on
core losses versus temperature. A lot of papers investigated core losses of spinel ferrites versus
temperature but it was mostly for Mn-Zn power ferrites [5] and not at high frequency. There are
very few papers concerning core losses versus temperature of Ni-Zn or Ni-Zn-Cu ferrites [6][7],
moreover, they only investigated losses of a single composition measured at low frequency (50
kHz). In order to understand how the ferrite composition influences the core loss, ferrites with
three Ni / Zn ratios were studied (Ni / Zn = 0.43, 1 and 3) with, for each ratio, cobalt substitutions
up to 0.035 mol per formula.

2 Experimental procedure
2.1 Sample preparation
Ferrites were synthesized using the conventional ceramic route. The raw materials (Fe2O3, NiO,
ZnO, CuO) were ball milled for 24 hours in water. Co3O4 was then added before the calcination
around 800C in air for 2 hours. The calcined ferrite powder was then milled by attrition for 30
min. The resulting powder was compacted using axial pressing. The sintering was performed at
935C for 2 hours in air. Magnetic characterizations were done on ring shaped samples with the
following dimensions : outer diameter = 6.8 mm; inner diameter = 3.15 mm; height = 4 mm.

2.2 Sample measurements


Bulk density was deduced from weight and dimensions. Saturation magnetization was
measured on a magnetic balance. Initial complex permeability was measured versus frequency
between 1 MHz and 1 GHz using an HP 4291impedance-meter. Static initial permeability ( s) was
defined as at 1 MHz because for these ferrites is constant from very low frequencies to the
megahertz range. For the permeability versus temperature measurements, the rings were wound
with a copper wire and placed in an oven going from 70C to 150C. s was deduced from the
inductance measured at 100 kHz by an 4194A impedance-meter Agilent. Core losses were
measured at 1.5 MHz and 25 mT using a Clark-Hess 258 wattmeter and a 100 W Kalmus HF
amplifier.

3 Results and discussion


3.1 Physicochemical characterizations
Three different series of ferrites were studied:

Ni0.24Zn0.56Cu0.20CoFe1.98O4-
Ni0.40Zn0.40Cu0.20CoFe1.98O4-'
Ni0.60Zn0.20Cu0.20CoFe1.98O4-''

Four formulations were done for each series, with cobalt rate of 0, 0.014, 0.028 and 0.035 mol
per formula. The copper rate was 0.20 mol to allow the densification below 950C. Three Ni / Zn
ratios were studied in order to investigate the influence of cobalt substitution on ferrite with
different magneto-crystalline anisotropy. Indeed, K1 of the host crystal increases with nickel
content [8].
The samples were sintered at 935C for 2 hours in air. Figure 1 shows the X-ray diffraction
pattern of a Ni0.40Zn0.40Cu0.20Fe2O4 ferrite sintered at 935C. Only the spinel structure can be
observed, none of the precursor oxides are present in the sintered materials.
The bulk densities of the sintered ferrites are shown in figure 2. All the ferrites have a low
porosity ( > 92 % of the theoretical density). The cobalt substitution does not seem to have a
significant effect on densification, a slight increase of the densification can however be noticed.
This phenomenon is probably a consequence of the slight increase in the iron default of the ferrite.
Microstructure of the ferrites were also observed, SEM pictures are shown in figure 3. The
grain size is not affected by the Ni / Zn ratio. Even if the nickel is known to lead to a more difficult
densification [9], it is not observed here. The cobalt rate does not change the microstructure. All
the ferrites exhibit the same kind of microstructure, with a low porosity and an average grain size
between 1.5 and 2 m. The grain size repartition is relatively homogenous, although one can see a
few larger grains with defaults inside.

3.2 Magnetic characterisations


Saturation magnetization (Ms) at room temperature was measured (see table 1). This parameter
mainly depends on the Ni / Zn ratio. Ms increases up to a Ni / Zn ratio close to 1, then, it decreases
with the zinc content. The behaviour of the developed ferrites is coherent with previous studies
concerning Ni-Zn [8] and Ni-Zn-Cu [9] ferrites. The maximum of the saturation magnetization is
obtained for the Ni0.40Zn0.40Cu0.20CoFe1.98O4-' ferrites. Copper slightly lowers Ms compared to the
corresponding Ni-Zn ferrite [10].
Cobalt substitution does not have a significant influence on the saturation magnetization.
Cobalt introduction must lead to an increase of the saturation magnetization, due to Co2+ ions
magnetic moment, which is higher than the other divalent ions present in octahedral sites (Ni2+ and
Cu2+) [11]. The measurement device used for this study is probably not precise enough to discern a
variation in Ms with such a small amount of Co2+.
For each ferrite, the static initial permeability and the core loss were measured versus
temperature. The results are shown in figure 4.
The initial static permeability versus temperature of the cobalt substituted ferrites is not
monotonous ; A local maximum can be observed even if for high s samples, it is flattened. This is
due to the contribution of the cobalt ions to the magneto-crystalline anisotropy (K1). Several
studies were carried out on this phenomenon, which can be useful to increase the permeability
around a particular temperature [12]. The permeability is due to two contributions : the domain

wall displacements and the magnetization rotation :

3 M s2
s 1 = .
.D for the domain wall motion contribution [13]
16 K 1
2 M s2
s 1 .
3 K1

for the spin rotation contribution [14]

With D the average grain size and K1 the magneto-crystalline anisotropy of the ferrite. In this
study, we consider that the grain size is similar whatever the composition, so this parameter does
not affect the permeability. The variation of permeability versus temperature is then only
depending on the variations of Ms and K1 versus temperature.
As the saturation magnetization of these ferrites is monotonically decreasing versus
temperature, such a change in permeability is therefore due to a change in magnetic anisotropy. K1
of the Ni-Zn-Cu spinels is weak and negative (between 2 and 6,5.103 J/m3, for NiFe2O4,
ZnFe2O4 and CuFe2O4 [8]). The cobalt ferrite has a high and positive K1 (close to 300.103 J/m3 at
room temperature [8]). Addition of a small amount of cobalt will thus lead to a compensation of
K1. Looking at the previous relations, if there is a magneto-crystalline anisotropy compensation,
the permeability will go through a maximum. This explains the apparition of a local maximum in
s(T) curves of cobalt substituted ferrites at a compensation temperature (T0) increasing with the
cobalt content and K1 of the Ni-Zn-Cu host crystal.
The compensation temperature of the three series of ferrites are shown in table 2, these results
are established from s(T) curves (Figures 4.A1, B1 and C1). For a given Ni /Zn ratio, T0 increases
with the cobalt content. For the same cobalt rate, T0 increases with the nickel content, i.e. with
magneto-crystalline anisotropy of the Ni-Zn-Cu host crystal. At low temperature, the magnetocrystalline anisotropy is positive due to Co2+ ions contribution. At high temperature, Ni-Zn-Cuhost crystal contribution becomes preponderant and K1 is negative. The measurements are thus
coherent with the single-ion model theory.
The cobalt substitutions are also known to pin the domain walls and to lower the domain wall
displacements contribution to the permeability. This results in a decrease of s with the increase of
the cobalt content, as can be seen in figures 4.A1 and 4.B1. For the third series (Ni / Zn = 3, figure
4.C1), the magneto-crystalline compensation is particularly marked. The permeability of cobalt
substituted ferrites can then become higher than that of the cobalt-free ferrite (curve B, figure
4.C1). It seems that for these ferrites, a slight cobalt substitution leads to a smaller K1 than that of
the cobalt-free ferrite.
Temperature dependence of core loss
Core loss variations mainly depend on saturation magnetization and effective anisotropy (since
we consider that the microstructures are similar for all the materials). Indeed, it is known that
larger grain size can increase core loss [15]. For the cobalt-free ferrites these two parameters
decrease versus temperature.
The Ni0.24Zn0.56Cu0.20Fe1.98O4 ferrite (curve A of the figure 4.A2) has core loss decreasing until
20C and rapidly increasing above 120C. To understand this behaviour, we have to look at the
temperature dependence of the permeability. Until 80C, the anisotropy decreases faster than the
saturation magnetization, which results in an increase of the permeability and a decrease of the
core loss. Above 80C, the initial static permeability reaches 1000, shifting the resonance
frequency towards 3 MHz. As the measurements are done at 1.5 MHz, relaxation losses become
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therefore predominant and lead to a fast increase of the core loss at high temperature.
When the nickel content increases, the Curie temperature rises. For the
Ni0.40Zn0.40Cu0.20Fe1.98O4- ferrite (curve A, figure 4.B2), Tc is around 340C. The core loss
measurements between 50 and 150C are continuously decreasing. This is again related to the
variation of permeability which constantly increases while maintaining a resonance frequency far
enough from 1.5 MHz.
For the Ni0.60Zn0.20Cu0.20Fe1.98O4 ferrites (curve A, figure 4.C2), one can note that the
permeability is almost constant in the studied temperature range. The core losses are thus nearly
stable between 50 and 150C, a slight decrease can be observed at high temperature. Concerning
the core loss values of the Ni-Zn-Cu ferrites, the higher the magneto-crystalline anisotropy, the
higher the core loss. The power losses at room temperature increase from 600 mW/cm3 to 2800
mW/cm3 when nickel content goes from 0.24 mol to 0.60 mol per formula.
Cobalt substituted ferrites have a completely different behaviour. The core loss goes through a
minimum around T0 (magneto-crystalline compensation temperature) and their values are also
highly reduced near this compensation compared to the cobalt-free ferrites. This phenomenon
appears to be similar to the K1 compensation observed in Mn-Zn spinels [12]. This compensation,
due to Fe2+ ions, also leads to a minimum in the core loss. If this is well known for Mn-Zn ferrites,
it is the first time that it is observed in Ni-Zn based ferrites.
Such low core losses around T0 are not only due to the K1 compensation but are also the result
of the cobalt induced anisotropy (Ku). Small amounts of Co2+ ions in Ni-Zn spinels are known to
pin the domain walls, however, the temperature dependence of this induced anisotropy is not well
known. In order to study this parameter, Core loss versus magnetic induction of the
Ni0.40Zn0.40Cu0.20Co0.028Fe1.98O4+ ferrite was measured at different temperatures (figure 5). The
cobalt substituted ferrites have not a classical behaviour of core loss versus induction. When
induction increases, the core loss increases almost linearly until a threshold induction
corresponding to the required energy to unpin the domain walls. Above this threshold induction
(which depends on K1 and Ku), the anisotropy induced by the cobalt is no longer efficient so the
core loss increases fast. This phenomenon appears clearly on figure 5 for the measurement at
20C, the core loss increases slightly up to 35 mT and then rises rapidly. When the temperature
increases, the threshold induction decreases and, for the measurement done at 100C, the core loss
nearly recovers a classical behaviour with an evolution proportional to the square of the magnetic
induction. This ferrite has a T0 close to 10C, therefore the measurements done on figure 5 tend to
prove that the cobalt induced anisotropy is more efficient around the magneto-crystalline
anisotropy compensation.
Consequently, around T0 the magnetic configuration is doubly favourable in order to have low
power loss with a weak effective anisotropy and an induced anisotropy that improve the linearity
of the ferrite. This can then lead to very low core loss of respectively 150 and 200 mW/cm3 (at 1.5
MHz, 25 mT and 20C) for Ni / Zn = 0.43 and Ni / Zn = 1 ferrites with cobalt content of 0.028
mol. The third series of ferrites have higher core loss with a minimum of 400 mW/cm3. It seems
that K1 of the Ni-Zn-Cu host crystal (which increases due to high nickel content) is too high to
have very low core loss.
3 Conclusion
The study of the temperature dependence of core loss of cobalt-substituted Ni-Zn-Cu ferrites
highlighted that the core losses were minimum around the magneto-crystalline anisotropy
compensation. This is extremely interesting for adapting the ferrite to the operating range
temperature for power applications. Today, power electronics need materials that can work at high

frequency and high temperature (> 80C). The ferrites studied in this paper can perfectly answer to
these issues. Indeed, for the Ni0.40Zn0.40Cu0.20CoFe1.98O4+ ferrites (figure 4.B2), core loss at 80C
can be divided by a factor 4 thanks to cobalt substitution. These materials represent also a real
improvement compared to the state of art Ni-Zn ferrite for radiofrequency, with core loss 4 times
lower than a commercial ferrite with s=120 (figure 6).

References
[1] T. Y. Byun, S. C. Byeon, K. S. Hong, Factors affecting initial permeability of Co-substituted
Ni-Zn-Cu ferrites, IEEE, vol 35, Issue 5, Part 2, pages : 3445-3447 (1999)
[2] R. Lebourgeois, J. Ageron, H. Vincent and J-P. Ganne, low losses NiZnCu ferrites (ICF8),
Kyoto and Tokyo, Japan (2000)
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Sikalidisb, The effect of Nb2O5 dopant on the structural and magnetic properties of MnZn
ferrites, Journal of Magnetism and Magnetic Materials Volume 250, Pages 98-109, (2002)
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on properties of NiZn and NiCuZn ferrites Journal of Magnetism and Magnetic Materials 310,
p1721, (2007)
[7] Y. Matsuo, M. Inagaki, T. Tomozawa, and F. Nakao, IEEE Transactions On Magnetics, Vol.
37, n. 4, (2001)
[8] J. S. Smit and H. P. J. Wijn, Ferrites, Philips technical library (1961)
[9] J. Ageron ,Thesis (1999)
[10] G. K. Joshi, A. Y. Khot and S. R. Sawant, Magnetisation, curie temperature and Y-K angle
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vol 65 n12, 1593-1595 (1988)
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Ions on the Electrical and Magnetic Properties of NiZnMe Ferrites, IEEE transactions on
magnetics, vol 36 n6 (2000)
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(1998)
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properties of nickelzinccopper ferrites, Journal of Magnetism and Magnetic Materials, Volume
312, Issue 2, Pages 328-330, (2007)

Ms
(emu/g)
65.5

Ferrites
Ni/Zn=0.43

Co=0

Ni/Zn=0.43

Co=0.014

65.5

Ni/Zn=0.43

Co=0.028

64.4

Ni/Zn=0.43

Co=0.035

65.2

Ni/Zn=1

Co=0

79.8

Ni/Zn=3

Co=0

72.4

Table 1 : Saturation magnetization at room temperature of materials sintered at 935C for 2


hours in air.

% Cobalt

T0
Ni /Zn = 0.43

T0
Ni /Zn = 1

T0
Ni /Zn = 3

0.014

-45C

-50C

-28C

0.028

-7C

5C

30C

0.035

3C

17C

50C

Table 2 : Magneto-crystalline anisotropy compensation of the three series of ferrites, determined


from s(T) curves.

Figure 1 : X-ray diffraction pattern of Ni0.40Zn0.40Cu0.2Fe1.98O4 ferrite (black curve), comparison


with JCPDF 00-052-0277 (red peaks).

Figure 2 : Density of the three series of ferrites sintered at 935C for 2 hours in air.

Ni/Zn=0.43 _ Co=0

Ni/Zn=1 _ Co=0

Ni/Zn=1 _ Co=0.028

Figure 3 : SEM Micrographics of three materials sintered at 935C for 2 hours in air.

Ni0.24Zn0.56Cu0.20CoFe1.98O4+

(4.A1)

(4.A2)

Ni0.40Zn0.40Cu0.20CoFe1.98O4+

(4.B1)

(4.B2)

Ni0.60Zn0.20Cu0.20CoFe1.98O4+

(4.C1)

(4.C2)

Figure 4 : Initial static permeability versus temperature and core loss at 1.5 MHz and 25 mT versus
temperature
of
Ni0.24Zn0.56Cu0.20CoFe1.98O4+,
Ni0.40Zn0.40Cu0.20CoFe1.98O4+
and
Ni0.60Zn0.20Cu0.20CoFe1.98O4+ ferrites

10

Figure 5 : Core loss of the Ni0.40Zn0.40Cu0.20Co0.028Fe1.98O4+ ferrite measured at 1.5 MHz versus magnetic
induction for different temperatures.

Figure 6 : Core loss versus temperature measured at 1.5 MHz and 25mT. Comparison between a commercial NiZn ferrite ( s=120) and the Ni0.40Zn0.40Cu0.20Co0.028Fe1.98O4+ ferrite ( s=130)

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