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Materials Science and Engineering B60 (1999) 156 – 162

Dielectric properties of NiZn ferrites prepared by the citrate


precursor method
A. Verma a, T.C. Goel a,*, R.G. Mendiratta a, M.I. Alam b
a
Department of Physics, Indian Institute of Technology, Hauz Khas, New Delhi 110 016, India
b
Central Electronics Limited, Sahibabad 201 010, U.P., India

Received 20 January 1999; accepted 25 January 1999

Abstract

Dielectric properties such as dielectric constant, e%, and dielectric loss factor, tan d  , are reported for different compositions of
NiZn ferrites prepared by the citrate precursor method and sintered in the temperature range 1100 – 1400°C. It is observed that
e% and tan d  for samples prepared in the present work are much lower than those normally obtained for NiZn ferrites prepared
by the conventional ceramic method. The low values are attributed to better compositional stoichiometry, single-phase spinel
structure and uniform microstructure of the samples. The low dielectric loss makes these samples especially attractive for use at
high frequencies. © 1999 Elsevier Science S.A. All rights reserved.

Keywords: Dielectric properties; NiZn ferrites; Citrate precursor method

1. Introduction constituent ions leading to stoichiometric compositions


as mixing takes place on an atomic scale in the solution
Nickel-zinc ferrite is a versatile technological mate- state. (b) No ball-milling is required in this process and
rial, particularly suited for high-frequency applications. hence there is little scope of contamination of the
The properties of ferrite materials are known to be materials. In the case of ferrites prepared by the con-
strongly influenced by their composition and mi- ventional method, there is invariably some possibility of
crostructure which in turn are sensitive to the process- introducing iron impurities into the ferrite due to abra-
ing methods used to synthesize them. Selection of an sion of steel balls during milling. The introduction of
appropriate process is, therefore, the key to obtaining impurities leads to inhomogeneity in the ferrite struc-
good quality ferrites. In an attempt to prepare high ture which has an adverse effect on some of the dieletric
performance ferrites with reproducible stoichiometric properties. In addition, milling also introduces lattice
compositions and desired microstructures, the present stress and strains which result in distorted structures.
work aimed at preparing NiZn ferrites using the citrate (c) As the crystal structure evolves during the thermal
precursor method. This approach is different from the
decomposition of the citrate precursor it is possible to
conventional ceramic or solid-solution methods which
control the grain size by a suitable heat treatment
have several disadvantages particularly with respect to
giving rise to a relatively uniform microstructure. Al-
phase purity, control of microstructure and defect
though there are a few reports [3–7] on the preparation
chemistry. The citrate process [1,2] is simple, easy and
of NiZn ferrites by wet chemical methods, the prepara-
does not require an elaborate and expensive experimen-
tal set-up. The main advantages of this method are: (a) tion of NiZn ferrite by the citrate precursor method has
Its capability to yield an homogeneous mixture of the not been reported. Also, there are hardly any reports
on the electrical properties of NiZn ferrites prepared by
the wet methods. It was therefore felt appropriate to
use the citrate precursor method to prepare NiZn fer-
* Corresponding author. Tel.: +91-11-686-1977; fax: + 91-11-686-
2037. rites and study the effect of processing on their dielec-
E-mail address: tcg@physics.iitd.ernet.in (T.C. Goel) tric properties.

0921-5107/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 9 2 1 - 5 1 0 7 ( 9 9 ) 0 0 0 1 9 - 7
A. Verma et al. / Materials Science and Engineering B60 (1999) 156–162 157

nature. This dried glassy citrate mixture was calcined at


1000°C for 1 h to obtain the spinel ferrite. The ferrite
powder thus obtained was pressed at a pressure of 10
tons to obtain pellets of 1.3 cm diameter and 1.5 mm
thickness. Polyvinyl alcohol (2% by weight) was used as
binder. The pellets were sintered in air over a range of
temperatures, 1100–1400°C, for a period of 1 h at a
heating rate of 150°C h − 1 and were subsequently fur-
nace-cooled. X-ray diffraction patterns of the ferrite
powder as well as the sintered pellets taken on a Rigaku
Geiger Flex 3 kW X-ray diffractometer revealed a
single-phase spinel structure. A typical diffractogram of
the NiZn ferrite powder obtained on calcination is
shown in Fig. 1. The photomicrographs of the fractured
surfaces of the ferrite samples were recorded on a
Cambridge Stereo Scan 360 scanning electron micro-
Fig. 1. X-ray diffractogram of NiZn ferrite powder (x= 0.35) ob- scope(SEM). For the dielectric measurements, silver
tained on calcination. paste was coated on polished pellets to provide electri-
cal contact. Dielectric constants were calculated from
2. Experimental the capacitance measurements made on a Hewlett-
Packard impedance analyser 4192-A in the frequency
Four different compositions of Ni1 − x Znx Fe2O4, with range 30 Hz–10 MHz. The values of dielectric loss, tan
x = 0.2, 0.35, 0.5 and 0.6, were prepared. The starting d  , were simultaneously recorded.
materials used in the preparation were nickel nitrate
(Merck, India), zinc nitrate (Merck, India), iron(III)
citrate (Merck, Germany) and citric acid (Merck, In- 3. Results and discussion
dia). The chemicals were weighed according to the
required stoichiometric proportion. Iron(III) citrate so- The frequency variations of the room temperature
lution was prepared in distilled water by heating at dielectric constant e%, and dielectric loss factor, tan d 
40°C with constant stirring. Nickel nitrate and zinc of NiZn ferrites prepared by the citrate precursor
nitrate were added to a solution of citric acid in dis- method are shown in Figs. 2–5. A decrease in the
tilled water. The solution was heated at 40°C for about dielectric constant with frequency is observed in the
30 min and added to the iron citrate solution under range 30 Hz–10 MHz for all compositions. Dielectric
continuous stirring. This mixture was evaporated to constants of ferrites sintered in the temperature range
dryness to obtain a homogeneous uniformly brown 1100–1300°C are observed to be quite low, between 30
coloured transparent material which was glass-like in and 400, at low frequencies from 30 to about 500 Hz.

Fig. 2. Frequency variation of dielectric constant, e%, and dielectric loss factor, tan d  , of Ni1 − x Znx Fe2O4 (x= 0.6) sintered at 1100, 1200, 1300
and 1400°C.
158 A. Verma et al. / Materials Science and Engineering B60 (1999) 156–162

Fig. 3. Frequency variation of dielectric constant, e%, and dielectric loss factor, tan d  , of Ni1 − x Znx Fe2O4 (x= 0.5) sintered at 1100, 1200, 1300
and 1400°C.

Above these frequencies, the values are much lower, quent formation of Fe2 + ions. The prolonged ball-
approaching the intrinsic value [8] due to the polaris- milling of the oxides could also result in Fe2 + being
ability of the oxygen ions. For the samples sintered at introduced into the ferrite due to abrasion of the steel
1400°C, comparatively higher values of the dielectric balls. Thus, ferrites prepared by the conventional
constant are observed. It may be pointed out that much method are invariably likely to have more Fe2 + and,
higher values of the dielectric constant, of the order of therefore, a higher dielectric constant. Koops [9] and
103 –104, with pronounced dispersions at around 103 Hz others [11–13] had given a similar explanation for the
have been reported [9] for NiZn ferrites prepared by the high values of the dielectric constant of ferrites pre-
conventional ceramic method. pared by the conventional method.
Polarisation in ferrites has largely been attributed to Since in the present work, no milling processes are
the presence of Fe2 + ions which give rise to heteroge- involved, and the sintering is done at relatively lower
neous spinel structure. Since Fe2 + ions are easily polar- temperatures, little deviation in stoichiometry is ex-
isable, the larger the number of Fe2 + ions the higher pected, thus giving greater structural homogeneity. Due
would be the dielectric constant. The very high values to this, low dielectric constant values are observed.
of dielectric constant obtained in the case of NiZn Compositional stoichiometry is an important require-
ferrites prepared by the conventional method, therefore, ment for obtaining low dielectric constants and low
suggest the presence of more Fe2 + ions rendering the losses [14]. As can be observed (Figs. 2–5), the samples
ferrite structure highly heterogeneous. The extent of sintered at 1200°C exhibit low dielectric constant even
Fe2 + ions in the ferrites largely depends upon the at lower frequencies and it remains nearly constant over
method of preparation. The conventional method of the entire frequency range studied. This suggests that
preparation requires the starting oxide materials to be Zn evaporation leading to Fe2 + formation and conse-
ball-milled and subsequent heat-treatment at high tem- quent heterogeneity in structure becomes significant
peratures of 1250 – 1400°C. The high temperature sin- only when samples are sintered at temperatures higher
tering proves deleterious as it results in Zn loss [10] than 1200°C. This is also supported by the density
from the ferrite due to volatilization and the conse- (calculated from the weight and bulk volume of the
A. Verma et al. / Materials Science and Engineering B60 (1999) 156–162 159

samples) data (Table 1). Higher porosity results in shows the least dielectric constant and dispersion, this
lower dielectric constants and dielectric losses. Accord- sample shows good promise for use in device applica-
ing to these arguments, it is expected that samples tions. The photomicrograph of this sample is shown in
sintered at 1100°C, would have a still lower dielectric Fig. 6. As can be seen, the microstructure consists of
constant. However, the reverse has been observed in the relatively small size grains (: 2 mm). It is to be noted
present studies. This is due to the fact that 1100°C is that, in general, the grain size and the size-spread for
not a sufficiently high temperature to result in homoge- samples prepared by the present method are much
neous spinel structure free from imperfections. It thus smaller than those for samples prepared by the conven-
seems that temperatures around 1200°C are appropriate tional method [16–18]. Small grains are preferred in
for sintering the samples in order to get good ferrites. ferrites [13] as oxidation advances faster in smaller
In addition to the sintering temperature, the amount grains thus leading to the acceleration of the Fe2 + to
of Zn in the samples also influences the dielectric Fe3 + transformation. Therefore, the probability of
properties of the ferrites in the following two ways: (a) Fe2 + formation in smaller grains is low resulting in
ferrites with a larger zinc concentration are likely to lower dielectric constants.
contain relatively greater amount of Fe2 + as the proba- The low dielectric constant values observed in the
bility of zinc evaporation would be more in these present work suggest that the resistivity of these sam-
samples, and (b) zinc brings about perfection in the ples should be high [13,19]. Higher values of resistiv-
ferrite crystal structure [15]. These two effects play ity(108 –1011 V cm) have indeed been observed in the
against each other in determining the sample properties. present work [20] as compared to those obtained (103 –
SEM photographs of various samples were taken to 106 V cm) for NiZn ferrites prepared by the conven-
understand the microstructure of the prepared ferrites. tional method [21,22].
It is observed that the average grain size increases from As can be seen in Figs. 2–5, the dielectric dispersion
about 0.6 mm for samples sintered at 1100°C to about in the samples is very small, extending up to about 103
8.0 mm for samples sintered at 1400°C. The correspond- Hz and is insignificant at higher frequencies. The low
ing values for the particle size-spread are from 0.5 to dielectric dispersion exhibited by the samples is due to
0.7 mm and from 4 to 13 mm, respectively. Since the their low dielectric constant values at low frequencies.
sample with composition x = 0.6 sintered at 1200°C Generally, ferrites with large dielectric constants are

Fig. 4. Frequency variation of dielectric constant, e%, and dielectric loss factor, tan d  , of Ni1 − x Znx Fe2O4 (x= 0.35) sintered at 1100, 1200, 1300
and 1400°C.
160 A. Verma et al. / Materials Science and Engineering B60 (1999) 156–162

Fig. 5. Frequency variation of dielectric constant, e%, and dielectric loss factor, tan d  , of Ni1 − x Znx Fe2O4 (x =0.2) sintered at 1100, 1200, 1300
and 1400°C.

found to exhibit pronounced dispersion in their dielec- The dielectric loss arises due to the lag of the polari-
tric spectra. Thus samples sintered at 1400°C which sation behind the applied alternating electric field and is
have a relatively higher dielectric constant are observed caused by the impurities and imperfections in the crys-
to exhibit marked dispersion. Samples sintered at tal lattice. Structural defects give rise to trapping cen-
1200°C are found to exhibit the least dispersion. This tres for the electrons, also known as correlated states
behaviour is quite similar to that observed by [26]. As indicated above, some of the curves show loss
Jankowski [23] and can be explained on the basis of the peaks at frequencies around 200 Hz and 105 Hz. These
many–body interactions [24]. Owing to the disordered peaks are as a result of resonance due to the matching
structure of the grain boundaries, the polarisation is of the time period of the applied electric field with those
due to discontinuous hopping of charges, electrons or of the corresponding relaxation phenomena. The re-
sponse time of the electrons in the trapping centres is
ions, between localised states as a result of many–body
higher than the time taken for hopping between the
interactions between its constituent parts.
sites of the charged particles. It thus follows that the
It can be seen from the loss curves shown in Figs.
peak around 200 Hz is due to the relaxation in the
2 –5 that: (a) the losses are frequency dependent, (b) the
loss values vary with composition and sintering temper-
Table 1
ature, and (c) certain curves show the presence of loss Density of NiZn ferrites sintered at different temperaturesa
peaks.
It is observed that the values of the loss factor for the Composition Ni1−x Znx Fe2O4 Density (g cm−3)
samples are significantly lower compared to those re-
A B C D
ported [9,25] for the samples prepared by the conven-
tional method. For instance, the loss factor for the x= 0.6 4.11 4.62 5.12 4.92
sample of the composition x = 0.6 sintered at 1200°C is x= 0.5 3.78 4.68 4.82 4.80
around 10 − 2 at frequencies around 105 Hz. The corre- x= 0.35 3.77 4.77 5.10 5.00
x= 0.2 3.63 3.79 4.20 4.40
sponding value reported in the literature [9] for the
sample prepared by the conventional method is more a
A, B, C and D refer to sintering temperatures of 1100, 1200, 1300,
than 2. and 1400°C, respectively.
A. Verma et al. / Materials Science and Engineering B60 (1999) 156–162 161

varies with the composition of the sample and the


sintering temperature. The higher values of losses for
x= 0.35 and x= 0.6 samples could be due to the higher
density and the presence of larger amount of Fe2 + ,
respectively.

4. Conclusions

The citrate-based preparations have resulted in a


dielectric constant and dielectric loss values appreciably
lower than those for the samples prepared by the
conventional ceramic method. This is a significant re-
sult of the present investigation and provides a conve-
nient and economical method for the preparation of
Fig. 6. Photomicrograph of the fractured surface of Ni1 − x Znx Fe2O4 better quality ferrites which can be used over a fre-
(x= 0.6) sintered at 1200°C. quency range much larger than that for which the
conventionally prepared ferrites can be used.
correlated states and the one at the higher frequency
(105 Hz) corresponds to the hopping of electrons. The
magnitude of the loss at 200 Hz would depend on the References
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