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Journal of Magnetism and Magnetic Materials 214 (2000) 55}60

Microstructure, frequency and temperature-dependent


dielectric properties of cobalt-substituted lithium ferrites
S.C. Watawe , B.D. Sarwade, S.S. Bellad , B.D. Sutar , B.K. Chougule *
Ferrite Materials Research Laboratory, Department of Physics, Shivaji University, Kolhapur 416 004, India
National Chemical Laboratory, Pune 411 008, India
Received 24 September 1999; received in revised form 2 February 2000

Abstract
Ferrites with the general formula Li
Co Fe
O (where x"0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7) were prepared by
 \V V  \V 
the standard ceramic method. AC resistivity (o ), dielectric constant (e) and dielectric loss tangent (tan d) were measured
!
as a function of frequency and temperature. The compositional variations of o and e with x show inverse trends with
"!
each other. The dielectric constant increases slowly from 0 to 450 with temperature in the beginning and sharply after
2003C. The e and o show a decrease with increase in frequency for all the samples. The variation of tan d with
"!
frequency shows cusps for all the samples except for x"0.5. These variations have been explained on the basis of Koop's
phenomenological theory, concentration of Fe> and Fe> ions on octahedral site and hopping frequency of electrons
between Fe> and Fe>.  2000 Published by Elsevier Science B.V. All rights reserved.
Keywords: Ferrites; Dielectric properties; Electrical properties; Microstructure

1. Introduction
The polycrystalline ferrites have very good dielectric properties that are dependent upon several
factors such as the method of preparation, substitution of di!erent cations, etc. Lithium and substituted lithium ferrites have been found to be very
good substitutes for garnets in microwave devices
due to their low costs, high resistivity and low eddy
current losses. The properties of lithium ferrites can
be tailor made by substituting them with di!erent
metal ions such as Co>,Cd>,Cu>,Ti>, Mg>,

etc., for device applications. Several studies have


been reported on additions of divalent, trivalent
and tetravalent ions in lithium ferrites [1}7]. However, not much has been reported in the literature
on dielectric properties of Co>-substituted lithium
ferrite. The Co> being a fast relaxing ion, enhances the microwave properties. We report here the
results on temperature and frequency-dependent
dielectric properties of cobalt substituted lithium
ferrites.

2. Experimental
* Corresponding author. Tel.: #91-0231-690571; fax: #910231-691533.
E-mail address: bkchougule@hotmail.com (B.K. Chougule).

The Co-substituted lithium ferrite samples having the general formula Li


Co Fe
O
 \V V  \V 
(where x"0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7) were

0304-8853/00/$ - see front matter  2000 Published by Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 8 8 5 3 ( 0 0 ) 0 0 0 3 3 - 0

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S.C. Watawe et al. / Journal of Magnetism and Magnetic Materials 214 (2000) 55}60

prepared by conventional double sintering ceramic


method. The presintering of the samples was carried out at 6003C for 12 h and the "nal sintering at
10003C for 24 h in air. The single phase formation
was con"rmed by X-ray di!raction patterns obtained by using PHILIPS PW-1710 X-ray di!ractometer with Cu K radiation (j"1.5418 As ). The
a
DC resistivity (o ) and the dielectric constant (e)
"!
of the samples in pellet form (1 cm diameter and
0.3 cm thick) were measured at room temperature
by two-probe method. The AC resistivity, dielectric
constant and dielectric loss tangent were measured
in the frequency range 1 kHz to 1 MHz at room
temperature using an HP 4284A LCR meter. The
variation of dielectric constant with temperature
was measured from room temperature to 4003C.

3. Results and discussion


3.1. Compositional variation of o

"!

and e

The variation of DC resistivity (o ) and dielec"!


tric constant (e) with cobalt content is shown in
Fig. 1. It is clear from the "gure that o and e
"!

Fig. 1. Variation of dielectric constant and DC resistivity with


Co> in Li
Co Fe
O ferrites.
 \V V  \V 

show inverse trends of variation with each other.


The DC resistivity is found to increase while dielectric constant is found to decrease upto x"0.4. The
sample with x"0.4 has maximum resistivity
(1.65;10 ) cm) and minimum dielectric constant
e (0.98;10). With further addition of cobalt o is
"!
found to decrease while e is found to increase.
Similar trend in the variation of o and e has been
"!
reported earlier by Shaikh et al. for Li}Mg}Zn
ferrites [1].
Both the dielectric constant and electrical conductivity are basically electrical properties and it
has been recognised that the same mechanism viz.
exchange of electrons between Fe> and Fe> is
responsible for both the phenomena. A strong correlation between conduction mechanism and the
dielectric behaviour of ferrites has been established
by Iwauchi [8] and Rezlescu et al. [9]. It has been
concluded that the electron exchange between
Fe>Fe> results in the local displacement of
charges, which is responsible for polarisation in
ferrites. The magnitude of exchange, which also
controls the conduction in ferrites, depends upon
the concentration of Fe>/Fe> ion pairs present
on B site.
The Fe> ion concentration is a characteristic
property of a given ferrite material and depends
upon several factors such as sintering time and
temperature, sintering atmosphere, annealing time,
etc., including the grain structure. Some amount of
Fe> ions are also formed due to possible evaporation of Li ions during sintering [10]. Sintering of
lithium ferrites is therefore carried out at lower
temperature (&10003C) in order to avoid lithium
loss during sintering.
The importance of microstructure in controlling
the electrical resistivity of ferrites has been stressed
by many earlier workers [11}13]. The relation between grain structure and dielectric constant is also
reported earlier by Kramer [14], Iwauchi [8] and
Larsenteau [15]. In polycrystalline ferrites the
grain boundaries, voids and the inhomogeneous
grain structure result in higher resistivity. This has
been evidenced in the case of cobalt containing
ferrites by us [16] and Song et al. [5]. According to
our present observation the grain size is minimum
with inhomogeneous nature at x"0.4 (2.0 lm).
The grain size is found to increase on either side of

S.C. Watawe et al. / Journal of Magnetism and Magnetic Materials 214 (2000) 55}60

57

x"0.4 to 6.7 lm for x"0.1 and 5.9 lm for x"0.7.


The porosity is also maximum in the case of the
sample with x"0.4 (16%). Hence, the rise in resistivity upto x"0.4 can be attributed to the porous
nature of this ferrite, which later on reduces due to
the re"ned structure of grains. Secondly, the Fe>
content is also reduced by 2.5!x/2 as the cobalt
content increases. Similar results have been reported earlier for Li}Cd ferrites by Radha et al. [6].
Since the dielectric constant is roughly inversely
proportional to the square root of the DC resistivity an inverse nature of variation of dielectric constant with x is observed.
3.2. Temperature variation of e
Figs. 2 and 3 show the variation of dielectric
constant (e) with temperature. It can be seen from
the "gures that the dielectric constant increases
slowly in the beginning (from 0 to 450) upto a certain temperature (2003C) and increases rapidly
thereafter. Since the resistivity of ferrites decreases

Fig. 3. Variation of dielectric constant (e) with temperature in


Li
Co Fe
O ferrites.
 \V V  \V 

with increase in temperature an increase in the


dielectric constant is expected. Such a behaviour
has been reported by Shaikh et al. [1] in the case of
Li}Mg}Zn ferrites and by Bellad et al. [17] in the
case of Li}Cd ferrites.
3.3. Frequency variation of o
!

Fig. 2. Variation of dielectric constant (e) with temperature in


Li
Co Fe
O ferrites.
 \V V  \V 

Fig. 4 shows the variation of AC resistivity with


log frequency at room temperature. All the samples
show a decrease in o with increase in frequency
!
from 1 kHz to 1 MHz, which is the normal behaviour of ferrites. The conduction in ferrites is
through exchange of electrons between Fe>
Fe> cations on B sites. The increase in frequency
of the applied "eld enhances the hopping of charge
carriers resulting in increase of conductivity and
decrease of resistivity. At higher frequencies AC
resistivity decreases and remains constant because
of the fact that hopping frequency can no longer

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S.C. Watawe et al. / Journal of Magnetism and Magnetic Materials 214 (2000) 55}60

Fig. 5. Variation of dielectric constant (e) with frequency in


Li
Co Fe
O ferrites.
 \V V  \V 
Fig. 4. Variation of AC resistivity (o ) with frequency in
!
Li
Co Fe
O ferrites.
 \V V  \V 

follow the frequency of the applied external "eld


leading to lower values of AC resistivity.
3.4. Frequency variation of e
Figs. 5 and 6 show the variation of dielectric
constant with frequency in the range 1 kHz to
1 MHz. The variation of dielectric constant with
frequency reveals the dispersion due to Maxwell}Wagner [18,19] type interfacial polarisation
in agreement with the Koops phenomenological
theory [20]. The dielectric constant decreases with
increasing frequency reaching a constant value for
all the samples at higher frequencies. The polarisation decreases with increase in frequency and attains a constant value beyond a certain frequency
limit.
3.5. Frequency variation of tan d
The variation of loss angle (tan d) with frequency
is shown in Figs. 7 and 8. It can be seen that all the

Fig. 6. Variation of dielectric constant (e) with frequency in


Li
Co Fe
O ferrites.
 \V V  \V 

S.C. Watawe et al. / Journal of Magnetism and Magnetic Materials 214 (2000) 55}60

Fig. 7. Variation of dielectric loss tangent (tan d) with frequency


in Li
Co Fe
O ferrites.
 \V V  \V 

samples show peaking behaviour except x"0.5.


The maxima occur between 55 and 65 kHz for all
the samples. The peaking behaviour in tan d occurs
when the jump frequency of electrons between
Fe> and Fe> is equal to the frequency of the
applied "eld [8,21,22].

Acknowledgements
The authors are thankful to Prof. R.C. Ayyer,
Microwave Laboratory, University of Poona, Pune
(India) for providing the experimental facilities.
One of us (SCW) is grateful to the University
Grants Commission New Delhi for the award of
fellowship under FIP programme.

References
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59

Fig. 8. Variation of dielectric loss tangent (tan d) with frequency


in Li
Co Fe
O ferrites.
 \V V  \V 

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