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DR.SUBHASH KULKARNI
Modern trend in materials science and related fields is the fabrication, characterization and applications of
materials.. In the present study, NiFe2O4 (Nickel ferrite) was prepared by microwave synthesis using urea as a
fuel .Nickel oxalate and iron oxalate were irradiated with microwaves in the presence of fuel to get nickel
ferrite. Microwave method is also clean and non-polluting..The dielectric properties and ac conductivity (ac)
have been studied for the prepared sample in the temperature range 00-7000 C and for different frequencies 1
KHz, 10 KHz, 100 KHz and 1MHz.The electrical conductivity (ac) results revealed a semiconductor behavior
with temperature. The dielectric behavior is explained by using the mechanism of polarization process. The
magnetic measurements on nickel ferrite were carried out by using a vibrating sample magnetometer in the
applied field 958.68 Oes at room temperature. The Hc values confirmed that hard ferrites were obtained by this
procedure.D.C Conductivity measurements were carried out on the nickel ferrite by using an electrometer in
the temperature range from 260 C to 4000 C.
Key words: Microwave route, nickel ferrite, ac conductivity, dielectric constant, dielectric loss.
1. Introduction
Ferrites form a very good class of electrical materials because of their high resistivity and low loss behaviour,
and hence have vast technological applications over a wide range of frequencies .Ferrites are preferred in the
field of electronics and telecommunication industry because of their novel electrical properties which makes
them useful in radiofrequency circuits, high quality filters, rod antennas, transformer cores, read/write heads for
high digital tapes and other devices . Hence it is important to study their dielectric behaviour at different
frequencies. The dielectric properties of ferrites are dependent on several factors, such as method of
preparation, heat treatment, sintering conditions, chemical composition, cation distribution and crystallite size
[1].
Ferrites, a distinct class of magnetic materials known as ferromagnetic have spinel structure. They consist of
spontaneously magnetized domains and show the phenomena of magnetic saturation and hysteresis. Spinel
ferrites possess properties of both magnetic materials and insulators and are important in many technological
applications. The interesting physical and magnetic properties of spinel ferrites arise from the ability of these
compounds to distribute the cations among the available tetrahedral (A) and octahedral (B) sites [2]. Spinel
ferrites have gained lot of attention because of their remarkably high electrical and magnetic flux induction.
They are considered as good dielectric and are found in many technological applications. Increased application
of ferrites has led to the development of many chemical methods which includes hydrothermal, co-precipitation
and sol-gel for the preparation of stoichiometric and chemically pure spinel ferrites [3].Use of microwave
energy for synthesis and processing of materials is an exciting new field in material science with enormous
potential for synthesizing new materials and novel microstructures. The growing interest during the past decade
is essentially due to the possibility of reduction in manufacturing cost on account of energy savings, shorter
processing times and improved product uniformity and yields. The fundamental difference in microwave
heating is that the heat is generated internally within the material instead of originating from external heating
sources and is responsible for the unique microstructure and uniformity. As a result of this internal and
volumetric heating, it is possible to heat materials rapidly and uniformly and to efficiently remove volatile
constituents [4].
Earlier, we had reported the synthesis and characterization on nickel ferrite [5].Recently, we have presented the
magnetic and transport properties of nickel ferrite [6].In this paper, we report the results on ac conductivity and
dielectric behavior of Nickel ferrite to understand conduction mechanism. Evaluation of magnetic and dielectric
properties of the composites and correlation of results may help in making composites for various applications.
Evaluation of ac conductivity gives a lot of information with respect to the usefulness of these materials for
various applications. Also the study of ac electrical conductivity throws light on the behavior of charge carriers
under an ac field, their mobility and the mechanism of conduction (Koops 1951; Brockman and White 1971;
Jankowski 1988).The dielectric properties of nickel ferrite could be varied by the addition of small traces of
cobalt, manganese and copper, and also by bringing deviation from stoichiometry (Van Uitest 1956a, b;
Malinafski & Babbitt 1964; Hudson 1970).
Nickel ferrites are known for high power handling capability at microwave frequencies due to their high curie
temperature which makes other magnetic properties of this series relatively independent of temperature [7].In
our earlier work [5], we carried out studies on the synthesis, characterization and IR studies of nickel ferrite. In
the present work, we report the study on the d .c conductivity, impedance characterization, resistivity and
magnetic properties of nickel ferrite. The study shows better utility of nickel ferrite, in order to tailor electrical
and magnetic properties of nickel ferrite.
2. Experimental
Details of the preparation of nickel ferrite had been reported in our previous work [5].In brief, the nickel
oxalate, iron oxalate and urea were mixed in weight ratio 1:1:5 and ground well in a pestle and mortar.
Resultant solid was placed in a crucible and ignited in microwave oven. The reaction was found to be
completed in about ten minutes at high power level and brown crystalline nickel ferrite material is formed. The
synthesis scheme is shown in fig (1)..Analysis of X-ray diffraction reveled that, the prepared nickel ferrite is
monophasic with cubic spinel structure.SEM images show that, the particles of NiFe2O4 form self assembled
irregular shaped blocks with globular arrangement .The infrared studies confirm the formation of nickel ferrite
materials [5].
0.006 2a 0.006
2b
0.005
0.005
ac S/cm
ac S/cm
0.004
0.004
0.003
0.003
0.002
0.002
0.001
0.001
0.000
0.000
0 100 200 300 400 500 600 700
0 0 100 200 300 400 500 600 700
Temprature C
0
Temprature C
0.06 1.4
0.05
2c 1.2 2d
ac S/cm
ac S/cm
1.0
0.04
0.8
0.03
0.6
0.02
0.4
0.01
0.2
0.00
0.0
-0.01 -0.2
0 100 200 300 400 500 600 700 0 100 200 300 400 500 600 700
0
Temprature C Temprature 0C
Fig: 2 (a-d) shows the variation of conductivity with temperature at[a] 1KHz [b] 10KHz[c] 100KHz [d].1MHz frequencies
The dielectric constant of any materials, in general, is directly related to dielectric polarization. The higher the
polarization, the higher will be the dielectric constant of the material. There are four primary mechanisms
causing polarizations; electronic polarization, ionic polarization, dipolar polarization and space charges
polarization. Their occurrence depends upon the electric frequency of the applied field. At low frequencies,
space charge polarization and dipolar polarization are known to play the vital role and both these polarizations
are temperature dependent. At high frequencies, electronic and ionic polarizations are main contributors, and
their temperature dependence is insignificant [10].In ferrites, the dielectric constant is expected to decrease
continuously with increase in frequency.
The variation of dielectric constant as a function of frequency for NiFe2O4 is shown in Fig3 [a-d].It can be seen
from the figure that the value of increases up to 10 KHz and decreases thereafter with increasing frequency
and this agrees with earlier report (Hana et al.1999 studied the preparation of NiFe2O4 by ceramic and wet
methods. They found that dielectric constant decreased with increasing frequency). The decrease of dielectric
constant with increase of frequency as observed in the case of nickel ferrite is a normal dielectric behavior.
When the frequency is increased, peak is increased up to 10KHz and later it decreases when the frequency is
increased to 1MHz.This decrease in occurs because beyond a certain frequency of the externally applied
electric field, the electronic exchange between ferrous and ferrite ions i.e. Fe2+ & Fe3+ cannot follow the
alternating field .In other words, the low frequency helps in aligning more dipoles in the field direction with the
result of an increase in the polarization as well as increase in , while by increasing frequency, the dipoles are
distributed and decreases[Reddy et al 1999].The rapid increase in the dielectric constant with temperature at
low frequencies suggests that the effect of temperature is more pronounced on the interfacial rather than on
dipolar polarization[11].
Variation of dielectric constant with temperature is shown in fig 3[a-d].From the graph it is clear that, the
dielectric constant initially increases gradually with temperature up to 2100C but beyond 2100C,a sudden
decrease in for 1KHz frequency is noticed .But around 900C a sudden increase in for 1KHz is noticed. On
increasing the temperature, electrical conductivity increases due to the increase in thermally activated drift
mobility of electric charge carriers according to hopping conduction mechanism. So, the dielectric polarization
increases causing a marked increase in as the temperature increases. [8][12]. Again around 2000C a fall in
is observed for the same frequency. This increase in for the nickel ferrite is observed at 1KHz, 10KHz.The
anomaly in variation of for all the frequencies is due to the transition of the sample from the ferrimagnetic
state [magnetically ordered] to the paramagnetic state [disordered state].The higher temperature peak at 10KHz
may be due to the space charges getting depleted resulting in a peak at a particular temperature as reported
earlier [Maheshkumar et al 1998].
25000 2a 2.5x10
12
3a 32 bb
20000 2.0x10
12
15000 12
1.5x10
'
'
10000
12
1.0x10
5000
11
5.0x10
0
0.0
-5000
0 100 200 300 400 500 600 700 0 100 200 300 400 500 600 700
0 0
Temprature C Temprature C
1.6x10
12 650
2d
32 cc 3d
12
1.4x10
12
600
1.2x10
12
1.0x10
550
11
8.0x10
'
'
11
6.0x10
500
11
4.0x10
11
2.0x10 450
0.0
-2.0x10
11 400
0 100 200 300 400 500 600 700 0 100 200 300 400 500 600 700
0
Tempratrue C
0 Temprature C
The dielectric properties can vary widely in solids as a function of temperature, frequency of applied electric
field, humidity, crystal structure and other external factors..It is important to note that the dielectric response of
a solid can be succinctly described by expressing the relative dielectric constant as a complex quantity made up
of a real component and an imaginary component, i.e.
*=' +j ------(1)
Where ' and are the real and imaginary part of dielectric constant, representing the amount of energy stored
in a dielectric material as polarization and the energy loss respectively, while applying an electric field as
reported earlier(J.Chand et al 2009).
The dependence of dielectric loss on frequency is shown in fig 4[a-d].It is clear that increased up to
10KHz and later decreased with increasing frequency. It is observed that the loss is very low at 1 KHz due to
low lattice polarization. However as the frequency increases, peak is observed at 10 KHz. As the frequency is
further increased, loss reduces as reported earlier (Khedr et al 2004) and is due to high lattice polarization.
It is observed from fig 4[a-d] that, loss increases with temperature until reaching a maximum. As the
temperature increases around 2000C, dielectric loss decreases and remains constant up to 6000C.The highest
value of is measured at a temperature around 2500C.However, the increase in with the temperature is due
to the relaxation of the dipole molecules coupled with the resulting drop in relaxation time. This in turn exerts a
double effect on the dielectric loss. On one hand the friction between the dipoles will be increased and on the
other hand the energy required to overcome the internal mechanical friction of the medium will be decreased
when the dipoles rotate through a unit angle [13].So, due to this dielectric loss increases.
12
0.00018 1.8x10
12
0.00016 1.6x10
4b
3a 3b
0.00014 4a 1.4x10
12
12
0.00012 1.2x10
12
0.00010 1.0x10
11
0.00008 8.0x10
''
''
11
0.00006 6.0x10
11
0.00004 4.0x10
11
0.00002 2.0x10
0.00000 0.0
11
-0.00002 -2.0x10
0 100 200 300 400 500 600 700 0 100 200 300 400 500 600 700
0 0
Temprature C Temprature C
11 -7
6x10 1.2x10
11
4 c3 c -7
1.1x10
4 d3 d
5x10
-7
11
1.0x10
4x10
-8
9.0x10
''
11
3x10
''
-8
8.0x10
11
2x10
-8
7.0x10
11
1x10 -8
6.0x10
0 -8
5.0x10
0 100 200 300 400 500 600 700 0 100 200 300 400 500 600 700
0
Temprature C 0
Temprature C
Fig 4 (a-d) shows the variation of dielectric permittivity (loss) with temperature at[a] 1KHz[b] 10KHz [c]100KHz[d]1MHz frequencies
Fig 5 shows the M-H curve of nickel ferrite. The area of the hysteresis loop corresponds to energy loss per
unit volume per cycle .The specific relationship of force to flux [field intensity H to magnetic moment density
M] is graphed in a form called the normal magnetization curve .It is possible to apply so much magnetic field
force to a ferromagnetic material that no more flux can be crammed in to it. This condition is known as
magnetic saturation .When the retentivity of a ferromagnetic substance interfaces with its remagnetization in the
opposite direction, a condition known as hysteresis occurs.
Ferromagnetic materials, which have tall, narrow hysteresis loops with small loop areas, are referred to as soft
ferrites. Good permanent magnets, on the other hand, should show a high resistance to demagnetization. This
requires that they be made with materials that have large coercive field intensities HC and hence fat hysteresis
loops. These materials are referred to as hard ferromagnetic materials .From Table-1, the value of HC is found
to be 958.68 Oe and as per this nickel ferrite may be considered as the hard magnetic material.
Figure 5 shows the hysteresis loop for nickel ferrite recorded using vibrating sample magnetometer. Various
magnetic properties such as saturation magnetization (Ms) remanence (Mr) and corecivity (Hc) are calculated
from the hysteresis loop and given in Table 1.. However the measured coercivity value of 958.68 Oe is much
larger and it can be attributed to the strength of magnetic moments formed [14].
Where R is the resistance values of the samples, A(cm2) the area of the electrodes and l (cm) the thickness of
the sample. Conductivity was calculated by using the formula
dc= l/ ------------------- (2)
10 -8
3.5x10 2.0x10
Conductivity
-8
1.8x10
10
3.0x10
-8
1.6x10
10
2.5x10 -8
1.4x10
-8
2.0x10
10 1.2x10
Conductivity
-8
1.0x10
Resistivity
10
1.5x10
-9
8.0x10
10
1.0x10 6.0x10
-9
-9
9
4.0x10
5.0x10
-9
2.0x10
0.0
0.0
9 -9
-5.0x10 -2.0x10
0 50 100 150 200 250 300 350 400 450
0
Temprature C
4. Conclusion
The ac electrical conductivity of Nickel ferrite is calculated by using a simple relationship in the form ac=2f
tan0 with data available from dielectric measurements. It is observed that, as the temperature increases, the
ac conductivity increases gradually with increasing frequencies reaching a maximum at 1MHz frequency.
Electrical properties of nickel ferrite show low electrical conduction. The conductivity of nickel ferrite can be
varied by using a suitable dopant material. Here, dielectric constant increases up to 10 KHz and with further
increase in frequency, it starts decreasing. At lower frequencies (10KHz), the increase in dielectric constant is
very large (2.5 1012) with an increase in temperature, while at higher frequency range (100KHz-1MHz), the
dielectric constant decreased (650).Dielectric loss is minimum or negligible at 1KHz frequency .It is maximum
at 10KHz (1.8 1012).As frequency increases further, loss reduces to a minimum( 1.2 10-7) at 1MHz
frequency. So, the dielectric loss is found to be smaller at high frequencies .The dc conductivity is found to be
very low. But the resistivity is found to be very high i.e3.231010 Ohm-cm. at a temperature of 1000 C and is
found to decrease with a rise in temperature .The obtained Hc value of 958.68 Oe indicates that the nickel
ferrite is a hard ferrite.
Acknowledgements
Authors are grateful to Dr.B.B.Lal, Principal, Rural Engineering College, Bhalki for his encouragement.
Authors would like to acknowledge Sri.Shahi.M.Lohar of Rural Engineering College, Bhalki for providing all
technical help while preparing the manuscript of the paper.
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Biographies of authors