Journal of Alloys and Compounds: Rapolu Sridhar, D. Ravinder, K. Vijaya Kumar

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Journal of Alloys and Compounds 645 (2015) 436442

Contents lists available at ScienceDirect

Journal of Alloys and Compounds


journal homepage: www.elsevier.com/locate/jalcom

Temperature-dependence thermoelectric power studies of mixed


NiCu nano ferrites
Rapolu Sridhar a, D. Ravinder b,, K. Vijaya Kumar c
a

Vignans Institute of Technology & Aeronautical Engineering College, Deshmukhi, Nalgonda 508284, Telangana, India
Department of Physics, Osmania University, Hyderabad 50001, Telangana, India
c
Department of Physics, JNTU Hyderabad College of Engineering, Nachupally (Kondagattu), Karimnagar 505501, Telangana, India
b

a r t i c l e

i n f o

Article history:
Received 1 April 2015
Received in revised form 5 May 2015
Accepted 7 May 2015
Available online 14 May 2015
Keywords:
NiCu nano ferrite
X-rd
TEM
FTIR spectra
Thermoelectric power
Charge carrier concentration

a b s t r a c t
Synthesized NiCu nano ferrites with the compositional formula Ni1xCuxFe2O4 (x = 0.0, 0.2, 0.4, 0.5, 0.6,
0.8 and 1.0) were prepared by the citrate-gel auto combustion technique. The prepared samples were
characterized using X-ray difractrograms (XRD), Transmission electron microscope (TEM) and Fourier
transforms infrared (FTIR). The X-ray difractrograms (XRD) clearly exhibited the existence of single phase
cubic spinel structure and the crystallite size was found in the range of 3658 nm. TEM micrographs
indicated the nanostructure nature with platelet shape. FTIR absorption spectra revealed the presence
of two signicant absorption bands m1 and m2 around 580 cm1 and 410 cm1 characteristic of spinel
ferrite. This conrms the formation of single phase spinel structure with two sub-lattices tetrahedral
(A) site and octahedral (B) site. The thermoelectric properties were carried out by the differential method
from room temperature to well beyond the transition temperature. The seebeck coefcient is negative for
all the compositions showing that these ferrites behave as n-type semiconductors. The transition
temperature determined from thermoelectric power studies, it was found that the transition temperature
decreases with increase of Cu concentration. The values of the charge carrier concentration and charge
carrier mobility have been computed from the observed values of the seebeck coefcient. The
temperature variation of the seebeck coefcient and carrier concentration is also discussed. On the basis
of these results an explanation for the conduction mechanism in NiCu nano ferrites is suggested.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Hall effect and thermoelectric power studies are widely used in
the analysis of the conduction mechanism in semiconductors.
Ferrites having low resistivity and low eddy current losses have
been found to be the most versatile to be used for technological
applications and these are low mobility semiconductors. In the
case of low mobility semiconductors such as ferrites, it is sometimes difcult to measure the Hall effect, hence to know about
the conduction mechanism in ferrites thermoelectric measurements is the only alternative [1]. The thermo e.m.f. and its sign
gives suitable information about the type of conduction in semiconductors, i.e., they are p-type or n-type. Thermoelectric effect
is the direct conversion of temperature differences to electric voltage and vice versa, and it can be used to generate electricity, measure temperature or change the temperature of objects.
Thermoelectric devices can be used as temperature controllers
Corresponding author. Tel.: +91 9246162228.
E-mail address: [email protected] (D. Ravinder).
http://dx.doi.org/10.1016/j.jallcom.2015.05.041
0925-8388/ 2015 Elsevier B.V. All rights reserved.

because the direction of heating and cooling is determined by


the polarity of the applied voltage.
During the past 10 years there has been considerable interest in
nding new materials and structures for use in clear, highly
efcient cooling and energy conversion systems [25].
Nanostructural materials have signicant applications for the next
generation thermoelectric devices. While the thermal transport
properties of bulk materials have been intensely studied, the
understanding of nanostructure thermoelectric properties and
their interrelation is still incomplete.
Several researchers [6,7] studied the electrical and thermal
power of the spinel ferrites and have found that they have semiconducting properties of n or p-type. Nickel and copper substituted
nickel ferrites are the important class of spinel ferrites [8] and
these are the resourceful and scientically important soft ferrite
materials because of their typical ferromagnetic properties, low
conductivity and thus lower eddy current losses, high electrochemical stability, catalytic behavior, etc. [912]. NiCu nano
ferrites are low cost materials and have important magnetic and
electrical transport properties for technological applications.

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R. Sridhar et al. / Journal of Alloys and Compounds 645 (2015) 436442

The substitution of Cu brings about a structural phase transition


accompanied by the reduction in the crystal symmetry due to
co-operative JahnTeller effect [13,14], which ultimately modies
the properties of nickel ferrite which are useful in many device
applications. As per the present authors knowledge no information
is available on thermoelectric power studies of mixed NiCu nano
ferrites in the literature. Moreover, there is need for through study
of thermoelectric power studies of copper substituted nickel nano
ferrites as a function of composition and temperature. Therefore a
systematic study of the thermo electric power of the mixed NiCu
nano ferrite system from room temperature to well beyond Curie
temperature was undertaken. The results of such a study presented
in this communication are explained on the basis of the conduction
mechanism.
2. Experimental details
2.1. Materials preparation
The NiCu nano ferrite powders having the compositional formula
Ni1xCuxFe2O4 (where x = 0.0, 0.2, 0.4, 0.5, 0.6, 0.8 and 1.0) were synthesized by
citrate-gel auto combustion technique. Analytical grade raw materials (Nickel
Nitrate (Ni(NO3)26H2O), Copper Nitrate (Cu(NO3)23H2O), Ferric Nitrate
(Fe(NO3)29H2O), Citric AcidCitrate (C6H8O7H2O) and Ammonia (NH3)) were used
to prepare the specimens of the mixed NiCu nano ferrites. Prepared metal nitrate
solutions were mixed with citric acid solution in 1:3 M ratio of nitrate to citric acid
and dissolved in deionized water. The pH of the solution was adjusted to 7 using
ammonia. The solution was heated at 80 C to transform into gel and then ignited
in a self-propagating combustion manner to form a uffy loose powder. The
as-burnt ferrite powders were grained by agate motor then calcined at 700 C for
5 h. the calcined ferrite powders were again grained by agate motor. As this method
is a chemical route it requires no ball milling hence little scope of contamination,
and better homogeneity. The sintered powders were mixed with 2% of PVA as a binder and uniaxially pressed at a pressure of about 35 tons cm2 to form pellets of
10 mm diameter and 23 mm thickness. These pellets were nally sintered at
1050 C for 12 h in a programmable furnace. Silver paste was applied on both sides
of the samples to make good ohmic contact.

3. Results and discussion


3.1. X-rd analysis
Fig. 1 shows the X-ray diffraction pattern of mixed NiCu nano
ferrite system. It can be seen from the Fig. 1 that the crystalline
phases compared with PDF-4 reference data from the international
centre for diffraction data (ICDD). All Bragg reections have been
indexed and all planes are the allowed planes which indicate the
formation of cubic spinel structure in single phase [18]. The values
of the crystal size vary between 36.7 nm and 58.91 nm shown in
Table 1.
3.2. TEM & SEM analysis
Transmission electron microscope (TEM) micrographs of
NiFe2O4 and Ni0.2Cu0.8Fe2O4 samples are illustrated in Figs. 2a
and 2b. SEM micrographs of Ni0.4Cu0.6Fe2O4 and Ni0.5Cu0.5Fe2O4
samples are illustrated in Figs. 2c and 2d. The micrographs indicated the nanostructure nature with platelet shape and the crystallite size is in nanometer.
3.3. FTIR spectra analysis
The FTIR spectra of the Ni1xCuxFe2O4 (x = 0.0, 0.2, 0.4, 0.5,
0.6, 0.8, 1.0) synthesis by Citrate-gel auto combustion method are
shown in Fig. 3. The spectra of all the ferrites have been used to
locate the band positions which are given in Table 1. In the present
study the absorption bands m1 and m2 are found to be around
580 cm1 and 410 cm1 for all the compositions which arises due
to vibration of ions in the crystal lattices [19]. This reveals the

2.2. Measurements
The structural characterization was carried out using X-ray Diffractometer
Bruker (Karlsruhe, Germany) D8 advanced system with a diffracted beam
monochromatic Cu Ka radiation (k = 1.5405 ) source between the Bragg angles
2080 in steps of 0.04/sec. Microstructure of the calcined nanocrystalline ferrite
system has been characterized by Transmission Electron Microscope (TEM,
Tecnai-12, FEI, Netherlands). The FTIR absorption spectra of synthesized
nano-ferrite powders were recorded at room temperature by Fourier Transform
Infrared Spectroscopy (Spectrum 100, Perkin Elmer, USA) in the range of 350
4000 cm1 with a resolution of 1 cm1 using KBr pellet method.
Thermo electric power measurements were made as a function of composition
and temperature by the differential method [15,16] from room temperature to well
beyond the transition temperature. The experimental arrangement with the sample
holder consists of 2 pairs of non magnetic copper electrodes among which the sample is xed to the upper electrode for additional heating to keep a temperature difference about 10 C between the 2 faces of the sample. The temperature of both
surfaces of the sample was calculated by using the relation.
Thermo electric power S = DE/DT
where DE is the thermo emf produced across the sample

Fig. 1. X-ray diffraction pattern of mixed Ni1xCuxFe2O4 nano ferrites.

DT is the temperature difference.


The charge carrier concentration was calculated using formula given by Morin
and Gebella [17].
Density of charge carriers n = NA exp (Se/K)
where NA is the density of states (NA = 1022 cm3)
S is Seebeck coefcient
e is charge of electron (1.6  1019 Coulombs)
K is Boltzmann constant (1.38  1023 Joule/Kelvin).
From the experimental values of the electrical conductivity (r) and carrier concentration (n), charge carrier mobility (l) was calculated by using the relation.
Charge carrier mobility l = r/ne
where e is the charge of electron.

Table 1
Crystallite size and FTIR parameters of mixed NiCu nano ferrites.
Sl. no.

1
2
3
4
5
6
7

Composition

Ni Fe2 O4
Ni0.8Cu0.2 Fe2 O4
Ni0.6 Cu0.4 Fe2 O4
Ni0.5 Cu0.5Fe2 O4
Ni0.4 Cu0.6Fe2 O4
Ni0.2 Cu0.8Fe2 O4
Cu Fe2 O4

Crystallite size (nm)

58.91
46.3
49.2
37.3
36.9
43.3
36.7

FTIR parameters

m1 (cm1)

m2 (cm2)

569.83
572.23
574.42
577.45
577.04
581.56
584.24

414.19
411.28
408.55
404.69
407.21
409.43
404.89

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R. Sridhar et al. / Journal of Alloys and Compounds 645 (2015) 436442

Fig. 2d. SEM images of Ni0.5Cu0.5Fe2O4 nano ferrite.


Fig. 2a. TEM image of NiFe2O4 nano ferrite.

Fig. 2b. TEM images of Ni0.2Cu0.8Fe2O4 nano ferrite.

Fig. 3. FTIR patterns of mixed Ni1xCuxFe2O4 nano ferrites.

to stretching vibration mode of Fe+3O2 in tetrahedral A-site,


while the low frequency band (m2) corresponds to Me+2O2 vibrations in octahedral sites. The variation in the band positions is due
to the difference in the Fe+3O2distances for the octahedral and
tetrahedral complexes [21].
3.4. Composition dependence of seebeck coefcient (S)

Fig. 2c. SEM images of Ni0.4Cu0.6Fe2O4 nano ferrite.

formation of single-phase spinel structure having two sub-lattices


tetrahedral (A) site and octahedral (B) site [20]. There is no absorption band in spectra for all samples above frequency bands
600 cm1. This is due to complete elimination of water content
and amorphous nature. The high frequency band (m1) corresponds

The values of the seebeck coefcient of all mixed NiCu nano


ferrites at room temperature were calculated from the observed
values of the thermo emf and are given in Table 2. It can be
seen from the Table 2 that the value of seebeck coefcient is
negative, indicating the majority charge carriers are electrons
hence the predominant conduction mechanism in these ferrites
is of n-type semiconductors. The seebeck coefcient value vary
from 150 lV/K to 40 lV/K as the copper content increases
in nickel nano ferrite as shown in Fig. 4. Similar behavior of
variation of seebeck coefcient with composition was observed
in NiMg ferrites [22]. The decrease in seebeck coefcient with
Cu concentration explained by hopping mechanism between
Fe2+ and Fe3+ ions [23].

Fe3 e ! Fe2

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R. Sridhar et al. / Journal of Alloys and Compounds 645 (2015) 436442


Table 2
Thermoelectric power data of mixed NiCu nano ferrites.
Sl. no.

Composition

Seebeck coefcient
(S) (lV/K)

Charge carrier
concentration (n) (1022/m3)

Charge carrier
mobility (l) (cm2/V s)

1
2
3
4
5
6
7

Ni Fe2 O4
Ni0.8Cu0.2 Fe2O4
Ni0.6Cu0.4 Fe2O4
Ni0.5Cu0.5Fe2O4
Ni0.4Cu0.6Fe2O4
Ni0.2Cu0.8Fe2O4
Cu Fe2 O4

150
130
110
100
60
50
40

11.902
11.629
11.362
11.231
10.721
10.598
10.475

4.2175  1009
2.8358  1008
3.5024  1008
3.7437  1008
4.7037  1008
1.1914  1007
2.8095  1007

Transition
temperature (K)

Curie temp (K)

TS

Tn

Tq

Tg

795.40
750.54
730.89
689.45
680.60
664.80
645.46

798.25
747.60
737.44
693.70
678.49
668.56
639.72

812.08
738.22
730.19
688.42
676.59
665.42
646.20

808
736
726
686
674
668
648

[28], thereby indicating that the change in the behavior of the


thermoelectric power with temperature may be due to magnetic
transition, where the material becomes the paramagnetic. Thus,
it is clear that incase of NiCu nano ferrites the thermoelectric
power is exhibiting a clear-cut and well-dened transition at the
Curie temperature. The value of thermoelectric power is maximum
at Ts (Kelvin). This clearly indicates that the magnetic ordering has
a marked inuence on the thermoelectric property of these ferrite
samples.
3.6. Composition dependence of the charge carrier concentration (n)
and the charge carrier mobility (l)

Fig. 4. Seebeck coefcient variation with composition.

3.5. Temperature dependence of the thermoelectric power (S)


Fig. 5(a)(g) shows the variation of the thermoelectric power(S)
of the Ni1xCuxFe2O4 (x = 0.0, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0) nano ferrites
with temperature. It can be seen that the value of thermoelectric
power for all mixed NiCu nano ferrites increases with increasing
temperature up to a certain temperature, which is designed as
transition temperature Ts (Kelvin). However, beyond this temperature the value of S starts decreasing with increasing temperature
and the thermoelectric power found as negative for entire temperature range as been investigated. A similar variation of thermoelectric power with temperature was observed [2426].
The seebeck coefcient variation with temperature can be
explained as, the hot surface of the material becomes positively
charged, as it loses some of its electrons. The cold surface of the
material becomes negatively charged due to the diffusion of free
electrons from the hot portion. On increasing the temperature,
the conduction mechanism becomes more probable that generates
electrons Fe2+ , Fe3+ + e. These electrons accumulate on the cold
portion, as a result, thermo emf increases hence, increases the
seebeck coefcient. After the transition temperature decrease in
seebeck coefcient may be due to lling up of oxygen vacancies
and migration of ions from one site to other thereby reducing the
concentration of mobile electrons [27].
The seebeck coefcient transition temperature Ts (Kelvin)
values for each composition are listed in Table 2. Fig. 6 shows
the variation of seebeck coefcient transition temperature with
composition. The measured transition temperature Ts (Kelvin) are
close and good agreement with curie temperature Tc (Kelvin) values from dc resistivity and loria technique which are reported

The computed values of charge carrier concentration and the


charge carrier mobility values for the different composition of
mixed NiCu nano ferrites are included in Table 2. It can be seen
that the value of the carrier concentration vary from
11.902  1022 to 10.475  1022 m3 and the charge carrier mobility
vary from 4.2175  1009 to 2.8095  1007 cm2/V s. Such low values of mobility have been reported by several researches [29,30].
Among all the mixed NiCu nano ferrites, the specimen with the
NiFe2O4 exhibits height value of seebeck coefcient and charge carrier concentration. It can also be seen from the Table 2 that the
value of charge carrier mobility increases with the increases Cu
concentration. Fig. 7 shows the variation of charge carrier concentration and charge carrier mobility with composition.
3.7. Temperature variation of the charge carrier concentration (n)
The temperature dependent charge carrier concentration is
shown in Fig. 8. It can be seen from the gure that the charge carrier concentration increases with increase in temperature up to a
certain temperature, which is designed as Tn (Kelvin). However,
beyond this temperature the value of charge carrier concentration
starts decreasing with increasing temperature for all the ferrites. It
can be seen from Table 2 the values of transition temperature are
by different technique are in good agreement obtained. Similar
variations of Tn and Tc were also observed by other researchers
[31,32].
4. Conclusions
Homogeneous and reactive nanostructured NiCu nano ferrites
were prepared by citrate-gel auto combustion method. X-ray
diffraction patterns shows the formation of the single phased cubic
spinel structure without any impurity peak and crystallite size vary
in the range of 3658 nm are obtained. TEM micrographs indicated
the nanostructure nature with platelet shape. FTIR absorption
spectra revealed the presence of two signicant absorption bands
m1 and m2 around 580 cm1 and 410 cm1 characteristic of spinel
ferrite, this conrms the formation of single phase spinel structure

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R. Sridhar et al. / Journal of Alloys and Compounds 645 (2015) 436442

Fig. 5. (ag) Temperature dependence thermoelectric power of mixed NiCu nano ferrites.

R. Sridhar et al. / Journal of Alloys and Compounds 645 (2015) 436442

441

charge carrier mobility increases with the increases Cu concentration. The values of transition temperature are by different technique are in good agreement obtained.
Acknowledgements
One of the authors (D.R.) is grateful to Prof. Sayanna, Head of
the department for his encouragement to carry out this research
work. One of the authors (R.S.) is grateful to Prof. N.
Venkateswarlu, principal, Vignans Institute of Technology &
Aeronautical Engineering College, Hyderabad. The author (K.V.K.)
is grateful to Dr. M. Thirumala Chary, Principal, Professor & HOD
of Chemistry, JNTUH College of Engineering, Nachupally,
Karimnagar (Dist).
Fig. 6. Seebeck and carrier concentration transition temperature variation with
composition.

Fig. 7. Charge carrier concentration and charge carrier mobility variation with
composition.

Fig. 8. Temperature dependent charge carrier concentration of Ni1xCuxFe2O4 nano


ferrites.

with two sub-lattices tetrahedral (A) site and octahedral (B) site. In
the present investigation NiCu nano ferrites are classied as
n-type semiconductors. The decrease in seebeck coefcient was
due to increase in resistivity for that particular composition.
Among all the nano ferrites the NiFe2O4 exhibits height value of
seebeck coefcient and charge carrier concentration. The value of

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