Journal of Alloys and Compounds 633 (2015) 104114

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Journal of Alloys and Compounds

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

Structural, magnetic and dielectric studies of copper substituted

nano-crystalline spinel magnesium zinc ferrite
H.M. Zaki a,b,, S.H. Al-Heniti a, T.A. Elmosalami b
a
b

Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia
Department of Physics, Faculty of Science, Zagazig University, Zagazig, Egypt

a r t i c l e

i n f o

Article history:
Received 30 November 2014
Received in revised form 27 January 2015
Accepted 30 January 2015
Available online 7 February 2015
Keywords:
Nanostructures
Co-precipitation
X-ray diffraction
Infrared spectroscopy
Magnetic properties

a b s t r a c t
Nano-crystalline Mg0.5Zn0.5xCuxFe2O4 (x = 0.0, 0.1, 0.2, 0.3, 0.4 and 0.5) ferrite powders were synthesized
using co-precipitation method. The inuence of Cu2+ ions substitution on the structural and magnetic
properties was investigated. X-ray diffraction measurements revealed the formation of nano-crystalline
ferrite with single cubic spinel phase. The lattice constant was found to decrease with increasing Cu2+
ions content. Infrared spectral analysis conrmed formation of the spinel structure for the respective
ferrite system. Magnetic data showed that the saturation magnetization (Ms) increases with Cu2+ concentration up to x = 0.2 and then decreases with further increase of Cu2+ ions in this ferrite system. The
proposed cation distribution deduced from X-ray diffraction, infrared spectra and magnetization data
indicated mixed ferrite type. Dielectric constants e0 , dielectric loss e0 0 , dielectric loss tangent tan d and
ac conductivity, rac, were investigated as a function of frequency and temperature. Inuence of Cu2+ substation on the ac conductivity exhibited signicant behavior at low frequencies and low temperatures,
T 6 100 C. Both dielectric constants (e0 , e00 ) found to increase with the increase of the temperature. At
low temperatures, dielectric loss tan d indicated a decrease with frequency with slight change at high
temperatures.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Nano-sized spinel-type ferrites having formula MFe2O4 structure (where M is a divalent metal cation) are promising materials
due to their interesting magnetic and electric properties with
chemical and thermal stabilities [1]. The structure of spinel ferrites
consists of a closed-packed oxygen arrangement in which 32 oxygen ions are packed in a unit cell and between the layers of oxygen
ions exist interstices which can be classied into two categories,
tetrahedral (A-site) and octahedral (B-site), depending on the coordination of the nearest neighboring oxygen. Ferrite materials are
used in many applications such as electronics, magnetic storage
and as contrast agents in magnetic resonance imaging (MRI) [2].
Much attention has been focused on Mg-ferrite due to its high electrical resistivity and porosity [35]. Moreover, Mg may increase the
sequences of the magnetic hysteresis, so it can be used as a diamagnetic dopant in ferrites. In sensors technology, Mg ferrite
was used as humidity sensor as reported by Shimizu et al. [6].
Corresponding author at: Department of Physics, Faculty of Science, King
Abdulaziz University, Jeddah, Saudi Arabia; Department of Physics, Faculty of
Science, Zagazig University, Zagazig, Egypt.
E-mail addresses: dakdik2001@yahoo.com, hmzaki@kau.edu.sa (H.M. Zaki).
http://dx.doi.org/10.1016/j.jallcom.2015.01.304
0925-8388/ 2015 Elsevier B.V. All rights reserved.

For example, one of the main factors which candidate Mg ferrite

in microwave applications is its very high specic resistance
(1081010 X cm) [7]. Doped Mg-ferrites particularly that containing divalent ions such as Zn2+ have conrmed to be among the best
alternatives to conventional materials used in particular applications such as switches, tiny inductors, antenna rods and recording
heads owing to their distinctive properties [8]. It has been concluded that addition of Cu2+ ions may improve the resistivity,
dielectric and magnetic properties of MgZn ferrites. Magnesium
ferrite, containing range of compositions is often used in order to
obtain highly dense and resistive ferrites [9,10]. Copper ferrite
doped with magnesium ions, is important spinel family member
[11,12]. Un-doped and substituted MgCuFe2O4 is a well-suited
materials for high frequency applications in the telecommunication eld due to their high resistivity and low eddy current losses.
They are used in radio frequency circuits, high quality lters, transformer cores and read/write heads for high-speed digital tapes
[13]. Recently there is a growing interest in using MgZn ferrites
in electronic devices instead of NiZn ferrites because of the
carcinogenic effects of nickel and their potential and environmental hazards, although they posses high permeability and high resistivity at higher frequencies [14]. MgCuZn ferrite has been
considered as an alternate system due to its high resistivity, high

H.M. Zaki et al. / Journal of Alloys and Compounds 633 (2015) 104114

Curie temperature and environmental stability [15]. In addition,

multilayer chip inductors (MLCIs) based on this ferrite system have
been developed for promising electronic applications. Such devices
are fabricated by laminating alternate layers of ferrite and conductors which then co-ring to form the monolithic structure appropriate for multilayer chip inductor applications (MLCIs) [16,17].
Metallic silver is usually used as the internal electrode material
of MLCIs due to its high conductivity and low cost. Silver as an
internal conductor has a melting point of 961 C. Consequently,
the ferrite powder is sintered at T < 961 C in order to co-re with
silver electrodes. Since the magneto-striction constant of MgCu
Zn ferrite is lower than that of NiCuZn ferrite, MLCI using
MgCuZn ferrite can provide better magnetic properties. Technologically, NiCuZn ferrite is preferred as magnetic material for
MLCIs because of its better properties at high frequencies and
lower densication temperatures [18,19]. In comparison, MgCu
Zn ferrites have similar magnetic properties as NiCuZn ferrites
with the advantage that the former is more economical [20] and
easy to synthesize. Murbe et al. [21] investigated MgCuZn ferrites for obtaining low sintering temperature, high permeability
and high thermal stability as multilayer chip inductor materials
alternative to the NiCuZn ferrite system. The study found that
MgCuZn ferrite is promising material for MLCIs applications
with high-performance and low cost.
This study describes the inuence of Cu2+ ions substitution in
place of Zn ions on the structural, dielectric and magnetic properties
of Mg0.5Zn0.5xCuxFe2O4 ferrites synthesized by co-precipitation
method. In addition, the inuence of cation redistribution between
the tetrahedral and octahedral sites on the structural and magnetic
properties of Cu-doped MgZn ferrites is also investigated.

105

nano-powder was washed several times with distilled water to remove impurities
and then dried at 85 C for 5 h. After drying, the powders were calcined at 900 C in
a programmable thermolyne furnace for 5 h to obtain a single spinel cubic phase. Xray powder diffraction patterns were scanned using Philips Xpert diffractometer
equipped with a graphite crystal monochromator and Copper target
(kka1 = 1.54056 ). The working conditions for the X-ray tube were 40 kV and
25 mA. Each X-ray scan was performed between 15 and 70 (2h). Fourier transform infrared spectra were measured by means of PerkinElmer spectrophotometer
model 1430 within the wave number range of 3501000 cm1 using KBr pressed
pellet technique. Magnetization measurements were performed at room temperature using vibrating sample magnetometer (Lake Shore 7400 series) with sensitivity
of 107 emu at the magnetic eld range 20 to 20 kG.
In the present study, ac conductivity and dielectric parameters were carried out
in the frequency range from 100 Hz to 1 MHz at the temperature range between
300 K and 673 K using LCR HI-Tester (HIOKI 3532-50). The pelletized samples with
diameter 12 mm and thickness of 4 mm were coated on both faces with silver paste
in order to form parallel plate capacitor.
The value of the real dielectric constant (e0 ) was calculated using the following
relation:

e0 Cd=Aeo ;

where C, d and A refer to capacitance, thickness and cross sectional area of the pellet.
The symbol eo is the permittivity of free space.
The complex dielectric constant was calculated using the relation:

e00 e0 tan d;

where tan d is the dielectric loss. Using the dielectric constant and dielectric loss, the
ac conductivity rac of the prepared samples was calculated using the following
formula:

rac e0 e0 tan d;

where x is the angular frequency.

3. Results and discussion

3.1. X-ray diffraction

2. Experimental details
Nano-crystalline powders of Mg0.5Zn0.5xCuxFe2O4 (x = 0.0, 0.1, 0.2, 0.3, 0.4 and
0.5) were synthesized using co-precipitation method. Stoichiometric quantities of
analytical grade MgCl26H2O, ZnCl2, CuCl2, FeCl36H2O and NaOH were mixed thoroughly in 150 ml distilled water using magnetic stirrer at 80 C. The precipitated

Fig. 1 shows typical X-ray diffraction patterns for the

synthesized Cu2+ substituted MgZn ferrites with some traces of
a secondary phase of Fe2O3 (JCPDS le No. 87-1166) for the sample
with concentration x = 0.3. The appearance of such secondary

Fig. 1. X-ray diffraction patterns of nanocrystalline Mg0.5CuxZn0.5xFe2O4 ferrites powders synthesized by co-precipitation method.

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H.M. Zaki et al. / Journal of Alloys and Compounds 633 (2015) 104114

Table 1
Bulk density (dbulk), percentage porosity (p%), lattice constants (aexp, ath), ionic radii (rA, rB), bond lengths (RA, RB), oxygen parameter (U), deviation of oxygen parameter (d),
tetrahedral (mT) and octahedral (mO) infrared bands for Mg0.5Zn0.5xCuxFe2O4 nano-crystalline ferrites.
Concentration (x)

0.0

0.1

0.2

0.3

0.4

0.5

dbulk (g/cm3)
P (%)
rA ()
rB ()
ath ()
aexp ()
RA
RB
U
d
mT (cm1)
mO (cm1)

4.8108
2.1
0.9572
0.5264
8.4297
8.4167
2.278
1.883
0.406
0.031
572.2
396.2

4.838
1.7
0.8336
0.5872
8.4016
8.4097
2.154
1.927
0.398
0.023
584.1
437.8

4.8704
1.06
0.7100
0.6480
8.3734
8.4059
2.031
1.976
0.390
0.015
585.5
436.5

4.9114
0.79
0.5314
0.6633
8.3717
8.3896
1.856
2.068
0.378
0.003
576
435.1

4.6374
6.3
0.5318
0.6601
8.3699
8.3887
1.856
2.068
0.378
0.003
586.4
433.1

4.6649
6.0
0.5550
0.6569
8.3682
8.3790
1.870
2.059
0.379
0.004
588.1
430.2

phase has been reported for some ferrite compounds in literature

[22]. The indexed peaks with diffraction planes (1 1 1), (2 2 0),
(3 1 1), (2 2 2), (4 0 0), (4 2 2), (5 1 1), (4 4 0), (6 2 0) and (5 3 3) indicated the cubic crystal structure of the spinel phase with Fd-3m
space group (JCPDS 10-0325) for all concentrations of the investigated ferrites. Values of the lattice constant were determined for
Mg0.5Zn0.5xCuxFe2O4 ferrites and are listed in Table 1. The deduced
lattice constant decreases with increasing Cu2+ ion substitution, a
similar behavior was reported by Bhosale et al. using oxalate precursors [23] and Sujatha et al. Studied Mg0.5Cu0.05Zn0.45Fe2O4
nanoparticles through solgel method got a nearly lattice constant
[24]. This behavior is attributed to the difference of the ionic radius
between Cu2+ ion (0.72 ) and that of Zn2+ ion (0.74 ) [25]. Consequentially, the substitution of Cu2+ ions in place of Zn2+ ions is
expected to decrease the lattice parameter of the unit cell. The Xray density (dx) of the compounds was determined using the
relation [26]:

ZM
dx
NA a3

where M is the molecular weight, Z is the number of molecules per

unit cell (Z = 8), NA is Avogadros number and a is the lattice constant of the unit cell. The X-ray density (dx) found to increase with
increasing Cu2+ concentration due to the decrease of the lattice constant as shown in Table 1. The porosity (P) of the samples was calculated using the following relation [27]:


P 1

dbulk
dx

Table 2
Particle size (D), surface area (S), magnetic moments (lth, lexp), saturation magnetization (Ms), coercivity (Hc) and remanence magnetization (Mr) for Mg0.5Zn0.5xCuxFe2O4 nano-crystalline ferrites.
Composition (x)

0.0

0.1

0.2

0.3

0.4

0.5

D (nm)
S (m2/g)
lth (lB)
lexp (lB)
Ms (emu/g)
Hc (G)
Mr (G)
Ms/Mr

51
24.46
1.50
1.794
45.424
33.612
3.2178
0.071

62
20.00
2.58
2.075
52.589
27.305
2.7598
0.053

45
27.38
3.66
2.197
55.722
22.153
2.0322
0.037

25
48.87
2.95
1.925
48.867
41.056
3.6258
0.074

76
17.02
1.95
1.747
44.398
32.273
2.8799
0.065

67
19.20
0.95
1.194
30.361
45.989
3.7240
0.123

2
2
2
3
2
3
2
Mg2
0:05y Zn0:5x Fe0:4x Cut Mg0:45y Cuxt Fe1:6xz Fez O4 ;

0:3 6 x 6 0:5
The average cation radius at the tetrahedral and octahedral
sites, rA and rB, are calculated for all samples using the above cation
distributions and given as [30]:

rA 0:05 y  rMg 0:5  x  r Zn 0:85  x  r Fe t  r Cu ;

0:0 6 x 6 0:2
0:05  y  rMg 0:5  x  r Zn 0:4 x  rFe t  r Cu ;
0:3 6 x 6 0:5


5

where dbulk is the bulk density, which was measured using the
Archimedes principle. The percentage porosity P (%) of the samples
decreases gradually with concentration up to x 6 0.3 indicating
dense packing. Samples with concentration x = 0.4 and x = 0.5 exhibit higher percentage porosity around 6% which may attributed to
the increase of their particle sizes as indicated in Table 2. This
dependence between porosity and particles size has been reported
for some ferrites [28].
In Mg0.5Zn0.5xCuxFe2O4 ferrites the Zn2+ ions exclusively
occupy the tetrahedral (A) sites, while most of the Mg2+ and Cu2+
ions prefer to occupy the octahedral sites (B). The Fe3+ ions are distributed among the tetrahedral and octahedral sites. Furthermore,
substitution of sufcient amount of Cu2+ ions may cause migration
of Fe3+ ions from (B) site to (A) site because the preferency of copper ions to be in the octahedral sites (B-sites) [29]. Considering the
X-ray, infrared and magnetization data the most reliable cation
distribution for the studied ferrites are given as:
2
2
2
3
2
3
Mg2
0:05y Zn0:5x Fe0:85x Cut Mg0:45y Cuxt Fe1:15x O4 ;

0:0 6 x 6 0:2

rB 1=20:45  y  r Mg x  t  r Cu 1:15 x  r Fe ;
0:0 6 x 6 0:2
1=20:45 y  r Mg x  t  r Cu 1:6  x  z  rFe zr Fe2 ;
0:3 6 x 6 0:5
where rMg, rZn, rFe and rCu are the ionic radii of Mg, Zn, Fe and Cu
ions, respectively. Table 1 shows the calculated structural parameters ath, rA and rB based on the proposed cation distributions. The
theoretical lattice parameter (ath) is calculated using the relation
given below, which relates the cation radius of the constituent elements to the lattice parameter at different lattice sites [31]:

p
8
ath p r A Ro 3r B Ro 
3 3

where rA and rB are the cations radii at the tetrahedral and octahedral sites, respectively and Ro is the oxygen ion radius (Ro = 1.32 )
[17]. The calculated and experimental values of the lattice parameters (ath, aexp) are given in Table 1. The value of ath vary linearly with
increasing Cu2+ concentration for all the samples. The data in Table 1
shows that the value of ath is slightly different from the experimental
value aexp. This small difference is attributed to the approximation

H.M. Zaki et al. / Journal of Alloys and Compounds 633 (2015) 104114

107

Fig. 2. Room temperature FTIR spectra of nanocrystalline Mg0.5CuxZn0.5xFe2O4 (0 6 x 6 1.0) ferrites.

Moment/Mass (emu/g)

X=0.0
X=0.1
X=0.2
X=0.3
X=0.4
X=0.5

the metallic ions, and in spinel like structures. The oxygen positional parameter has a value in the neighborhood of 0.375 for which
the arrangement of O2 ions equals exactly a cubic closed packing.
However, in actual spinel lattice this ideal pattern is slightly
deformed. The higher values of oxygen parameter obtained in this
study may be attributed to the small displacement of anions due
to the expansion of the tetrahedral interstices and the difference
in the chemical composition [34,35]. It is obvious from the data in
Table 1 that the oxygen position parameter decreases with increasing Cu2+ concentration up to x = 0.3 which causes decrease in lattice
parameter in this range as obtained from X-ray results.
The cationanion distances (the bond lengths) at the A-sites, RA,
and B-sites, RB, are calculated using the following relations [35]:

60

-60

-20000

-10000


p
1
RA a 3 d
8
0

10000


12
1
d
RB a
 3d2
16 2

20000

Field (G)
Fig. 3. Room temperature magnetic hysteresis loops for Mg0.5CuxZn0.5-xFe2O4
ferrites.

in the calculations of ath which assumes ideal unit cell of close

packed spinel structure where the anions and cations are regarded
as rigid spheres in perfect manner [32]. Using the values of both
experimental and theoretical lattice parameters, oxygen positional
parameter is calculated using the following relation [33]:

1
1
U p r A RO
4
a 3

where the symbols have their usual meaning. The calculated values
of the oxygen positional parameter are listed in Table 1. In most oxidic spinels, the oxygen ionic radius is apparently larger than that of

d U  U ideal
where d represents the deviation from the ideal oxygen parameter
Uideal (=0.375). Values of (U) for Mg1xZnxFe2O4 samples were found
by interpolation between those reported earlier for pure magnesium and zinc ferrites, which are 0.381 and 0.385 A, respectively
[36].
Table 1 also shows the variation of bond lengths RA and RB with
Cu2+ content. RA is the shortest distance between A-site cation and
oxygen ion and RB is the shortest distance between B-site cation
and oxygen ion. It is well known that there is a correlation between
ionic radius and lattice parameter. The data in Table 1 indicate that
with increasing Cu2+ concentration, radius of tetrahedral site is
decreased. The decrease in bond length RA can be attributed to
the decrease in lattice parameter (a) with increasing of Cu2+

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H.M. Zaki et al. / Journal of Alloys and Compounds 633 (2015) 104114

Fig. 4. Variation of the saturation magnetization (Ms) and X-ray diffraction

intensity ratios.

content due to the fact that the ionic radius of Cu2+ is smaller than
Zn constituent ions that it replaces.
3.2. Infrared spectroscopy
The formation of Mg0.5CuxZn0.5xFe2O4 (0 6 x 6 1.0) ferrites
were conrmed by Fourier transforms infrared spectroscopy (FTIR)
through the existence of characteristic vibrational bands of the tetrahedral (A) and octahedral (B) sites. According to Waldron [37]
there are four bands characterizing ferrites which can be easily
observed in the range of 200700 cm1. The difference in positions
of the bands for the various compositions was expected because of
the difference in the distances for the octahedral and tetrahedral
ions [38]. The four bands can be classied into two groups as
two high-frequency bands and two low-frequency bands. Waldron
attributed the higher absorption band, mT, around 600 cm1 to the
intrinsic vibrations of tetrahedral complexes and the band, mO,
around 400 cm1 to octahedral complexes. The low-frequency
band around 350 cm1 is related to the divalent octahedral
metaloxygen ion complexes while the band around 200 cm1 is
assigned to the divalent tetrahedral vibrations [39,40]. In our case
the low band around 200 cm1 is not observed due to the limited
range of the available spectrometer. It is well known that in ferrites, metal cations are situated according to the geometric conguration of the oxygen ion nearest neighbors in two different sub
lattices such as tetrahedral (A-sites) and octahedral sites (B-sites)
[41]. The band mT is assigned to the vibration of the bond between
the oxygen ion and the tetrahedral metal ion OMtetra and the band
mO is assigned to the vibration of the bond between the oxygen ion
and the octahedral metal ion OMocta [42]. The difference in band
positions is due to change in bond length of Fe3+O2 at tetrahedral
(0.189 nm) and octahedral (0.199 nm) sites respectively [43].
Generally, vibrational frequencies depend on cation mass, cationoxygen distance and the bonding force [44]. The frequencies of
the IR absorption bands and the assignment of these bands corresponding to the studied ferrite samples are shown in Fig. 2.
Fig. 2 exhibits two strong frequency bands (mT, mO) in all the
samples within the measured range 580 and 430 cm1 as the
characteristics bands for the spinel structure conrming the ferrite
structure, where Kamble et al. [45] reported the synthesis of
MgCuZn ferrite (Mg0.48Cu0.12Zn0.40Fe2O4) by ceramic and selfsustaining auto-combustion (sucrose) methods and IR absorption
bands were found to be in the expected high frequency range
(574.95 cm1 and 582.39 cm1) and low frequency range
(431 cm1) which forties the spinel phase and coincide with our

results. The positions of these bands are presented in Table 1 and

found to change slightly from one ferrite composition to another.
This suggests that the preparation method, particle size, substitution with different ions and porosity play an important role in
inuencing the band positions. For example, in the present study
it is observed that there is a small shift in the frequency band mT
and mO for the ferrite samples after substituting with copper ions.
The frequency is inversely proportional to reduced mass and
bond length. According to the IR spectra, it is found that the
frequency band mo shifts towards higher wave number as Cu2+ ions
substituted at concentration (x = 0.1). This may be due to the large
radius of Cu2+ ions (0.72 ) occupying octahedral sites to that of
Fe3+ ions with radius (0.64 ). As a result, Fe3+ ions are pushed
towards oxygen ion resulting in reduced Fe3+O2 bond length.
There is an inverse relation between wave number and bond
length which produces slight change in the size of octahedron
and eventually a shift in mo band position is observed. In addition,
the migration of some Cu2+ ions to tetrahedral sites as observed
from IR spectra would increase the values of mT with increase of
Cu2+ concentration. The slight increase of both mT and mo with
increasing Cu2+ could also be due to the difference in the ionic
radius between Cu2+ and Zn2+ and the difference of their masses
in both sites. This increase in frequency bands (mo and mT) are consistent with the reduction in unit cell dimensions [46]. A similar
shift in peak positions was found with the increasing Cu2+ concentration has also been reported [47]. This behavior was attributed to
preparation conditions which affect the grain size and density.
3.3. Magnetization
Room temperature magnetization hysteresis curves of the samples calcined at 900 C (Fig. 3) show that the saturation magnetization is achieved at a eld of 20 kG. From the gure it is also clear
that, all the curves of different compositions produced narrow
loops, with a behavior characteristic of soft magnetic materials
(easy magnetization and demagnetization with low coercivity
implied reduced hysteresis losses in the present samples which
is an important requirement for a good electromagnet). The values
of saturation magnetization (Ms), coercivity (Hc), remanent magnetization (Mr) and magnetic moment (lB) are listed in Table 2. Fig. 3
shows plots of the saturation magnetization (Ms) as a function of
copper content. It is clear that, the saturation magnetization
increases linearly with increasing copper concentration up to
x = 0.2 followed by a remarkable decrease. The observed variation
in saturation magnetization can be explained on the basis of cation
distribution and the exchange interactions between A and B-sites,
respectively. The AB interaction is known to be the strongest and
dominates over the BB and AA interactions. According to Neels
two sub lattice model of ferri-magnetism [48] saturation magnetization is given by MS = MBMA in which MB and MA are the octahedral and tetrahedral sub lattice magnetizations, respectively. The
initial increase in the MS value is attributed to the fact that Cu2+
ions with magnetic moment of 1 lB preferentially tend to migrate
to the B-sites by replacing non magnetic Zn2+ ions with zero lB
which have a stronger preference for the tetrahedral (A) site. Thus,
Zn2+ displaces Fe3+ from A to B site and the increase of Cu2+ ions in
B-sites would increase the magnetization of these sub lattice sites.
As the magnetic spin of neighboring A and B-sites are anti-ferromagnetically coupled (due to the super exchange interaction in ferrite lattice), the net result is an increase in magnetic moment on
the B sub-lattice, and thus the net magnetic moment of the spinel
ferrite increases with Cu2+ concentration up to x = 0.2 as shown
from Fig. 4. The infrared spectrum of samples with composition
x = 0.3 to x = 0.5 clearly indicates the presence of Fe ions in its divalent state (Fe2+) beside the trivalent state (Fe3+). So the existence of
Fe2+ ions in B-sites will reduce the magnetization of these samples.

109

H.M. Zaki et al. / Journal of Alloys and Compounds 633 (2015) 104114

-2.0
-2.5
-3.0

x=0.3

log (-1m-1)

log (-1m-1)

-3.5
-4.0
-4.5

x=0.0

-5.0
RT
o
100 C
o
200 C
o
300 C
o
400 C

-5.5
-6.0
-6.5

-2

-4
RT
o
100 C
o
200 C
o
300 C
o
400 C

-7.0
-6
2

log (Hz)

log (Hz)
0

x=0.1

x=0.4

-2

log (-1m-1)

log (-1m-1)

-2

-4

RT
o
100 C
o
200 C
o
300 C
o
400 C

-6

-4

RT
o
100 C
o
200 C
o
300 C
o
400 C

-6

-8
2

log (Hz)

log (Hz)
0

-2

-1
-2

x=0.2

log (-1m-1)

log (-1m-1)

-3

-4

-5

RT
o
100 C
o
200 C
o
300 C
o
400 C

-6

x=0.5

-3
-4
RT
o
100 C
o
200 C
o
300 C
o
400 C

-5
-6

-7
-7
2

log (Hz)

log (Hz)

Fig. 5a. The frequency dependence of the ac conductivity at selected temperature for the Mg0.5CuxZn0.5xFe2O4 ferrites.

The continuous decrease in magnetization for these samples would

reect the increase of the occupation of Fe2+ ions of B-sites for samples with x = 0.3 up to x = 0.5. Further, the migration of Mg2+ to A
sites, accompanied with migration of Fe3+ ions to B-sites will lead
to an increase in magnetization in B-sites up to x = 0.2 and hence to
the increase of the saturation magnetization of the MgCuZn
ferrite. Moreover, the rate of increase in magnetization with concentration (x) shows a decline which indicates an increase of Fe3+
in A-site with increasing Cu2+ ions conrming the validity of the
proposed cation distribution for x > 0.2. The decrease in Ms for
x P 0.30 may be also explained assuming the cation redistribution
in which Cu2+ ion can force some of Fe3+ ions to migrate from B-site

to A-site. Moreover, the creation of some Fe2+ with lower magnetic

moment (4 lB) will result in reduced magnetization of B sites and
consequently the net magnetization of the samples. However, Mg2+
can also migrate from B-sites to A-sites depending upon heat treatment as discussed in the cation distribution of the studied ferrites
in section one. One can conclude that the saturation magnetization
of the investigated samples by this technique is better than that
reported by other ceramic technique [45,49] and auto-combustion
route [50]. That mean the used method (co-precipitation) has ability of improving the ferrite with higher saturation magnetization
with low sintering time which make this ferrite important over a
wide range of frequency.

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H.M. Zaki et al. / Journal of Alloys and Compounds 633 (2015) 104114

1.0

log x show straight lines with different slopes at high-range of frequency and low temperature (i.e., for T 6 100 C) whereas for
T > 100 C the behavior of the conductivity becomes less frequency
dependent and almost have a constant value. In other words, the
elevated temperatures enhance the conductivity in which the rate
of enhancement is noticed to be higher in the region of relatively
low temperature. Generally, the behavior of the electrical conductivity can obey the relation:

x=0.0
x=0.1
x=0.2
x=0.3
x=0.4
x=0.5

0.8

0.6

0.4

r r0 expE=kT

0.2

0.0

250

300

350

400

450

500

550

600

650

700

T (K)
Fig. 5b. Effect of temperature on the variation of the exponent factor (s).

According to Ohnishi and Teranishi [51], the intensity ratios of

planes I(2 2 0)/I(4 40 ), I(4 0 0)/I(4 2 2) and I(2 2 0)/I(4 0 0) are considered to be sensitive to any change in cation distribution. The intensities of (2 2 0) and (4 2 2) planes are mostly sensitive to cations on
the tetrahedral sites [52,53], while the intensity of (4 0 0) plane
depends on the existence of cations in both sites. In the present
investigation (2 2 0), (2 2 2), (4 0 0) and (4 2 2) planes were used to
calculate the intensity ratio using the integrated intensity of the
X-ray diffraction patterns. The trends of the intensity ratios
I(2 2 0)/I(2 2 2), I(4 0 0)/I(4 2 2) and I(2 2 0)/I(4 2 2) match the behavior of saturation magnetization. This trend conrms the sensitivity
of this ratios to the distribution of cations between A and B sites
which found to be in good agreement with the proposed cation distribution in this study. The comparison of X-ray diffraction line
intensity ratios for various possible cation distributions for the
studied compositions is shown in Fig 4. I suggest to be in a separate
Table to avoid the problem of the huge error bars.
It has been reported that nanosized materials possess signicantly distinguished physical and chemical properties from those
of bulk materials due to the their extremely small particle size or
large surface area [54,55]. For example, it has been found that
the surface area of the nanoparticles play an important role in
the eld of nanomagnetism [56]. Consequently, the surface area
is calculated for all compositions using the following relation [57]:

6000
Ddbulk

10

where k is Boltzmann constant, E is the activation energy required

for hopping of charge carriers, T is the absolute temperature and
r0 represents specic conductivity. Fig. 5 shows that the studied
samples have semiconducting behavior with temperatures as indicated from the increase of rac with increasing in temperature at
selected frequencies. An obvious dispersion behavior is observed
at T 6 100 C whereas at higher temperature range the conductivity
seems to be less temperature-dependent. The increase of conductivity rac with increasing temperature may be ascribed to the increase
in the drift mobility and charge carriers hopping frequency. This
behavior is consistent with the relation; r = nel; in which e is the
charge of the electron, l is the drift mobility of charge carriers
and n is the concentration of charge carriers (n = ne + nh, where
the subscripts e and h refer to electron and hole respectively, as
charge carriers responsible for the conduction process). Ferrites
are considered as semiconductors with low-mobility, so the activation energy is often associated with concentration rather than their
mobility of charge carriers.
It is pertinent to mention that the type of the conduction mechanism basically based on the variation of the exponent s with temperature. The values of the exponent factor s as a function of
temperature were derived from the slope of the curves shown in
Fig. 5a. The variation of s with temperature for the present samples
is plotted in Fig. 5b. Recently, number of theoretical models as the
small polaron (SP) model, the overlapping large polaron-tunneling
(OLPT), the correlated barrier-hopping (CBH) and quantum
mechanical tunneling (QMT) model have been assumed as applicable models for explaining the conduction mechanism in ferrite
materials [60,61]. In the present investigation, the observed
decrease of s values with the increasing of temperature agree well
with the correlated barrier-hopping (CBH) model. Similar behavior
has been reported by Zaki [62], Farea et al. [63] and Ghatak et al.
[64]
3.5. Dielectric constant

where D is the particle size in nm and dbulk is the bulk density of the
particle in g/cm3. The calculated surface area of the nanoparticles
increases with the reduction of the particle size as listed in Table 2.
The saturation magnetizations (Ms) is sensitive to the particle size
or surface area. It is obvious from Table 2, that as the particle size
decreases the surface area increases and the Ms value is increased
too. This behavior is observed for samples with compositions
x = 0.1, 0.2 and 0.3 where the particle size decreases from 62 to
25 nm. Other samples with concentration x = 0.4 and 0.5 exhibit
signicant decrease of the saturation magnetization due to the
increase of their particles sizes or decrease in surface area. This correlation between the particle size and magnetic properties has been
reported for some ferrites compounds [58,59].
3.4. AC conductivity
Fig. 5a indicates the variation of conductivity rac as a function of
frequency at particular temperatures. The plots of log rac against

Different parameters can vary the dielectric properties of solids

such as temperature, frequency of applied electric eld, crystal
structure, humidity and some other external factors [65]. The
dielectric response of a solid can be described by expressing the
relative dielectric constant as a complex quantity consists of a real
component (e0 ) and an imaginary component (e00 ) i.e.,

e e0  ie00

11

The real part of dielectric constant represents the amount of energy

stored in a dielectric material as polarization while the imaginary
part, represents the energy loss. The effect of frequency on both
parts of the relative dielectric constant (e0 , e00 ) at different temperatures are shown in Figs. 6 and 7, respectively. It is found that all the
samples show similar behavior with frequency. As a general trend,
the dielectric constant decreases with increasing frequency. Furthermore, the dispersion in dielectric constant is more signicant
at low frequencies in comparison to high values. The decrease in
e00 is more obvious as compared to the e0 as the frequency increases
from 100 Hz to 1 MHz.

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H.M. Zaki et al. / Journal of Alloys and Compounds 633 (2015) 104114
4

10

x=0.0

103

'

'

RT
o
100 C
o
200 C
o
300 C
o
400 C

10

RT
o
100 C
o
200 C
o
300 C
o
400 C

x=0.3

104

102
101

10

100
10-1

10

logf (Hz)

logf (Hz)

RT
o
100 C
o
200 C
o
300 C
o
400 C

x=0.1
3

10

'

'

10

RT
o
100 C
o
200 C
o
300 C
o
400 C

x=0.4
4

102

10

10

100

logf (Hz)

logf (Hz)

105

10

x=0.2

RT
o
100 C
o
200 C
o
300 C
o
400 C

10

x=0.5

RT
o
100 C
o
200 C
o
300 C
o
400 C

10

10

'

'

103

102
1

10

101

10

logf (Hz)

100

logf (Hz)

Fig. 6. The frequency dependence of dielectric constant e0 at selected temperature.

The observed behavior of the dielectric constant can be

explained on the basis of MaxwellWagner [66,67] and Koops theory [68]. According to these two models, ferrites in general are considered to be consist of grains and grain boundaries. The grain
boundary is more resistive than that of the grain itself. Moreover,
at higher frequencies the grains are found to be more effective,
on contrast with the grain boundaries, which are predominant at
lower frequencies. As the frequency increases, the charge carriers
responsible for the polarization lack behind the applied eld. This
behavior will appear as dielectric relaxation in the obtained results.

The observed peaks in the graphs of the dielectric constant (e0 )

with frequency at different selected temperatures may be
explained utilizing the Rezlescu model [69]. According to this
model, the inverse peaks observed in Fig. 6 can be ascribed to
the contribution of the two different types of charge carriers to
the polarization. For the studied samples, the presence of two different types of charge carriers, electron transfer between Fe2+ and
Fe3+as n-type, and hole exchange between Cu+ and Cu2+ at the
octahedral sites as p-type may be enhance the conduction process
[70,71]. In terms of the polarity, the direction of the holes transfer

112

H.M. Zaki et al. / Journal of Alloys and Compounds 633 (2015) 104114

x=0.0

10 8

RT
o
100 C
o
200 C
o
300 C
o
400 C

10

"

10 6

"

105

RT
o
100 C
o
200 C
o
300 C
o
400 C

x=0.3

10 5
10 4
10 3
10 2

100

10 1
1

logf (Hz)

logf (Hz)
10 8
RT
o
100 C
o
200 C
o
300 C
o
400 C

x=0.1

106

RT
o
100 C
o
200 C
o
300 C
o
400 C

10 6
10 5

104

"

"

105

x=0.4

10 7

10 4
103

10 3

102

10 2

101

10 1
1

logf (Hz)

logf (Hz)
10 9
RT
o
100 C
o
200 C
o
300 C
o
400 C

x=0.2

105

10 8

x=0.5

RT
o
100 C
o
200 C
o
300 C
o
400 C

10 7

"

"

10 6
10 5
10 4
10 3
10 2
100

10 1
1

logf (Hz)

logf (Hz)

Fig. 7. The frequency dependence of dielectric loss (e00 ) at selected temperature for the Mg0.5CuxZn0.5xFe2O4 ferrites.

is opposite to that of the electrons under the effect of the applied

external electric eld beside the mobility of holes is relatively very
small with respect to that of electrons. As a result of that, the resultant polarization of both types of charge carriers will give raise to
the appearance of peaks as shown in Fig. 6. Such peaking behavior
has been also observed for CuNi, CuMn and CuZn ferrite [69]
and NiZn ferrite [72].
The high values of the dielectric constant may be correlated to
the space charge polarization mechanism. In such mechanism
the conductivity of grain boundaries having high resistance differs
from that of grains with low resistance, hence the charge carriers
face different resistances causing an accumulation of charges at
separating boundaries which in turn produces an increase in the
dielectric constant.

The variations of the two parts of dielectric constants (e0 ; e00 ) as

a function of temperature for Mg0.5Zn0.5xCuxFe2O4 ferrites at
selected frequencies were found to increase with increasing in
the temperature conrming the semiconducting nature of the
samples. For more details, at relatively low temperatures the
charge carriers can not align themselves in the direction of
applied eld which result as an increase in the polarization and
hence in the dielectric constant. As the temperature increases,
the thermal energy increases and more bound charges get liberated which result as an increase of the mobility of charges that
would enable them to orient easily in the direction of the applied
eld. This, in turn, enhances their contribution to the space
charge polarization causing a pronouncing increase in the value
of dielectric constant.

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H.M. Zaki et al. / Journal of Alloys and Compounds 633 (2015) 104114

10 3

10 6

x=0.0

x=0.3
RT
o
100 C
o
200 C
o
300 C
o
400 C

RT
o
100 C
o
200 C
o
300 C
o
400 C

10 4

tan

tan

10 2

10

10 1

10 3
10 2
10 1

10 0

10 0
1

logf (Hz)

10 2

10 1

10 0

10 0
2

RT
o
100 C
o
200 C
o
300 C
o
400 C

x=0.4

logf (Hz)

logf (Hz)

x=0.2

RT
o
100 C
o
200 C
o
300 C
o
400 C

10 4

tan

10 2

x=0.5

10 5

RT
o
100 C
o
200 C
o
300 C
o
400 C

10 3

tan

10 2

10 1

10 3

tan

10 3

tan

10 4

RT
o
100 C
o
200 C
o
300 C
o
400 C

x=0.1

10 4

logf (Hz)

10 3
10 2

10

10 1
10 0

10 0
1

logf (Hz)

logf (Hz)

Fig. 8. The frequency dependence of dielectric loss tangent (tan d) at selected temperatures for the Mg0.5CuxZn0.5xFe2O4 ferrites.

There are different types of polarization which contribute to the

dielectric constant; dipolar, electronic, ionic, and interfacial
polarizations. Interfacial and dipolar polarizations depend on temperature and found to play main role at low frequency region. The
interfacial polarization increases as the temperature increase
owing to creation of crystal defects, consequently, dipolar polarization decreases. The effect of temperature is more distinct on the
interfacial than on dipolar polarization, so the overall effect is the
observed rapid increase in the dielectric constant with temperature at low frequencies. At high frequencies, electronic and ionic
polarizations are the main contributors to the dielectric constant
and their temperature dependence is irrelevant [73,74].

3.6. Dielectric loss tangent (tan d)

The dielectric loss factor (tan d) characterizes the energy loss.
The dielectric loss arises when the applied ac eld leads the polarization and can be expressed according to Eq. (2).
Many factors can affect the dielectric losses of the samples as
impurities, imperfections in the crystal lattice and the density of
the samples. Fig. 8 shows the variation of loss tangent tan d with
frequency at selected temperatures. It was found that tan d
decreases with increasing frequency for all samples. A decreasing
behavior was reported by Penchal Reddy et al. [75] for
Polycrystalline MgCuZn ferrites with chemical formula

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H.M. Zaki et al. / Journal of Alloys and Compounds 633 (2015) 104114

Mg0.50xCuxZn0.50Fe2O4 prepared by microwave sintering method.

The frequency response of tan d shows small peaks or relaxation
processes in some samples as for x = 0.1, 0.3, 0.4 and 0.5. The difference in environment of different ions in a condensed material leads
to the distribution of relaxation processes. For observing a maxima
in the dielectric loss the following condition must be veried:

xmax: s 1
where xmax 2pf max . The relaxation time
ing probability per unit time p as:

s 1=2p or xmax: 2p

12

s is related to the jump13

According to Eq. (12), the Debye relaxation process occurs when the
jumping rate becomes approximately equals to applied eld
frequency which is known as ferrimagnetic resonance [76].
The disappear of the resonance peaks at the compositions,
x = 0.0 and 0.2 may be ascribed to the relatively high resistivity
of these samples or due to shifting of their positions to higher
frequencies beyond the applied range of frequency.
4. Conclusion
Nano-crystalline Mg0.5CuxZn0.5xFe2O4 (0 6 x 6 1.0) ferrite
powders were synthesized by co-precipitation technique. Lattice
constant showed decreasing trend with increasing of Cu2+ concentration due to smaller ionic radius of Cu2+ ions in comparison to
zinc ions. As the lattice constant decreases the X-ray density
increases and the porosity decreases indicating dense packing of
the samples. The magnetic behavior of the nano-crystalline ferrites
exhibited some sensitivity to the particle size and surface area.
Variation of saturation magnetization with Cu content was
explained in terms of the cations redistribution between the sub
lattices A and B and X-ray intensity ratios of the diffraction lines
sensitive to the tetrahedral and octahedral sites. The decrease of
the dielectric constant at low frequency and the appearance of
anomalous dispersion behavior was explained in the light of
MaxwellWagner and Koops models of polarization. Contribution
of two types of charge carries as electrons and holes in the conduction mechanism was attributed to the appearance of two opposite
resonance peaks in plots of the dielectric constant with frequency.
Dielectric loss tan d found to decrease with frequency at low temperatures without signicant change at high temperatures.
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