Journal of Molecular Structure 1024 (2012) 7783

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Journal of Molecular Structure

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

Structure renement, cation site location, spectral and elastic properties

of Zn2+ substituted NiFe2O4
Sagar E. Shirsath a,b,, S.M. Patange c, R.H. Kadam c, M.L. Mane a, K.M. Jadhav a
a

Department of Physics, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad 431 004, MS, India
Department of Physics, Vivekanand College, Aurangabad 431 004, MS, India
c
Materials Research Laboratory, Srikrishna Mahavidyalaya Gunjoti, Omerga, Osmanabad 413613, MS, India
b

h i g h l i g h t s
" Cation distribution carried out by Rietveld renement.
2+

" Zn

substitution decrease the interatomic distance and elastic properties.

2+
substitution.

" Curie and Debye temperature decreases with Zn

a r t i c l e

i n f o

Article history:
Received 10 February 2012
Received in revised form 4 May 2012
Accepted 7 May 2012
Available online 15 May 2012
Keywords:
Structure renement
Infrared spectroscopy (IR)
Dielectric properties
Elastic properties

a b s t r a c t
NiZn ferrite samples with the chemical formula Ni1xZnxFe2O4 (x = 0.0 to x = 1.0) were prepared by solid
state reaction. Using the Rietveld renement the discrepancy factor, interatomic distance, atomic coordinates, cation occupancy and degree of inversion have been determined. SEM images revealed that the
Zn2+ promotes grain growth in NiFe2O4. The IR spectra show two absorption bands in the wave number
range of 400600 cm1. The IR data have been used to calculate elastic moduli such as stiffness constant
(C11, C12), longitudinal wave velocity (Vl), shear wave velocity (VS), mean wave velocity (Vm), Young modulus (E), bulk modulus (K), rigidity modulus (G), Poisson ratio (r) and Debye temperature (hE). The values
of elastic moduli and Debye temperature decreases with increasing Zn2+ composition x. AC susceptibility
measurement conrms the decrease in Curie temperature with increasing Zn2+ content. Dielectric loss
(e}) increases with increasing Zn2+ content.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Among the different type of spinel ferrites, NiZn ferrites are
the most versatile magnetic materials for the global use. They have
many applications in low- and high-frequency devices and play a
useful role in many technological applications such as microwave
devices, power transformers in electronics, rod antennas and
read/write heads for high-speed digital tape. The important properties of ferrites are; high resistivity, low dielectric losses, mechanical hardness, high Curie temperature, chemical stability [13].
Both nickel and zinc ferrites have cubic spinel structures; the
lattice constants are not greatly different and the two ferrites are
soluble in each other. Each zinc cation in zinc ferrite (ZnFe2O4) carries zero net electronic spin and is situated at the center of a tetrahedron of oxygen ions. The array of all such sites occupied in the
Corresponding author at: Department of Physics, Dr. Babasaheb Ambedkar
Marathwada University, Aurangabad 431 004, MS, India. Tel.: +91 02402240950;
fax: +91 02402361270.
E-mail address: shirsathsagar@hotmail.com (S.E. Shirsath).
0022-2860/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molstruc.2012.05.014

perfect lattice is called the sublattice. The iron cations occupy sites
surrounded by an octahedron of oxygen ions. For nickel ferrite (NiFe2O4), the nickel carried two net spins and occupies the B site
while the iron occupies the A site and one half of the B site. The
question of the distribution of nickel on the B sublattice and, the
in the case of mixed ferrites, of distribution of zinc on the A sublattice have been discussed earlier and it is concluded that the nickel
probably is randomly oriented on the B sublattice and that the zinc
on the A sublattice is also randomly oriented for the mixed ferrites
[4,5].
In the light of above discussion and importance of NiZn ferrite
we have focused the present study to cation distribution by Rietveld renement and elastic properties because of following.
In the recent past, there has been an increasing interest among
the researchers to apply the Rietveld method [6] for cation distribution and in structurally characterizing the ferrites materials
[710]. Rietvelds renement based on structure and microstructure renement has been adopted in the present analysis for precise determination of several microstructural parameters. Studies
of the elastic constants are important in order to understand the

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S.E. Shirsath et al. / Journal of Molecular Structure 1024 (2012) 7783

behavior of the engineering materials. Elastic constants relate closely to many physical properties of solids, such as acoustic-phonon
frequencies and internal stress, Debye temperature. Furthermore,
they provide a sensitive probe of phase transitions and an indication of the nature of interatomic and interionic binding forces in
the material [1113]. Therefore, there is a need for a thorough
study of the elastic behavior of these ferrites with new compositions possessing certain desired elastic properties in view of their
extensive applications.
2. Materials and preparation
Ferrite samples of the Ni1xZnxFe2O4 system with x values ranging from 0.0 to 1.0 in the steps of 0.2, were prepared by the solid
state reaction [14,15]. The chemical reaction is expressed as;
1173K

1323K

12h

12h

NiO ZnO 2Fe2 O3 ! NiZnFe2 O4 ! NiZnFe2 O4

Intimate mixtures of all the samples, after weighing in correct
proportions from the AR grade NiO, ZnO and Fe2O3 powders, were
ground thoroughly to obtain good homogeneity and then pre-sintered at 1173 K for 12 h. The pre-sintered powders were again
ground and granulated using 2% polyvinyl alcohol as a binder.
The granulated mixture was then palletized in disk shaped form
at a pressure of 6 ton/in2 and in the nal sintering process, the
samples were placed in a Indfur programmable furnace at 1323 K
for 12 h in atmospheric air and then slowly cooled to room temperature at the rate of 2 K/min.
The samples were powdered for X-ray investigations. Part of the
powder was X-ray examined by Phillips X-ray diffractometer
(Model 3710) using Cu Ka radiation (k = 1.5405 ). The data were
processed to analyze all of the samples using the computer Program FullProf.2k (Version 4.30 Apr2008-ILL JRC) in the Rietveld
method for structure renement. Program renement of the rst
samples was started with the space group Fd3 m, origin at 3 m,
O in 32e, A-site in 8f and B-site in 16c. In the rst step the global
parameters, such as 2h-zero and background, were rened. In the
next step, the structural parameters such as lattice parameter,
atomic coordinates, and site occupancy, were rened. The ac susceptibility measurements were carried out by double coil set up
operating at a frequency of 263 Hz and in rms eld of 100 Oe
was used to record temperature variation in susceptibility. Infrared
spectra (IR) were recorded in the range of 350800 cm1 at room
temperature by IR spectrometer (Bruker). To record IR spectra,
the samples were powdered and mixed with KBr in the ratio of
1:250 by weight. The mixed powders were then pressed in a cylindrical die to obtain disk shaped pellets of about 1 mm thickness.
The frequency dependent dielectric loss measurements were carried out on HIOKY 3532-50 LCR meter at room temperature in
the frequency range 100 Hz1 MHz.
3. Results and discussion
3.1. Structural properties
The prepared NiZn ferrite samples with spinel structure AB2O4
have a face centered cubic crystalline lattice and space group
Fd3 m (JCPDS 10-0325 data). The Rietveld rened X-ray diffraction
pattern of the typical composition x = 0.4 is shown in Fig. 1. Typical
composition x = 0.4 presented in manuscript, as x = 0.4 is nearly a
middle composition in the whole system. The pattern shows the
formation of single phase cubic spinel structure without any signature of secondary phase. The data were processed to realize the
conditions of the FullProf software program for the structure
renement. XRD renement was continuous until convergence

Fig. 1. Rietveld rened XRD pattern for x = 0.4.

was reached with a goodness factor close to 1. All the results obtained from the renement of the structure are correlated with
Zn2+ content x. The values of the discrepancy factor (Rwp) and expected values (Rexp) with the goodness of t index (v2) are listed
in Table 1. Our Rietveld rened values are in good agreement with
literature report for other ferrite systems [16,17].
The lattice constant calculated by the Rietveld method and the
values are listed in Table 2. The increase in lattice parameter with
increasing Zn content can be explained on the basis of the ionic radii.
The radius of the Zn2+ (0.83 ) ion is greater than that of the Ni2+
(0.78 ) [18], and this difference in ionic radius cause to expand lattice with Zn2+ substitution. The variation of lattice parameter with
zinc substitution obeys Vegards law [19]. The enhancement in the
lattice constant is normally attributed to the interface structure
with a large volume fraction [20]. The enhanced role of the surface
is clearly visible in the variation in the lattice constant. The average
crystallite size (t) was determined using the line broadening of the
most intense (3 1 1) diffraction peak using the DebyeScherrer formula [21]. The values of the crystallite size are given in Table 2. It is
observed from Table 2 that the crystallite size is increases from 1.29
to 3.5 lm with the increasing Zn substitution in NiFe2O4. The bulk
density (q) was calculated using the relation discussed elsewhere
[22]. It is observed from Table 2 that bulk density increases with
increase in Zn2+ content. The increase in the density is correlated
with increase of atomic weight of substituted Zn2+ ions instead of
Ni2+ ions. The atomic weights of Zn2+ and Ni2+ are 65.38 and 58.69
amu, respectively. This increase in density may also be a fact that
Zn2+ is acting as slight accelerator of grain growth and favouring
densication. This is evidence of accelerated densication during
the sintering process which led to reduction of pore fraction as
evidence from Table 2.
The Rietveld renement method [23] was used to determine the
cation distribution. The nal results of cation distribution obtained
from the Rietveld renement are given in Table 3. Electronegativity
(EN) is a measure of attraction towards the valence electrons, and

Table 1
Discrepancy factor (Rwp), expected values (Rexp) goodness t factor (v2). Values
enclosed in the square bracket denote the estimated error.
Comps. x

Rwp (%) [0.2]

Rexp (%) [0.2]

v2 [0.1]

0.0
0.2
0.4
06
0.8
1.0

6.37
7.68
9.24
9.72
10.23
11.13

3.22
3.66
4.62
4.42
5.22
4.84

1.97
2.10
2.00
2.2
1.96
2.3

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S.E. Shirsath et al. / Journal of Molecular Structure 1024 (2012) 7783

complexes at around 600 and 400 cm1 respectively are observed

which indicates formation of spinel ferrite structure. Absorption
at m1 is caused by stretching of tetrahedral metal ion and oxygen
bonding, while m2 is caused by vibrations of oxygen in the direction
perpendicular to the axis joining the tetrahedral ion and oxygen
ion. In his pioneering work, Waldron [29] attributed the m1 band
to the intrinsic vibrations of the tetrahedral groups corresponding
to the highest restoring force and m2 bands to the octahedral groups
which are bond-bending vibrations.
It is clear from Table 4 that the central frequency of the principle
band m1 reduces and m2 shifts gradually towards the high frequency
side. It can be recalled here that Zn2+ ions largely occupied tetrahedral A-site in cation distribution. Zinc ions have larger ionic radius
and have higher atomic weight as compared to nickel ions which affects band positions and is the important reason of the observed
shift in the band position with increasing zinc content in the ferrite.
The force constants corresponding to the tetrahedral and octahedral complexes are calculated by using the standard formulae given below [30]:

Table 2
Lattice constant (a), bulk density (q), pore fraction (f) and crystal size (DXRD) of
Ni1xZnxFe2O4. Values enclosed in the square bracket denote the estimated error.
Comps. x
0.0
0.2
0.4
0.6
0.8
1.0

a ()
[0.002]

q (gm/cm3)
[0.05]

(f)
[0.005]

DXRD (lm)
[0.2]

8.335
8.350
8.375
8.386
8.398
8.408

4.88
4.95
4.99
5.02
5.06
5.11

0.0801
0.0787
0.0668
0.0509
0.0360
0.0226

1.29
1.87
1.94
2.06
2.23
3.50

more electronegative ions are known to prefer octahedral site. The

Electronegativity of Zn2+, Ni2+ and Fe3+ atoms are 1.65, 1.91 and
1.83, respectively [24]. According to this measure, Ni2+ and Fe3+
should prefer octahedral and Zn2+ ions should occupy tetrahedral
site. The tendency of Zn2+ cation to occupy to tetrahedral A-site
is consistent with that reported by Ahmed Farag et al. [25]. The
electronic conguration of Zn2+ has also marked preference for
the tetrahedral site, since their 4s and 4p or 5s and 5p electrons
can form covalent bond with the 2p electron of oxygen ion. Also
by considering the site preference energy of the cations, Zn2+ ions
have strong preference towards tetrahedral (A) site whereas Ni2+
has slight afnity towards octahedral [B] site and Fe3+ has no definite site preference. The Table 3 indicates that most of the Zn2+
occupies tetrahedral (A) site, and most of the Ni2+ have occupied
octahedral [B] site and Fe3+ occupies, both tetrahedral and octahedral sites. Our determination of cation distribution of NiZn ferrite
is in good agreement with the cation distribution of NiZn ferrite
reported by other methods [2628].
Representative micrographs for Ni1xZnxFe2O4 ferrite system
are shown in Fig. 2. The surface morphology of the samples as seen
from the SEM consists of grains varying from 2 to 4 lm. The grains
could be seen clearly and these grains usually contained a very
large number of atoms. The observation conducted indicated that
the growth of the grains was normal as there was a rather narrow
range of grain sizes. There were very few grains which grew rather
large but they appeared to have no defects, i.e., their growth was
also normal. Some cavities have been observed on the surface as
seen in micrographs.

K T 7:62  M 1  t21  102

K O 10:62 

1a

M2
 t22  102
2

1b

where KO is the force constant of octahedral site, KT is the force constant of tetrahedral site, M1 molecular weight of tetrahedral site, M2
molecular weight of octahedral site, m1 the corresponding center
frequency on tetrahedral site, and m2 the corresponding center frequency on octahedral site. The molecular weights M1 and M2 for
each sample are calculated from the cation distribution. The force
constant is a second-order derivative of potential energy with respect to the bond length, the other independent parameters being
kept constant. In the present system it is observed from Table 4 that
the force constants KT and KO decrease with the increase in zinc concentration. It is an established fact in IR studies that the force constant is inversely proportional to the bond length [31]. The bond
lengths RA and RB are found to increase with content of zinc (Table
4). The increase in bond length suggests that the inter-atomic distance increases with increase in Zn2+ ions.
The analysis of IR spectra with precise crystallographic knowledge helps us to determine the elastic parameters, Debye temperature, longitudinal and shear velocities. The Debye temperature (hI)
is a fundamental attribute of solid connecting elastic properties
with thermodynamic properties such as specic heat, melting temperature, or vibrational entropy. The Debye temperature of all
samples was calculated by using the relation [32].

3.2. Spectral properties

Infrared spectroscopy (IR) is employed to determine the local
symmetry in crystalline solids. The increase in the concentration
of divalent ion such as Zn2+ in Ni-ferrites may give rise to structural
change within the unit cell without affecting the structure as a
whole. Such structural changes brought about by metal ions
strongly inuence the lattice vibrations.
The infrared spectra of the powder samples for all the compositions of Ni1xZnxFe2O4 is shown in Fig. 3. Two absorption bands
corresponding to the vibration of tetrahedral and octahedral

hI

hC v av
k

where

v av

vA vB
2

Table 3
Values of atomic coordinates (x, y, z), occupancy (g) and degree of inversion (d) of Ni1xZnxFe2O4. The estimated error for occupancy (g) is 0.02 and for degree of inversion it is
0.005.
Atom

O
Ni
Zn
Fe
Ni
Zn
Fe
d

x = 0.0

x = 0.2

x = 0.4

x = 0.6

x = 0.8

x = 1.0

x=y=z

x=y=z

x=y=z

x=y=z

x=y=z

x=y=z

0.2531
0.5000
0.5000
0.5000
0.1250
0.1250
0.1250
0.456

4.000
0.97
0.00
1.03
0.03
0.00
0.97

0.2522
0.5000
0.5000
0.5000
0.1250
0.1250
0.1250
0.564

4.0000
0.76
0.04
1.20
0.04
0.16
0.80

0.2521
0.5000
0.5000
0.5000
0.1250
0.1250
0.1250
0.642

4.0000
0.55
0.05
1.40
0.05
0.35
0.60

0.2515
0.5000
0.5000
0.5000
0.1250
0.1250
0.1250
0.725

4.000
0.34
0.06
1.60
0.06
0.54
0.40

0.2502
0.5000
0.5000
0.5000
0.1250
0.1250
0.1250
0.821

4.000
0.13
0.07
1.80
0.07
0.73
0.20

0.2488
0.5000
0.5000
0.5000
0.1250
0.1250
0.1250
0.845

4.000
0.00
0.08
1.92
0.00
0.92
0.08

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S.E. Shirsath et al. / Journal of Molecular Structure 1024 (2012) 7783

Fig. 2. SEM images of (a) x = 0.2, (b) x = 0.4, (c) x = 0.6, and (d) x = 0.8.

x = 1.0

Transmission (%)

x = 0.8

Table 4
The Infra red absorption bands (m1 and m2), Force constants (Kt and Ko) and Bond
lengths (RA and RB) of Ni1xZnxFe2O4. Values enclosed in the square bracket denote the
estimated error.
Comp. x

x = 0.6

x = 0.4
x = 0.2
x = 0.0

0.0
0.2
0.4
0.6
0.8
1.0

m1

m2
(cm1) [3]

Kt  105
(dynes/cm2)

Ko

(cm1) [3]

RA ()
[0.01]

RB ()
[0.025]

602
606
598
592
586
585

416
419
421
426
430
431

2.41
2.37
2.31
2.25
2.21
2.28

1.36
1.33
1.29
1.24
1.22
1.26

0.628
0.677
0.695
0.712
0.729
0.773

1.007
1.093
1.240
1.379
1.522
1.874

Stiffness constant C 11

K
a

where K is average force constant and a is lattice constant.

Wavenumber (cm-1)
Fig. 3. IR Spectra of Ni1xZnxFe2O4.

mA is the frequency of the primary band of A-site, mB is the frequency

of the primary band of B-site, 
h h=2p; h is the Plank constant, k is
the Boltzmanns constant and C = 3  1010 cm/s; is the velocity of
light. Fig. 4 shows the variation of Debye temperature (hI) with
composition x. It is observed from Fig. 4 that the Debye temperature
decreases with increase in Zn content x, the observed variation is
due to the small decrease in wave number of bands.
3.3. Elastic properties
In general, there are thirty-six elastic moduli, but in the case of
isotropic and homogeneous material like spinel ferrite and garnet,
the elastic moduli can be reducing to three moduli. For spinel ferrite
system, elastic constant and Debye temperature can be calculated
using IR data using the relation discussed elsewhere [33,34]. The
stiffness constants C11 and C12 were calculated using relation [35].

Stiffness constant C 12

rC 11
1  r

where r is Poissons ratio. Using Eqs. (3) and (4) the stiffness constant is calculated and the variation is shown in Fig. 5. It can be seen
from Fig. 5 that both the stiffness constant were decreases with increase in Zn content x.
The values of Poissons ratio (r) were calculated using the relation discussed elsewhere [36] and the values are presented in Table
5. The values of Poissons ratio are decreases from 0.297 to 0.316
with the increasing substitution of Zn2+ ions. According to the theory of elasticity the values of Poissons ratio must lays in between
1 and 0.5 for the good elastic behavior, so it is worth to mention
here that our values are in good agreement with theory of elasticity. The other elastic moduli for cubic structure are calculated
using following relation [36]:

Youngs modulus E

C 11  C 12 C 11 2C 12
C 11 C 12

Rigidity modulus G

E
2r 1

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S.E. Shirsath et al. / Journal of Molecular Structure 1024 (2012) 7783

Table 5
Values of Vl/q and VS/q, Poissons ratio (r) and Curie temperature (Tc) of
Ni1xZnxFe2O4. Values enclosed in the square bracket denote the estimated error.

738

E
I

720

736

700
734
680
660

732

640

Debye temperature ' I' (K)

Debye temperature 'E' (K)

740

Comp. x

Vl/q [0.02]

VS/q [0.02]

r [0.002]

Tc (K) [10]

0.0
0.2
0.4
0.6
0.8
1.0

1.329
1.297
1.269
1.239
1.219
1.205

0.776
0.755
0.724
0.688
0.660
0.648

0.297
0.297
0.301
0.307
0.312
0.316

830
756
645
546
464

730

where G0 is rigidity modulus with correct zero pore fraction. The

values of Vl and Vs used to calculate mean wave velocity (Vm) which
used to calculate Debye temperature was calculated using formula

620
0.0

0.2

0.4

0.6

0.8

1.0

Zn content x
Fig. 4. Variation of Debye temperature (hI and hE) with composition x.

Bulk modulus K

1
C 11 2C 12
3

Debye temperature hE
7

The Youngs modulus (E), bulk modulus (K) and rigidity modulus (G) are calculated using the relation 57 and the variation are
presented in Fig. 6. It can be observed from Fig. 6 that the values
of Youngs modulus, bulk modulus and rigidity modulus decreases
with Zn concentration x. According to Wooster work [37] this
behavior of elastic moduli is attributed to inter-atomic binding between various atoms of the spinel lattice. The inter-atomic binding
between various atoms weakened continuously and therefore elastic moduli decreases with Zn content x. In NiZn ferrite repulsion
between electron increases as Zn increases. Weakening of strength
of interatomic boding with increasing Zn concentration in NiFe2O4
can be explained as: the Fe3+ ions with 3d5 outer most orbital congurations are replaced by Zn2+ ions with completely lled 3d10
conguration. It is well know that the completely lled orbit is
more stable than that of half lled orbit. In the present case Ni2+
ions with partially lled outermost orbit (3d8) are replaced by
Zn2+ ions having completely lled outermost orbit (3d10), which
do not contribute to the bond formation. Further, Zn2+ ions do
not strengthening the inter-atomic binding with Fe3+ ions due to
the low ionization enthalpies, and Zn2+ ions also have the extra stability i.e. full-lled 3d10.
The longitudinal elastic wave velocity (Vl) and transverse (Shear)
wave velocity (Vs) was calculated using following equations,

Longitudinal velocity V l

 1=2
C 11

TransverseShearvelocity V s

 1=2
G0

10

where h is planks constant, k is Boltzmanns constant, N is Avogadros number, M is molecular weight, q is number if atom in the unit
formula (in the present case q = 7), q is the density of the sample
and Vm mean wave velocity. This mean velocity is given by

"
!#13
1 2
1
Vm

3 Vs3 V 3l

11

The values of longitudinal wave, shearing wave and mean wave

velocity are calculated using relation 8, 9 and 11 respectively. It is
observed from Fig. 7 that the wave velocity is decreases with increase in Zn content x. It is observed from Fig. 7 that the values of
transverse wave are less than longitudinal waves. This is due to
when a wave travels through a material, due to transfer of energy,
it makes the particle vibrate. The vibrating particles collide with
other particles which results in other particles to vibrate. In case
of transverse waves, the particle in a medium vibrates perpendicular to the direction of propagation of wave motion, and hence it requires a larger energy to make the neighboring particle vibrate. This
results in reduction in the energy of waves, and hence the velocity
of the transverse waves is about half that of longitudinal waves
[12]. The values of wave velocities are similar to other ferrites those
obtained from UPT method [38]. The variation of Debye temperature (hE) is shown in Fig. 4, the Debye temperature decrease with
Zn content x. Debye temperature represent the temperature at
which nearly all modes of vibration in solid are excited and decrease in Debye temperature implies the decrease in the rigidity


1=3
h 3qqN
 Vm
k 4pM

180

C11
C12

224

96

220
216

94

212
208

92

204

Stiffness Constant 'C12' (GPa)

Stiffness Constant 'C11' (GPa)

98

Moduli constant (GPa)

160
228

140
120
Youngs
Bulk
Rigidity

100
80
60
0.0

0.0

0.2

0.4

0.6

0.8

1.0

0.2

0.4

0.6

0.8

1.0

Zn content x

Zn content x
Fig. 5. Variation of stiffness constant C11 and C12 with composition x.

Fig. 6. Variation of Young modulus, bulk modulus, rigidity modulus with composition x.

S.E. Shirsath et al. / Journal of Molecular Structure 1024 (2012) 7783

6525

4000

6450
6375

3800
6300

3600

6225

3400
3200

0.0
0.2
0.4
0.6
0.8
1.0

Dielectric loss (")

Vm
VS
VL

4200

wave velocity 'VL' (m/sec)

Wave velocity 'VS and Vm' (m/sec)

82

6150
0.0

0.2

0.4

0.6

0.8

1.0

Zn content x
Fig. 7. Variation of longitudinal wave velocity (Vl), shear wave velocity (VS), mean
wave velocity (Vm) with composition x.

Log f
of the ferrite. Fig. 4 shows that the Debye temperature (hI) obtained
from IR data are compared with Debye temperature (hE) values obtained from the elastic constant data. The values of Vl/p and VS/p are
calculated and included in Table 5. Following this work, Anderson
[39] has demonstrated that Vl/p and VS/p are constant for a large
number of oxide minerals having the same mean atomic weight.
It can be seen from the Table 5 that the values of Vl/p and VS/p
are fairly constant since NiZn ferrites have nearly the same mean
atomic weight. This shows that the elastic behavior of mixed NiZn
ferrites is similar to that of oxide minerals. A similar behavior was
also observed by several investigators in rocks [40,41] and ferrites
[42,43].
3.4. Magnetic susceptibility and dielectric loss
Magnetic susceptibility primarily depends upon the magnetic
ordering present in the compound which varies as a function of
method of preparation, chemical composition, microstructure
and grain size. The variation of AC susceptibility as a function of
temperature and composition x is studied in the present work.
Thermal variation of AC susceptibility of all the samples is shown
in Fig. 8. All the samples exhibit ferrimagnetic behavior, which decreases as Zn-content x increases. The plots of vT/vRT are used to
determine the Curie temperature (Tc) and the values are given in
Table 5. It is clear from Table 5 that Curie temperature goes on
decreasing with the addition of non-magnetic Zn content. According to Neels model AB interaction is most dominant in ferrites,

Fig. 9. Variation of dielectric loss (e00 ) with log f.

therefore, Curie temperature of the ferrites are determined from

the overall strength of AB interaction. The strength of AB inter2
action is a function of the number of Fe
 Fe3
linkages,
A O
B
3+
which in turn, depends upon the number of Fe ions in the formula unit and their distribution amongst tetrahedral (A) and octahedral [B] site. In the present system Ni2+ (2lB) ions are replaced
by Zn2+ (0lB) ions. This results in decreasing the AB interaction,
which lead to decrease in Curie temperature (Tc).
Dielectric loss (e00 ) in ferrites is contributed by several structural
and microstructural factors. The variation of dielectric loss (e00 ) is
shown in Fig. 9. The variation of dielectric loss (e00 ) with frequency
can be explained on the basis of dispersion due to the Maxwell
Wagner interfacial polarization with Koops phenomenological
theory [44]. Dielectric loss decreases with the increase of frequency. It is because of decrease in polarization with the increase
in frequency. Ultimately, it reaches a constant value. Previous reports have quoted a similar kind of trend with the change in frequency [45,46]. Rabinkin and Novikova [47] pointed out that
polarization in ferrites is similar to that of conduction. The electron
exchange between Fe2+ M Fe3+ results the local displacement of
electrons in the direction of the applied eld that determines the
polarization. Polarization decreases with the increase in value of
frequency and then reaches a constant value. Dielectric loss (e00 )
has large value at lower frequency. It is because of the predominance of species like Fe2+ ions, oxygen vacancies, grain boundary
defects, interfacial dislocation pile-ups, voids, etc. [48,49]. The
decreasing trend in e00 with the increase in frequency is natural
due to the fact that any species contributing to polarizability is
found to show lagging behind the applied eld at higher frequencies [50].

T /RT

4. Conclusions

Temperature (K)
Fig. 8. Plots of vT/vRT with temperature of Ni1xZnxFe2O4.

Zn2+ substituted nickel ferrite with the chemical formula Ni1x

ZnxFe2O4 (x = 0.0 to x = 1.0) were synthesized by solid state reaction. The lattice constant of the NiFe2O4 is increases with increase
in Zn2+ substitution. Rietveld rened cation distribution suggests
that Ni2+ and Zn2+ have a strong preference towards the octahedral
B- and tetrahedral A-site respectively, whereas Fe3+ occupies both
the A- and B-sites. Infrared spectroscopy (IR) technique was used
to locate the band position of the intrinsic vibration. The positions
of the m1 and m2 bands are attributed to the intrinsic vibrations of
tetrahedral and octahedral groups, respectively. The band frequency m1 slightly decreases with increasing Zn2+ substitution,
whereas band frequency m2 increases. The variation in band fre-

S.E. Shirsath et al. / Journal of Molecular Structure 1024 (2012) 7783

quencies is attributed to the different distributions of iron, nickel

and zinc on the tetrahedral and octahedral sites. The bond length
increases with increase in Zn2+ substitution which suggests the
weakening of inter atomic bonding and it is highest for x = 1.0 composition. The elastic properties and Debye temperature decreases
with Zn2+ substitution due to the Ni2+ ions with partially lled outermost orbit (3d8) are replaced by Zn2+ ions having completely
lled outermost orbit (3d10), which do not contribute to the bond
2
formation. The weakening of the Fe
 Fe3
A O
B interaction results in a decrease in the Curie temperature. Dielectric loss (e}) decreases with increasing frequency and increases with increasing
Zn2+ content. Dielectric loss for x = 1.0 is the highest one among
all the compositions.

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