The magnetic properties of the prepared samples are
carried out using the vibrating sample magnetometer
ABSTRACT
Ni-Zn-Al ferrite nanoparticles having the general
formulae of Series-I:
Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2,
1.4, 1.6, 1.8 and 2.0) and Series-II: Nix Zn1-x Al1.0 Fe1.0
O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) are prepared and
synthesized by the sol-gel auto combustion technique.
The prepared samples have been characterized by
XRD, FTIR and SEM with EDX. The magnetic, dielectric
and electrical properties are characterized by vibrating
sample magnetometer (VSM), LCR impedance meter
and two-probe method respectively.
The X-ray diffraction studies are carried out using
Rigaku
X-ray diffractometer (Philips X Pert X-ray diffractometer
of wavelength 1.5406 0A). XRD analysis helps us to find
out the structural properties like lattice constant,
average grain size, X-ray density and porosity. FTIR
study is carried out by FT/IR-4000, JASCO, Japan in
the range 400 4500 cm-1 at room temperature.
Surface morphology and stoichiometric purity of the
prepared ferrite samples are examined by SEM (Carl
Zeiss Model EVO 18) attached with Oxford EDX
system.
(Lakeshore VSM 718 model) at room temperature.
Based on the hysteresis loops the magnetic properties
like saturation magnetization, magnetic moment,
coercivity and residual magnetization could be
explained.
The dielectric behaviour of prepared nanoferrite circular
pellet samples is studied by the LCR impedance meter
(Model 6500P Precision LCR Meter, Wayne Kerr,
Germany). The properties such as dielectric constant,
dielectric loss tangent and AC conductivity of prepared
ferrite samples are calculated as a function of applied
frequency and temperature.
The DC resistivity and activation energy in ferro and
para magnetic regions are calculated with two-probe
method in the temperature range 294 873 K. Curie
temperature is calculated by the two-probe method
(Model DNM-121, SES Instruments Pvt. Ltd, Roorkee)
and also by Lorie-Sinha technique. It is observed that
both values are agreed well with each other.
V-I characteristics of ferrite samples are studied with
Keithely 4200 semiconductor characterization system.
These characteristics showed diode like dynamic
properties. It showed non-linear behaviour in resistance
due to the application of different biasing voltag
The cubic spinel ferrites are synthesized using various
methods like co-precipitation method, citrate precursor
method, self combustion method, sol-gel auto-
combustion method, hydro thermal method, ceramic
technique, solvothermal method, flash combustion
technique, chitosan method etc. But the sol-gel auto
combustion method gives successful homogeneous
mixture of composition and control over the size of
crystallites with the sintering temperature.
Spinel ferrites are the most important magnetic
materials exhibiting lot of interesting applications in
technology and industry. In the spinel structure the
magnetic ions are distributed between two different sub-
lattices namely tetrahedral (A) and octahedral [B] sites.
The properties of ferrites may vary with the ions
distribution at tetrahedral (A) site and octahedral [B]
sites, type of cation substitutions, method of
preparation, preparation conditions and defects in the
crystal structure. In the literature a large numbers of
reports are available on the structural, magnetic,
dielectric and electrical properties of Nickel-Zinc ferrites
with divalent, trivalent and tetravalent ion substitutions.
The Ni-Zn ferrites have wide range of applications in
different fields.
Sanjeev Kumar et. al [1] prepared and studied the
structural and magnetic properties of Ni1-x Znx Fe2 O4 (x
= 0.0, 0.2, 0.4, 0.5, 0.6, 0.8 and 1.0) nano-crystals by
the inverse micro emulsion technique using CTAB as
surfactant and kerosene as an oil phase. The XRD
pattern shows the successful formation of single phase
spinel structure and the particle size is found in the
range of 15 nm. It is noticed that the Zn substitution
changed the lattice constant from 8.341 to 8.35 . The
nanocrystals magnetism property is changed from
ferromagnetic to super paramagnetic behaviour at x =
0.0 i.e., pure NiFe2O4 ferrite changed from super
paramagnetic to paramagnetic at
x = 1.0 by increasing zinc concentration. The Curie
temperature is observed to decrease with an increase in
the zinc concentration.
Raghavender et. al [2] studied the structural and
magnetic properties of Ni1-x Znx Fe2 O4 (0.0 x 0.5)
thin films grown on R-cut Al2O3 (0001) substrates by
using pulsed laser deposition (PLD) method and shown
the formation of single phase cubic structure. The thin
films show the ferromagnetic behaviour in the
temperature range from 300 K down to 5 K. They
observed that the magnetization and coercivity is
strongly dependent on Zn substitution. At x = 0.4 they
found that magnetization is improved due to fabrication
technique, low dimensionality and annealing conditions
will favour the existence of Fe2+ in the thin films. Higher
coercive field thin films are used as potential candidates
for modern miniaturization of electronic devices.
Shinde et. al [3] studied the magnetic properties
(magnetization, AC susceptibility, cation distribution and
Curie temperature) of
Ni1-x Znx Fe2 O4 (x = 0.0 - 1.0) ferrites using an oxalate
co-precipitation method. It is noticed that the saturation
magnetization increased by increasing the Zn content
up to x = 0.4 and further it is decreased. It is also
observed that the variation of AC susceptibility with
temperature explained the formation of single domain
particle nature for compositions x 0.2, and multi-
domain particle nature for the compositions x 0.4. The
Curie temperatures are found to decrease with
increasing the zinc composition. Finally, they noticed
that above the room temperature for the composition
x = 1.0 exhibits the paramagnetic behaviour.
Rimi Sharma and Sonal Singhal [4] studied the
structural, magnetic and electrical properties of Znx Ni1-x
Fe2 O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) ferrites using
sol-gel method. XRD pattern confirmed the formation of
spinel cubic structure. TEM result showed the particle
size in the range of 15 20 nm for the samples sintered
at 1000 0C. The FTIR spectra showed two fundamental
absorption bands around 580 cm-1 and 430 cm-1 as the
main characteristic of ferrite. VSM results reveal that the
saturation magnetization increased up to x = 0.4 and
then it is decreased, where as coercivity is decreased
with increasing the Zn composition. It is found that the
DC resistivity increases continuously by increasing the
Zn composition, this may be due to decrease in Fe2+
Fe3+ hopping. Finally, they observed that an increase in
photo catalytic degradation of methylene blue is found
with increasing the Zn content.
Rama Krishna et. al [5] prepared and studied the
structural and thermo electrical properties of Ni1-x Znx
Fe2 O4 where (x = 0.0, 0.2, 0.4, 0.6, 0.8, 0.9 and 1.0)
ferrites using the citrate gel auto-combustion method.
The XRD technique supported the formation of single
phase spinel structure. The Seebeck coefficient of the
samples is determined from thermo e.m.f
measurements by keeping a fixed temperature
difference of 10 K across the pellet and its value is
found negative, which is showing that the majority
charge carriers are electrons. The variation of thermo
electric power and charge carrier concentration both are
discussed on the basis of composition and temperature.
 3
Mohit et. al [6] synthesized and characterized the
structural, optical and dielectric properties of Nix Zn1-x
Fe2 O4 (0 x 1) ferrites using the auto combustion
technique. The XRD results support the formation of
spinel structure with average crystallite sizes in the
range 18 23 nm. It is observed that the lattice
parameter increased from 0.8372 to 0.8429 nm with
increasing Zn composition. FTIR spectra showed two
fundamental absorption bands in the range 588 - 556
cm-1 and 430 - 409 cm-1 as the main characteristic of
ferrite. Photo luminescence analysis indicated the
intense emission in the wavelength range lying in the
blue-green region. The highest intensity is observed for
x = 0.2 and explained with the help of disordered cluster
model. The composition at x = 0.2 showed the lowest
dielectric loss and highest dielectric constant in the
studied frequency range of 1 to 107 Hz. The AC
conductivity explained power law behaviour and
conduction behaviour with the help of hoping
mechanism.
Tayade et. al [7] synthesized and characterized the
structural properties of Ni1-x Znx Fe2 O4 (x = 0, 0.1, 0.2
and 0.3) ferrites by sol-gel auto combustion technique.
Formation of single phase spinel structure with a
crystallite size in the range of 20 30 nm is observed
from XRD analysis. The lattice parameters found to
increase with increasing the Zn2+ concentration.
Srinivas et. al [8] prepared and studied the structural
and magnetic properties of Nix Zn1-x Fe2 O4 (x = 0.5, 0.6
and 0.7) using the
co-precipitation technique and heat treated at 200 0C.
XRD and FTIR studies supported the formation of spinel
phase structure of the samples. It is also found that the
crystallite size, saturation magnetization, blocking
temperature increased where as lattice parameter and
coercive field decreased with the increase of Ni2+ ion
concentration. VSM results supported that all particles
exhibit
superparamagnetic behaviour at room temperature.
Hemeda et. al [9] prepared and studied the structural
and electrical properties of Zn1x Nix Fe2 O4 Ferrites (x =
0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) using the combustion
technique. The XRD analysis showed that the samples
are formed as single phase spinel cubic structure. The
SEM study revealed that the samples consist of grains
with relatively homogeneous distribution and it is found
that an average size varying from 0.85 to 0.92 m. It is
observed that the AC resistance decreases by
increasing the applied frequency from
1 KHz to 10 KHz. As the applied frequency increases
the charge hopping also increased hence the resistivity
decreased.
Kumbhar et. al [10] prepared and studied the structural
and electrical properties of Nix Zn1-x Fe2 O4 (x = 0.5, 0.6,
0.7, 0.8, 0.9 and 1.0) Ferrites using spray pyrolysis
technique. XRD pattern showed that the prepared
samples are polycrystalline with spinel cubic structure.
The SEM images showed that the films are soft and
uniform in nature. Frequency dependence of dielectric
constant explains the dielectric dispersion due to the
Maxwell-Wagner type of interfacial polarization. It is
observed that the DC resistivity of the prepared thin
films decrease with increasing the temperature because
of semiconductor nature. And it is also noticed that the
drift mobility of charge carriers increased with increasing
the temperature.
Yan et. al [11] prepared and studied the structural and
magnetic properties of Nix Zn1-x Fe2 O4 (x = 0.2, 0.4, 0.6
and 0.8) ferrites by the solvothermal method. The XRD
pattern confirms the formation of single phase spinel
cubic structure. The EDX spectra showed that as-
prepared Nix Zn1-x Fe2 O4 nano ferrite samples contain
Ni, Zn, Fe and O, and no contamination element is
detected. According to VSM results it is noticed that the
saturation magnetization increased with increasing Zn2+
ion concentration. The magnetic Nix Zn1-x Fe2 O4
microspheres are expected to apply in bionanoscience
and electronic devices technology.
Wu et. al [12] successfully synthesized and
characterized the structural and magnetic properties of
Ni0.5 Zn0.5 Lax Fe2x O4 (x = 0, 0.1, 0.2, and 0.3) ferrites
using the solid-state reaction method at low
temperatures. The X-ray data confirmed the successful
formation of single phase spinel structure at 600 0C.
They noticed that the magnetic properties of Ni0.5 Zn0.5
Lax Fe2x O4 ferrites depend on the composition and
sintering temperature. Also observed that La3+ ions can
improve the coercivity of Ni0.5 Zn0.5 La0.3 Fe1.7 O4 and got
the largest value of coercivity around 120 Oe at 800 0C.
A. A. Bayoumy [13] prepared and characterized the
Mg0.8-x Znx Ni0.2 Fe Cr O4 (x = 0.0, 0.2, 0.4, 0.6 and 0.8)
ferrites by the sol-gel template using cationic, anionic
and non-ionic surfactants. The XRD results confirmed
the polycrystalline single-phase cubic spinel structure
with average crystallite size in the range of 10-15 nm.
VSM results said that the magnetic hysteresis loops are
very narrow which conclude that prepared powders
showed superparamagnetic nature. The samples
showed smaller magnetization values due to the larger
 4
surface-to-volume ratio and spin canting on their
surface.
K. Arjun Kumar and D. Ravinder [14] synthesized and
characterized the electrical transport properties of
erbium doped
NiZn ferrites Ni0.7 Zn0.3 Erx Fe2-x O4 (x = 0.2, 0.4, 0.6,
0.8 and 10) by double sintering ceramic technique. The
Seebeck coefficient (S) values supported that the
investigated samples have been classified as n type
semiconductors. It is observed that the activation
energy in the paramagnetic region is higher than that in
the ferrimagnetic region. The resistivity and
thermoelectric power for gadolinium doped ferrite
samples are found higher than the erbium doped
ferrites. The higher resistivity can be explained due to
the increase in the lattice strain, this is because of the
higher ionic radius of gadolinium compared with the
erbium.
Abdullah Dar et. al [15] prepared and studied the
magnetic and dielectric properties of Ni0.5-x Cu0.2 Zn0.3
Mgx Fe2 O4 (0.0 x 0.4) ferrites using sol-gel
technique. It is found that the permittivity increased to
maximum value of around 8102 F/m for x = 0.4
sample. A significant decrease in loss tangent and
power loss has been observed with the increase of Mg
compositition. Also observed that the magnetic
properties are improved in the magnesium substituted
nickel copper zinc nanoferrite and the coercivity is found
to decrease with Mg content. Low coercivity materials
find wide usage in power applications.
Samoila et. al [16] synthesized and characterized the
structural and magnetic properties of Ni0.8 Zn0.2 Fe1.98
Dy0.02 O4 ferrites are prepared by sol-gel auto
combustion method using four different
chelating/combustion agents: citric acid, tartaric acid,
urea and cellulose. The XRD and IR spectra confirmed
the formation of single spinel cubic structure. The best
catalytic activity is belonging to the sample attained
using urea, which shows the smallest grain size, the
highest specific surface area (BET measurements) and
DyFeO3 phase. The ferrimagnetic behaviour for all the
samples exists independently of fuel agent.
S. A. Saafan and S. T. Assar [17] prepared and studied
the dielectric behaviour of Li0.1 (Ni1-x Znx)0.8 Fe2.1 O4 (x =
0.0 1.0) ferrites prepared by the chemical co-
precipitation technique. The AC electrical conductivity of
the samples increased with increasing temperature,
which showed the semiconducting behaviour of both
bulk and nano samples. The significant decrease in AC
conductivity, dielectric constant and dielectric loss is
observed with composition. The decrease in
conductivity and dielectric losses may be useful in many
applications for the reduction of eddy current effects.
K. Arjun Kumar and D. Ravinder [18] prepared and
studied the electrical conductivity of NiZnGd mixed
ferrites using the conventional double-sintering method.
It is observed that the activation energy in the
paramagnetic region is higher than in the ferromagnetic
region. They also noticed that the high activation energy
and low conductivity values of ferrites.
Arjun Kumar et. al [19] prepared and studied the
structural and the high frequency dielectric performance
of Ni0.7 Zn0.3 Erx Fe2-x O4
(x = 0.2, 0.4, 0.6, 0.8 and 1.0) ferrites using the
conventional double sintering ceramic technique. The
XRD analysis showed the formation of spinel cubic
structure. It is observed that the dielectric constant
increased steadily with increasing the temperature up to
a certain level, known as the dielectric transition
temperature (Td). Beyond this temperature the dielectric
constant values for all samples found to decrease
continuously.
S. R. Kulkarni [20] prepared and studied the structural,
dielectric, magnetic and DC resistivity of Mn0.1 Ni0.6 Zn0.3
Inx Fe2-x O4
(x = 0.05, 0.1, 0.15 and 0.2) ferrites using sol-gel
technique. The XRD analysis showed the formation of
spinel cubic structure. DC resistivity, AC resistivity and
the dielectric permeability are calculated and noticed
that the highest resistivity value of the sample is at x =
0.1. The VSM analysis showed that all the samples
exhibit the super paramagnetic behaviour and the
maximum saturation magnetization (36.2 emu/g) and
low coercivity (7 Oe) is observed for the sample for x =
0.1. It is observed that the saturation magnetization
increased with In3+ substitution up to x = 0.1 and further
it decreased rapidly. These materials may be applied in
high frequency electronic devices.
Sujatha et. al [21] synthesized and characterized the
effect of sintering temperature (900 0C, 950 0C and
1030 0C) on the structural, magnetic and dielectric
properties of Ni0.50 Cu0.05 Zn0.45 Fe2 O4 ferrites using sol
gel technique by using polyvinyl alcohol as a chelating
agent. XRD pattern showed the formation of single
phase cubic spinel structure. Microstructure and grain
size of the samples are investigated by FESEM. It is
observed that homogeneous grains of polyhedral shape
are independent of temperature but the grain size is
found to increase with increasing sintering temperature.
It is also observed that the saturation magnetization
 5
increased with sintering temperature up to 950 0C and
further it decreased. Low magnetic losses, high
saturation magnetization and high frequency stability of
permeability are observed in the samples which is
sintered at 950 0C.
A. T. Pathan and A. M. Shaikh [22] synthesized and
characterized the structural properties of Li0.5 Ni0.15 Co0.1
Zn0.5 Fe2 O4 ferrites using the auto combustion
technique. The XRD study found the particle size is
around 23 nm which is very close to the particle size 30
nm obtained from TEM analysis. The lattice constant of
the prepared sample is found as 8.376 . IR spectra
showed two main bands observed around 600 and 400
cm-1 as the main characteristic feature of a ferrite.
Navneet Singh et. al [23] prepared and studied the
structural, magnetic and dielectric properties of Ni0.5-x
Zn0.5 Mgx Fe2 O4 Ferrites using the solgel auto
combustion technique. The XRD pattern supported the
formation of spinel structure which is very well
agreement with TEM results. IR spectra showed the two
frequency bands around 569 cm-1 and 400 cm-1, which
is the main characteristic feature of ferrite. The dielectric
measurements reveal that the dielectric constant,
dielectric loss and AC conductivity are found to
dependent on applied frequency of external field,
temperature and microstructure of the samples. VSM
measurements reveal that the coercivity decreases and
saturation magnetization increases with increasing Mg2+
ions and it is noticed that saturation magnetization (Ms)
and Coercivity (Hc) depends on annealing temperature.
Ali Ghasemi et. al [24] synthesized and studied the
structural and magnetic properties of Ni0.6 Zn0.4 Fe2-x
Crx/2Alx/2O4 (x = 0.0 0.5) ferrites using the sol-gel auto
combustion method. It is noticed that the XRD analysis
confirmed the formation of single-phase cubic spinel
structure. FTIR results indicated the formation of
functional groups belonging to Ni-Zn spinel ferrites from
the sol-gel preparation. FESEM micrographs
demonstrated the nanoparticles with narrow size
distribution. According to the VSM results it is observed
that the saturation magnetization decreased with
increasing the composition.
Mahesh Kumar et. al [25] prepared and characterized
the structural, magnetic and DC resistivity of Ni0.65 Zn0.35
Fe2-x Gdx O4
(x = 0.00 5 mole %) ferrites using sol-gel method.
XRD analysis confirmed the formation of spinel cubic
structure. Lattice constant is slightly increased with
increasing the gadolinium substitution. The VSM results
showed that the saturation magnetization initially
decreases rapidly up to 2 mol% of gadolinium and then
it decreased slightly for higher concentrations. It is
observed that at room temperature the DC resistivity
gradually decreased with increasing gadolinium
concentration except for 1 mol %. The decrease in DC
resistivity might be understood due to the formation of
secondary phase of GdFeO3 along with the NiZn
ferrite.
Ati et. al [26] studied the structural and magnetic
properties of
Ni1-x Cox Fe2-x Alx O4 (x = 0.0, 0.2, 0.4, 0.6 and 0.8)
ferrite nanoparticles prepared using the co-precipitation
method. XRD analysis showed the formation of single
phase spinel structure. Particle size is found in the
range 15 - 19 nm for samples annealed at 600 0C. The
VSM results support the ferromagnetic behaviours of
CoAl substituted Ni ferrite nanoparticles. The
improvement of magnetic properties with the increase of
CoAl contents is recognized to anisotropic nature of
the ions. This method is simple, economic and produces
large scale high quality Ni nanoferrite powders which
are used in memory devices.
H. F. Abosheiasha and S. T. Assar [27] prepared and
characterized the structural, magnetic and thermal
properties of Ni0.92 Ca0.08 Fe2 O4 Ferrites using the citrate
precursor method. The grain size of the sintered
samples are predicted from XRD and TEM, it has been
found that particle size is increased by increasing the
sintering temperature than increasing the sintering time.
The remanent magnetization and saturation
magnetization of the samples are decreased with
increasing the sintering temperature and time. Finally
they noticed that the sintering process resulted in high
densification, less porosity and greater thermal
diffusivity of the samples.
Sujatha et. al [28] investigated the structural, magnetic,
electrical and dielectric properties of Ni0.5-2x Mgx Cu0.05
Zn0.45+x Fe2 O4 (x = 0.0, 0.04, 0.08, 0.12 and 0.16)
ferrites by solgel method using polyvinyl-alcohol as a
chelating agent. The XRD study confirmed the formation
of single spinel structure and the FTIR spectra showed
two main bands (400 cm-1 and 600 cm-1) which support
the feature of a ferrite. VSM study revealed that the
gradual decrease in coercivity and magnetization with
the substitution of Ni, Zn and Mg. It is observed that the
dielectric loss and dielectric constant both decreased
with the composition. Finally, it is also noticed that the
substitution of Mg and Zn for Ni in Ni-Cu-Zn ferrite
samples can enhance resistance of the samples. These
 6
samples exhibit good electromagnetic properties that
are suitable for high frequency electronic applications.
Pervaiz and Gul [29] studied the Al3+ and Cr3+
substituted Co-Ni ferrites with the compositions of 0.0 to
0.25 by using the sol-gel method. XRD analysis
revealed the formation of the mixed spinel structures.
The particle size, lattice constant and X-ray density
decreased with increasing the composition due to
decrease in the ionic radii and atomic weights of the
doping cations. DC resistivity of cobalt ferrites is
improved by increasing the Al3+ and Cr3+ up to
x = 0.2, further it deceased at x = 0.25 due to the
increase of Fe3+/Fe2+ ion pair concentration which is
responsible for the electrical properties. It is observed
that the dielectric constant and dielectric loss decrease
with increase of composition (x). AC conductivity is
observed to increase linearly with the applied field that
shows an increase in the conductivity and small polaron
conduction mechanism. VSM studies investigated that
both coercivity and magnetization values decreased
with increase of the Al and Cr concentrations. High DC
resistivity and low dielectric value of Ferrites are used in
high frequency and electromagnetic wave absorbing
devices.
Arjun Kumar et. al [30] prepared and studied the
structural and electrical conductivity of Ni1-X CuX Fe2 O4
(X = 0, 0.2, 0.4, 0.5, 0.6, 0.8 and 1.0) by using the
Citrate gel auto combustion method. The X-ray
diffraction pattern confirmed the formation of single
phase spinel structure with the average crystallite size
in the range 36 58 nm. It is observed that with
increasing the Cu composition the X-ray density and
porosity is increased where as the bulk density
decreased. The DC electrical conductivity is observed to
increase with increasing the Cu composition and
attained the maximum value at x = 1.0. The activation
energy is found to decrease with increasing Cu
substitution.
Ranjith Kumar et. al [31] synthesized and characterized
the structural and magnetic properties of Mn1-x Nix Fe2
O4 ferrite nanoparticles using the thermal evaporation
with egg white technique. The FTIR spectra revealed
that the high and low frequency bands formations
between 600 400 cm-1 is the common feature of
ferrites. VSM results revealed the magnetic properties
of MnNiFe2O4 at different annealing temperatures and
have been observed that the saturation magnetization
increased with annealing temperature due to increase in
the particle size.
Satish Verma et. al [32] synthesized and studied the
structural and magnetic properties of Mg0.2 Mn0.5 Ni0.3 Inx
Fe2-x O4 ferrites with x varying from 0.1 to 0.3 in steps of
0.1 using citrate precursor technique. XRD study
confirmed the formation of single phase cubic spinel
structure. TEM images confirmed the formation of micro
structure. Initially, the lattice constant increased up to x
= 0.1 and then it is decreased with increasing of
composition. The non-linear behaviour of lattice
constant is explained due to substitution of larger In3+
ions (0.91) with smaller Fe3+ ions (0.67) in Mg-Mn-Ni
ferrite. They observed that the initial permeability kept
fairly constant over a wide frequency range (0.075
10MHz) and got the low values of relative loss factor
(10-6 10-5) in the same frequency range are the main
success of their investigations. These Ferrites find wide
usage in microwave devices.
N. M. Deraz and A. Alarifi [33] processed and evaluated
the structural and magnetic properties of the alumina
doped nickel ferrite nanoparticles by the combustion
technique. The X-ray analysis showed that all samples
are formed into spinel cubic structure.
The lattice parameters are observed to decrease by
increasing the alumina content. Remarkable changes
are observed in the microstructure and porosity of nickel
ferrite by increasing the alumina. It is also observed that
the alumina doping will increase the surface area of Ni
ferrite, hence the saturation magnetization is found to
decrease.
Kumar et. al. [34] synthesized and characterized the
structural and magnetic properties of Ni1x Cux Fe2 O4 (x
= 0.0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and 1.0)
Ferrites using the sol-gel technique. The XRD pattern
clearly showed the formation of single phase spinel
structure. The lattice parameter is found to increase with
increasing the copper concentration. VSM analysis
revealed that the saturation magnetization exhibits a
non-collinear ferrimagnetic structure for x = 0.0 to 0.5
and exhibits the Neels collinear ferrimagnetic structure
for x = 0.5 to 0.9 suggesting a change in magnetic
ordering.
Uday Bhasker Sontu et. al [35] synthesized and
characterized the structural, magnetic and electrical
properties of Co1-x Nix Fe2 O4
(x = 0.0, 0.25, 0.5, 0.75 and 1.0) ferrites using the self-
combustion method. XRD pattern confirmed the spinel
cubic structure. Lattice constant values are observed to
decrease with increasing the nickel composition. VSM
analysis revealed that the saturation magnetization,
remanent magnetization and coercivity decreased with
 7
increase of nickel concentration. It is found that the
magnetic and electrical properties can be tuned by
varying the nickel concentration.
Pervaiz and Gul [36] prepared and studied the
structural, magnetic, high frequency AC response and
DC resistivity of Ni Hox
Fe2-x O4 (x = 0.0 - 0.15) Ferrites by sol-gel auto
combustion method. XRD pattern revealed the
formation of spinel cubic structure and SEM images
showed the spherical and uniformly distributed
homogenous nanoparticles. Lattice parameter
increased and crystallite size decreased with increasing
the concentration of Ho3+ ions. VSM results showed that
the saturation magnetization decreases with increasing
Holmium ion substitution. It is found that the frequency
dependent dielectric parameters like relative permittivity
and dielectric loss decreased by increasing the Ho3+ ion
concentration. It is also noticed that the DC resistivity
increases from 107 -cm to 1010 -cm with holmium
ions substitution. High frequency behaviour, low losses
and high DC resistivity materials are used in
electromagnetic devices.
H. M. Abdullah and Thomas Moyo [37] synthesized and
characterized the Ferrites of Mnx Ni1-x Fe2 O4 (x = 0.1,
0.3 and 0.5) by glycol-thermal technique. The XRD
results supported the formation of spinel structures with
average crystallite sizes of about 8.5 nm. VSM analysis
showed that the samples exhibit low remanent
magnetization and coercive field. Mossbauer analysis
revealed the super paramagnetic behaviour of samples.
Sridhar et. al [38] synthesized and characterized the
structural properties of Ni1-x Cux Fe2 O4 (x = 0, 0.2, 0.4,
0.6, 0.8, 0.9 and 1.0) ferrites prepared by citrate gel
technique. The XRD pattern confirmed the formation of
single phase cubic spinel structure with an average
crystallite size in the range of 36 - 58 nm. The lattice
constant is found to decrease with the increase of Cu
composition. It is also observed that the X-ray density
and the distance between the magnetic ions are found
to increase by increasing the Cu composition.
Khan et. al [39] prepared and studied the structural,
magnetic and high frequency dielectric response of Zn1-
x Tbx Fe2 O4 (x = 0.0, 0.03, 0.06, 0.09, 0.12 and 0.15)
ferrites by the micro emulsion method. The XRD pattern
confirmed the single spinel structures with grain sizes in
the range of 16 24 nm. The VSM results revealed that
Tb3+ doped zinc ferrites show ferrimagnetic nature. The
dielectric measurements showed that the dielectric loss
and dielectric constant of the samples are found to
decrease with increase in Tb3+ composition and applied
frequency. The prepared materials can be used in
memory devices and high frequency applications.
Manikandan et. al [40] studied the structural, optical and
magnetic properties of Zn1-x Cux Fe2 O4 (x = 0.0, 0.1,
0.2, 0.3, 0.4 and 0.5) ferrites by the microwave
combustion method. The XRD study confirmed the
formation of a single phase spinel structure with an
average crystallite size in the range of 41 46 nm. It is
also observed that the lattice parameters value
decreased from 8.443 to 8.413 with increasing the Cu
composition. VSM study revealed that for lower Cu
composition (x 0.2) samples showed the
superparamagnetic nature and for higher Cu
composition (x 0.2) it changes into ferromagnetic
behaviour. They noticed that saturation magnetization
value changes with Cu composition. The maximum
saturation magnetization of 58.58 emu/g is observed for
Cu0.5 Zn0.5 Fe2 O4 composition.
H. Anwar and A. Maqsood [41] studied the structural,
electric and magnetic properties of Mn0.5 Zn0.5-x Cdx Fe2
O4 (x = 0.0 0.35) ferrites synthesized by the solgel
auto combustion technique. The XRD study supports
the formation of a single phase spinel structure and the
average crystalline size found in the range 24 50 nm.
The dielectric properties and AC conductivity are
studied in the frequency range
20 - 5 MHz. The low dielectric constant and loss tangent
is observed for x = 0.25. The DC resistivity is attained
high value as 2.2 x 1011 -cm at 373 K and the
activation energy values speak the conduction in Cd2+
doped Mn-Zn ferrite due to the hopping of polarons.
VSM study carried out to measure the magnetic
moment and the saturation magnetization is observed to
increase the cadmium composition up to x = 0.25.
Finally, it is noticed that the addition of cadmium
enhanced the electrical and magnetic properties of Mn-
Zn Ferrites. The substitution of Cd2+ ions may modify
the electrical and magnetic properties in Mn-Zn ferrites
which are suitable for power applications and
microwave devices.
Sattar et. al [42] studied the magnetic and electrical
resistivity of Li0.3+0.5x Zn0.4 Zr0.4 Fe2.3-1.5x O4 (x = 0.0,
0.01, 0.02, 0.03 and 0.05) Ferrites by the standard
ceramic method. VSM studies reveal that the saturation
magnetization increased up to x = 0.02 and then it is
further decreased. The initial permeability increased,
where as the Curie temperature is almost constant with
increasing the composition. It is also observed that the
DC resistivity depends on the composition and
explained due to the hopping conduction mechanism.
 8
Santosh Bhukal et. al [43] prepared and studied the
structural, magnetic, electrical and optical properties of
Co0.6 Zn0.4 Crx Fe2-x O4
(x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0) Ferrites by solgel
auto-combustion technique. XRD pattern supports the
formation of single cubic spinel structure. It is observed
that the lattice parameter decreased by increasing the
Cr3+ substitution. This is due to difference in the ionic
radii of Cr3+ (0.68 ) as compared with Fe3+ (0.73 ).
The electrical resistivity is observed to increase with
increasing Cr3+ content and the resistivity of all the
samples is found to decrease with increasing
temperature, which also showed the semiconductor
behaviour of the samples. The drift mobility is found to
increase with increasing temperature because of the
improved mobility of charges due to thermal activation.
Finally, the saturation magnetization decreased with
increasing the Cr3+ content due to the lesser magnetic
moment of Cr3+ ion (3B) than that of Fe3+ ion (5B).
Arjun Kumar et. al [44] prepared and studied the
structural properties of Co0.5 Ti0.5 Zn Fe O4 ferrites by the
sol-gel technique at different temperatures. The XRD
analysis showed the formation of spinel cubic structure
and it is found that the grain size increased from 48 nm
to 83 nm by increasing the sintering temperature. IR
spectral bands are observed around 600 cm-1 and 400
cm-1 of the tetrahedral and octahedral sites respectively.
The AC electrical resistivity is found to decrease with
increasing sintering temperature and the resistivity of
the samples is noticed to decrease with increasing the
frequency up to 10 MHz.
Raut et. al [45] prepared and characterized the
structural and magnetic properties of Co1-x Znx Fe2 O4
(0.0 x 1.0) ferrites by the
sol-gel auto combustion technique. Single phase cubic
structure is confirmed by XRD analysis. Compositional
stoichiometric ratio is confirmed by EDAX technique. It
is found that the lattice constant and X-ray density
increased with the increase of Zn2+ ion concentration.
FTIR spectrum confirmed two absorption bands near
400 cm-1 and 600 cm-1 characterizing the ferrite nature
of the prepared samples. According to the VSM results
it is observed that the magnetic properties like
saturation magnetization, remanent magnetization and
coercivity are observed to decrease with increasing Zn2+
ion concentration.
Samad Zare et. al [46] prepared and studied the
structural and magnetic properties of Co1-x Znx Fe2-x Alx
O4 (0.0 x 1.0) ferrites by the sol-gel auto
combustion method. The XRD spectra revealed the
formation of single phase spinel cubic structure. It is
found that the average size of nanoparticles is in the
range 17-30 nm. The FTIR spectra confirmed the two
characteristic absorption bands around 600 cm-1 and
400 cm-1. Saturation magnetization is found to increase
up to x = 0.4 while remanence magnetization and
coercivity decrease with increasing Zn2+ and Al3+ ion
concentration.
Hamed Bahiraei et. al [47] synthesized and
characterized the structural and electromagnetic
properties of Mg0.3 Cu0.2 Zn0.52 Alx Fe1.98-x O3.99 (0.00 x
0.06) Ferrites through the nitratecitrate auto
combustion route. The XRD pattern showed the
formation of spinel cubic structure. FTIR spectra
indicated two fundamental absorption bands
corresponding to the tetrahedral and octahedral sites
respectively. It is found that the density and grain size
increased with increasing Al3+ ion concentration. At
room temperature the VSM study confirmed that the
saturation magnetization increases up to x = 0.015,
further it is decreased by increasing the Al3+ ion
concentration. The permeability increased and Curie
temperature decreased with increasing Al3+
concentration.
Surender Kumar et. al [48] prepared and studied the
structural and DC resistivity of Mn0.4 Zn0.6 Iny Fe2-y O4
(0.0, 0.035, 0.070 and 0.100) ferrites by the oxalate co-
precipitation technique. It is observed that the lattice
constant, crystallite size and X-ray density increased
with increasing the indium ion substitution. The DC
resistivity observed to increase with indium ion
substitution. Differential method is used to study the
thermoelectric power and it is observed that the thermo
e.m.f remains constant with increasing temperature.
Balaarjunlakshmi et. al [49] studied the structural and
dielectric properties of Cox Cu1-x Fe2 O4 (x = 0.0, 0.2,
0.4, 0.6, 0.8 and 1.0) ferrites by the co-precipitation
method. The XRD pattern showed the formation of
spinel structure with crystalline size in the range 3 18
nm. The crystallite size is decreased with Cu content.
The FTIR spectra showed two main absorption bands
around 500 cm-1 to 400 cm-1 which corresponds to the
vibration modes of all spinel compounds. It is also
observed that the dielectric constant changes from
522.31 to 10.44 and it is noticed that the high value is
due to the lower grain size and high value of crystallites.
Muthuram et. al [50] synthesized and characterized the
structural, electrical and magnetic properties of Mg Cex
Fe2x O4 (x = 0.01, 0.012, 0.014 and 0.016) ferrites by
the sol-gel route. The XRD results showed the spinel
 9

structure with the average particle size in the range 46 explained on the basis of MaxwellWagner type of
82 nm. It is observed that the lattice parameter interfacial polarization in accordance with the Koops
decreased with composition and crystallite size is found theory. VSM study revealed that the magnetic moment
to increase with Ce3+ content. The dielectric properties of the prepared samples decreased with an increase of
are studied for the ferrite samples in the frequency Al3+ ion doping.
range 2.4 to 4 GHz. The VSM results confirmed that the Rajesh Babu et. al [54] prepared and studied the
coercive field and saturation magnetization increased structural and magnetic properties of Ni0.5 Zn0.5 Alx Fe2-x
with the increase of Ce3+ composition. The variation of O4 ferrite nanoparticles by using the nitrate citrate auto
magnetic properties with doping content is explained on combustion technique. The XRD pattern clearly showed
the basis of particle size. The samples exhibited the the formation of single phase spinel structure. It is
piezoelectric properties confirming the smart behaviour observed that the lattice constant and saturation
of the ferrites. magnetization decreased with increasing the Al3+
S. C. Bhatt and Manish Uniyal [51] synthesized and concentration. The decrease in the magnetization is
Characterized the structural and dielectric properties of explained due to the canted spin structure present in the
K1-x Nax NbO3 (X = 0.0, 0.2, and 0.4) ferrites by the B-B sites. It is also found that the canting angle
conventional solid-state reaction method and sintering increases from 49.66 to 61.83 by increasing the Al3+
process. At room temperature the XRD study revealed concentration.
that all samples exhibited the orthorhombic structure.
The dielectric and electrical properties of the prepared
samples is investigated at applied frequency of 1 MHz
in the temperature range, 45 0C - 245 0C. It is noticed
that the loss tangent, dielectric constant and electrical
conductivity increased with increasing temperature.
Mukherjee et. al [52] prepared and studied the magnetic
and electrical properties of Multiferroic (Y, Mn)
substituted BiFeO3 by using a simple solgel route. The
XRD pattern confirmed the formation of a single phase
spinel structure. TEM study gave the particle size in the
range of 30 32 nm. The VSM studies revealed that the
samples exhibit the superparamagnetic behaviour up to
room temperature. They also noticed that reduction of
oxygen vacancies and bismuth vacancies can improve
the ferroelectric behaviour. The DC electrical properties
are estimated in the temperature range 298523 K and
explained using the hopping mechanism and calculated
the density of states at Fermi level. They also explained
the ac conductivity nature of the samples by considering
the correlated barrier hopping model and calculated
relaxation time, effective barrier height of the samples.
Mohd. Hashim et. al [53] synthesized and characterized
the structural, magnetic and electrical properties of Ni0.7
Zn0.3 Fe2-x Alx O4 (0.0 x 0.5) ferrites by the citrate-gel
auto combustion method. XRD study confirmed the
formation of single phase spinel structure with an
average grain size of 13 nm to 17 nm. The lattice
parameter is found to decrease with increasing Al3+
content. EDX pattern confirms compositional formation
of synthesized ferrites. The variation of dielectric
properties like , " and tan with applied frequency
showed the dispersion behaviour which can be
 10
3.1 Introduction
Research on ferrite nanoparticles is a great interest due
to their broad applications like magnetic memory [1],
magnetic fluids, permanent magnets, microwave
devices, disk recording, magnetic refrigeration systems
and high density information storage, co-efficient
hyperthermia for cancer therapy [2, 3] and catalysts [4].
Several researchers chose the various preparation
methods like
sol-gel auto combustion technique, spark plasma
sintering method, auto-combustion method, co-
precipitation method, reverse micelle process method
etc. Controlling the different properties of ferrites may
depend from method to method, preparation technique
and sintering conditions.
Present research work deals with the preparation of
Ferrites having the general formula of Series-I: Ni0.5
Zn0.5 Alx Fe2-x O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4,
1.6, 1.8 and 2.0) and Series-II:
Nix Zn1-x Al1.0 Fe1.0 O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0)
and they are prepared by sol-gel auto combustion
technique. The structural properties of nanoferrite
particles are investigated by using the various
techniques like X-ray diffraction (XRD), Scanning
electron microscopy (SEM) with Energy dispersive
spectroscopy (EDX) and Fourier transform infrared
radiation (FTIR).
To study the properties of the prepared nanoferrite
samples, the various characterization techniques are
used. The magnetic properties are studied with the help
of vibrating sample magnetometer (VSM), dielectric
properties using LCR impedance meter, DC resistivity
with two probe experimental set-up and I-V
characteristics by Keithely 4200 semiconductor
characterization system.
Present work deals with the preparation of Ni-Zn-Al
Ferrites using sol-gel auto combustion technique which
is a simple process and most economical. The main
advantages of sol-gel method compared to the
conventional methods are:
Sol-gel technique becomes most popular
because of its low processing temperature, the
possibility of controlling the size, high chemical
homogeneity and morphology of particles.
This method produces the high quality of
mixed ferrites.
One of the most important features of doped
sol-gel compounds is its nature for preserving the
chemical and physical properties of the dopants.
This method provides an excellent
homogenous grouping of constituent metallic ions of
compositions.
Sol-gel technique is well known as green
method.
In sol-gel method the reaction does not
require any special conditions and can be performed
easily.
In this method the chemical reactions include
a Series of simple hydrolysis and condensation process.
The main thought behind sol-gel method is to
dissolve the compound in a liquid in order to bring it
back as a solid in a controlled way.
Sol-gel technique gives the final product in
the form of small particles, which are easily sinterable.
3.2. Chemicals used for preparation of the ferrite
nanoparticles
The high purity analytical grade {AR} chemicals are
used for the preparation of Al3+ ion substituted Ni-Zn
Ferrites of Series-I and Series-II by sol-gel auto
combustion technique which is shown in Table 3.1.
3.2.1 Apparatus used for the preparation of ferrite
nanoparticles
The apparatus used for the preparation of Ni-Zn-Al
Ferrites are digital balance with accuracy of milligram,
magnetic stirrer with hot plate (2mLH), glass beakers,
500 ml measuring jars, KBr pellet press (5 tons), muffle
furnace (maximum 1000 0C), mortar pestle.
3.2.2 Synthesis route
The chemicals used in the prepared compositions are
nickel nitrate (Ni (NO3)2. 6H2O), zinc nitrate (Zn
(NO3)2. 6H2O), aluminium nitrate (Al (NO3)3. 9H2O),
ferric nitrate (Fe (NO3)3. 9H2O), citric acid (C6 H8 O7)
and ammonia (NH3). The complex solution of nickel
nitrate, zinc nitrate, aluminium nitrate and ferric nitrate
prepared by stoichiometric ratio and dissolved in
deionized water then citric acid is added to the prepared
solution in 3:1 ratio. Then the complex citrate solution is
heated on the hot plate with an arrangement of
magnetic stirrer until we get a homogenous solution.
Ammonia (NH3) is added drop by drop to the
homogenous solution to adjust its pH value at 7. The
solution is heated around 100 0C till the water is
completely evaporated.
The resulting gel is further heated around 300 0C on
the stirrer and the dried gel became a loose brown
powder. Finally, the loose brown powder is ground in a
mortar around half an hour. The complete experimental
procedure is shown in the Figure 3.1.
 11

Figure Error! No text of specified style in document..1:

Flow chart of sol-gel auto combustion technique
3.2.3 Calcination
The powder is calcinated in air at 600 0C for 5 hours in a
muffle furnace that is below its melting point. During this
process there is a possibility of partial formation of the
ferrite.
3.2.4 Pelleting the powder sample
The calcined fine powder again ground in a mortar
around 15 to 20 minutes and pelletized with the
dimensions around 1-2 mm thickness

Table Error! No text of specified style in document..1 :
List of chemicals used for the preparation of Ni-Zn-
Al Ferrites
and 10 mm diameter by using KBr hydraulic press by
applying a pressure of 5 tons/inch2 up to 10 minutes.
3.2.5 Sintering the pellet samples
This is the final and important step to form the ferrite.
Again the pellets are subjected to sintering by keeping
the constant temperature at 600 0C for 5 hours. During
the sintering process inter diffusion process occurs in
between the adjacent grains and they stick together,
hence the porosity decreases due to diffusion of the
ions. Iron, nickel and other ions can survive more than
one valance state as Fe3+ will change to Fe2+, and Ni2+,
Zn2+, Al2+ changes to Ni3+, Zn3+, Al3+ ions [5]
respectively.
3.3 X-Ray diffraction (XRD)
X-ray diffraction (XRD) is non-destructive type of
method that can analyze in order to identify crystalline
materials and the unit cell. The X-ray diffraction
technique is broadly used in various fields like material
science, geology and engineering to quickly identify the
unknown crystalline materials. The XRD technique
requires a pure, fine and homogeneous powder sample
for the determination of the bulk composition. This
method is also suitable for the identification of fine
grained materials.
This technique is invented by Max von Laue in 1912
and discovered that the crystalline materials act as a
diffraction grating for
X-ray wavelengths (~ 1 to 2 ) similar to the atomic
plane spacing in a crystal lattice [6]. When the
wavelength of the X-ray used is approximately equal to
inter planar distance of the crystal then the
X-ray radiation provides the diffraction pattern.
3.3.1 Braggs Law
The X-ray diffraction technique works on the Braggs
law which states X-rays reflected from different parallel
planes of a crystal interfere constructively when the path
difference is an integral multiple of the wavelength of X-
ray radiation.
i.e.
2d sin = n
3.1
Where, Wave length of the X-ray radiation,
Braggs angle
The crystalline structures are mainly studied by using
the following techniques.
12
Laue technique
Rotating crystal technique
Powder crystal technique
Laue and rotating crystal techniques are suitable for the
sample which is available in the form of single crystal.
But the powder crystal technique is suitable for the
sample which is especially in the form of powder.
3.3.2 Powder crystal technique
Power crystal technique is applied to study the structure
of fine powder crystalline materials using the X-ray
diffraction technique. Peter Debye and the German
physicist Paul Scherrer invented this method in 1916,
thus it is named as Debye-Scherrer method. This
technique is highly preferred when the sample is
available in the form of powder. This technique is also
used in mineralogy and chemistry for the finding of
different minerals and chemical compounds.
In this technique the powder crystal sample is placed in
contact with the X-ray beam so that it fulfils the Braggs
condition for diffraction. Consequently the
corresponding diffraction pattern is achieved on the
photographic film and further investigated the crystal
structural properties. The experimental set-up for Philips
XPert Diffractometer (Debye-Scherrer technique) is
shown in Figure 3.2.
Figure Error! No text of specified style in document..2:
Philips XPert Diffractometer
The powder sample is loaded in a glass capillary tube of
dimensions of approximately 0.5 mm in diameter, with a
glass thickness of around 0.01 mm. A film strip is used
for intensity recording. The film is placed around the
circle and the diffracted pattern is recorded on the film in
the possible 2 range. The recorded diffraction pattern
can be
directly viewed on the monitor. The most modern
diffractometers are equipped with a focusing
monochromator which allows the removal of the K2
radiation to give sharper peaks.
Generally in Debye-Scherrer method a narrow parallel
beam of monochromatic X-rays are used with the
wavelength of 1.5418 .
By the X-ray diffraction data the crystallite size is
calculated by the Debye-Scherrer formula (Equation
3.2).
t=
0.9
cos
3.2
 13

Where, t - crystallite size (nm), - wave length of X-ray

radiation,
- full width at half maxima (FWHM) and - Braggs
angle
3.3.3 Identification of ferrites from XRD data
The peak positions of X-ray diffraction data will give
each crystalline plane characteristic of synthesized
powder sample. In general, the characteristic planes of
single spinel cubic structure are (220), (311), (400),
(222), (422), (331), (333), (511), (440), (531), and (422)
[7]. Comparing the above characteristic planes with inter
planer distance (d) the values of powder crystal
structure can be estimated.
3.4. X-ray diffraction analysis of Ni-Zn-Al Ferrites
The Ni-Zn-Al nanoferrite particles are prepared and
characterized by X-ray diffraction pattern of Series-I and
Series-II. XRD analysis is done by the Philips X Pert X-
ray diffractometer with the wavelength () is equal to
1.5406 which is shown in Figure 3.2
3.4.1 X-ray diffraction analysis of Series-I ferrite
nanoparticles
The X-ray diffraction pattern of Series-I powder samples
is shown in Figure 3.3 and variation of lattice constant,
X-ray density, bulk density, porosity, crystallite size,
hopping lengths (LA and LB) with composition (x) are
tabulated in Table 3.2.
The XRD pattern of Series-I ferrite nanoparticles are
shown in Figure 3.3 and it is clear that all the samples
are showing the single phase spinel cubic structure. The
broadening of XRD peaks indicates the nano crystalline
structure of ferrites [8, 9]. The impurity peaks are
observed in the samples due to partial oxidation of the
spinel
Ni-Zn ferrites [10, 11]. The average crystallite size of the
ferrite nanoparticles are calculated from the most
intense peak (3 1 1) of XRD data by the Debye-Scherer
formula. From X-ray diffraction analysis it is found that
the crystallite size decreased from 51.47 to 17.15 nm by
increasing the Al3+ ion substitution [12].
3.4.2 Lattice constant
The lattice constant (a) values of prepared nanoferrite
samples is calculated by the following relation.
a = dh2 + k 2 + l2

3.3
Where, d inter planar spacing for a plane (hkl)
 14

Figure Error! No text of specified style in document..3 :

X-ray diffraction patterns of Ni0.5 Zn0.5 Alx Fe2-x O4
(x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8 and
2.0)

Table Error! No text of specified style in document..2:

Lattice constant (a), X-ray density (x), bulk density
(B), Porosity (P), crystallite size (t), tetrahedral and
octahedral lengths (LA and LB) of Ni0.5 Zn0.5 Alx Fe2-x
O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0,
1.2, 1.4, 1.6, 1.8 and 2.0)

Figure Error! No text of specified style in document..4 :
Variation of crystallite size with composition (x) of
Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0,
1.2, 1.4, 1.6, 1.8 and 2.0)
Figure Error! No text of specified style in document..5:
Variation of lattice constant with composition (x) of
Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0,
1.2, 1.4, 1.6, 1.8 and 2.0)
It is found that the lattice constant decreased from 8.472
to 8.205 with increasing the Al3+ ion substitution. This
is due to the larger Fe3+ (0.645 ) ions are replaced by
the smaller Al3+ (0.55 ) ions. The similar tendency is
discussed elsewhere in aluminium substituted Ferrites
[13-17].
3.4.3 X-ray density, Bulk density and Porosity
The X-ray density of the powder samples is determined
by the following equation.
8M
x = 3
Na
... 3.4
Where, xX-ray density, Mmolecular weight of the
sample,
NAvogadro number and a lattice constant
The X-ray density of Series-I ferrite nanoparticles is
observed to decrease from 5.373 to 4.328 g/cm3 with
increasing of Al3+ ion substitution. This may be
explained on the basis of molar mass of Al3+ (26.98 g
mol-1) which is lower than that of Fe3+ (55.85 g mol-1)
[18]. Another reason for this behaviour is explained due
to decrease in the lattice constant and particle size [12].
The bulk density of the prepared ferrite samples is
determined by the following equation.
B = 2
m 3.4.5 X-ray diffraction analysis of Series-II ferrite
r t
... 3.5
Where, bulk density, m mass of the pellet, r
radius of the pellet and t thickness of the pellet
It is observed that the bulk density increased from 4.072
to 4.152 g/cm3 and porosity is decreased from 24.21 to
4.06% with increasing the Al3+ ion substitution. This may
be explained that the bulk density and porosity are
inversely related to each other [18].
The variation of composition (x) with X-ray density,
bulk density and variation of composition (x) with
porosity is shown in Figure 3.6 and 3.7 respectively.
15
Figure Error! No text of specified style in document..6 :
Variation of density with composition (x) of
Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0,
1.2,
1.4, 1.6, 1.8 and 2.0)
Figure Error! No text of specified style in document..7:
Variation of porosity with composition (x) of
Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0,
1.2,
1.4, 1.6, 1.8 and 2.0)
3.4.4 Hoping lengths of tetrahedral and octahedral
sites
The hopping lengths of tetrahedral (LA) and octahedral
(LB) sites of Series-I ferrite nanoparticles are calculated
by equations 3.6, 3.7 and furnished in Table 3.2.
3
LA = ( )a
4
...
3.6
2
LB = ( )a
4
3.7
Where, a lattice constant
The LA and LB values are decreased from 3.668 to
3.552 and 2.994 to 2.900 respectively with increase
of Al3+ ion substitution [18]. From equations 3.6 and 3.7,
the hopping lengths are directly proportional to lattice
constant, hence it is understood that as the lattice
constant decreases the hoping length decreases.
Similar results are observed in Mg-Ni Ferrites [19].
nanoparticles
The X-ray diffraction pattern of Series-II powder
samples having the general formula of Nix Zn1-x Al1.0
Fe1.0 O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) is shown in
Figure 3.8. The XRD pattern of Series-II ferrite
nanoparticles calcined at 600 0C is shown in Figure 3.8.
It is found that the XRD results confirmed the single
phase spinel cubic structure [20, 21]. The average
crystallite size of the powder nanoparticles is calculated
by Debye-Scherer formula (Equation 3.2). X-ray
diffraction analysis confirmed that the average crystallite
size is decreased from 45.74 to 14.70 nm by increasing
the Ni2+ ion substitution. The structural data is furnished
in Table 3.3.
 16

Figure Error! No text of specified style in document..8:

X-ray diffraction pattern of Nix Zn1-x Al1.0 Fe1.0 O4 (x =
0.0, 0.2, 0.4, 0.6, 0.8 and 1.0)

Table Error! No text of specified style in document..3 :

Lattice constant (a), X-ray density (x), bulk density
(B), Porosity (P), crystallite size (t), tetrahedral and
octahedral lengths (LA and LB) of Nix Zn1-x Al1.0 Fe1.0
O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0)

Figure Error! No text of specified style in document..9:
Variation of crystallite size with composition (x) of
Nix Zn1-x Al1.0 Fe1.0 O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and
1.0)
3.4.6 Lattice constant
The lattice constant values of prepared ferrite
nanoparticles are calculated using the Equation 3.3. It is
observed that the lattice constant linearly decreased
from 8.334 to 8.281 with increasing the Ni2+ ion
substitution indicating the lattice shrinkage. The linear
variation of lattice constant can explain by Vegards law
[22]. The decrease in the lattice constant with the
increase of Ni2+ ion substitution may be explained due
to the substitution of smaller Ni2+ (0.74) ions in place
of larger Zn2+ (0.84 ) ions in the ferrite system. Similar
results are reported by several investigators in case of
Ni-Zn Ferrites [23 - 27].
3.4.7 X-ray density, Bulk density and Porosity
The X-ray density of the Series-II powder samples is
determined by Equation 3.4 and it is found to decrease
from 4.869 to 4.807 g/cm3 with increasing of Ni2+ ion
substitution. This is due to the replacement
Figure Error! No text of specified style in document..10:
Variation of lattice constant with composition (x) of
Nix Zn1-x Al1.0 Fe1.0 O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and
1.0)
of higher atomic mass of Zinc (68.38 amu) by lower
atomic mass of Nickel (58.69 amu). The obtained
results are well agreed with the reported values by
several investigators in case of Mg-Ni Ferrites [28, 29].
The bulk density of the prepared ferrite samples is
determined using the Equation 3.5. It is noticed that the
bulk density increased from 3.784 to 3.997 g/cm3 and
porosity decreased progressively from 22.28 to 16.85 %
with increase of Ni2+ ion substitution and it is clear that
the nickel ferrite is having the least porosity. Increasing
the Ni2+ ion substitution the porosity decreases which
confirms densification of the material [30]. It is clear that
the bulk density and porosity are inversely related with
each other. Hence an increase in the bulk density will
decrease the porosity.
The variation of X-ray density, bulk density with
composition (x) and variation of porosity with
composition (x) is shown in Figure 3.11 and 3.12
respectively.
17
Figure Error! No text of specified style in document..11:
Variation of X-ray and bulk density with
composition (x) of Nix Zn1-x Al1.0 Fe1.0 O4 (x = 0.0, 0.2,
0.4, 0.6, 0.8 and 1.0)
Figure Error! No text of specified style in document..12:
Variation of porosity with composition (x) of
Nix Zn1-x Al1.0 Fe1.0 O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and
1.0)
3.4.8 Hoping lengths of tetrahedral and octahedral
sites
The hopping lengths of tetrahedral (LA) and octahedral
(LB) sites of Series-II Ferrites are calculated with the
help of Equations 3.6 and 3.7. It is noticed that LA and
LB values are decreased from 3.609 to 3.586 and
2.946 to 2.927 respectively with increasing of Ni2+ ion
substitution. It is clear that the hopping lengths are
directly proportional to lattice constant. Hence as the
lattice constant decreases the hoping lengths decrease.
Similar trend is observed in the earlier reports for Ni-Zn
Ferrites [31].
3.5 Fourier transform infrared spectroscopy (FTIR)
Fourier Transform Infra Red (FTIR) is preferred method
of IR spectroscopy shown in Figure 3.13. In this
technique the IR radiations are sent through the sample,
then few of the IR radiation are absorbed by the sample
and remaining will be transmitted through the sample.
The resulting spectrum corresponds to the molecular
absorption and transmission which will generate a
molecular fingerprint of the sample. It is clear that no
two same molecular structures give the identical IR
spectra. This makes IR spectroscopy as a very helpful
technique for identifying different types of compounds.
Further, the peak size of spectrum indicates directly the
amount of material present. FTIR analysis identifies the
unknown materials that can give a fair idea about the
quality and quantity of components in a mixture. In
ferrites the IR spectra gives two absorption bands
arising from inter atomic vibrations are measured and
force constants calculated for the stretching of bonds
between octahedral or tetrahedral metal ions and oxide
ions. These force constants will be in agreement with
the elastic and thermodynamic properties of the
compounds. They are sensitive for distribution of metal
ions between the alternate sites. The integrated
vibrational band intensities are measured; they are
 18
compatible with predominantly ionic bonding for these
structures.
Figure Error! No text of specified style in document..13:
Block diagram of FTIR (model Nicolet 6700)
3.5.1 FTIR analysis of Series-I ferrite nanoparticles
The FTIR spectra of Series-I ferrite nanoparticles is
shown in Figure 3.14 and the tetrahedral frequency (1)
and octahedral frequency (2) values are shown in
Table 3.4. It is found that the tetrahedral frequency band
(1) is observed in the range 624 635 cm-1 and
octahedral frequency band (2) is in the range 417 - 420
cm-1. These bands are the common characteristics of
spinel cubic ferrite structures. The similar kinds of
results are reported in the literature [32, 33].
Figure Error! No text of specified style in document..14:
FTIR spectra of Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.0, 0.2,
0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8 and 2.0)
Table Error! No text of specified style in document..4:
Tetrahedral and octahedral vibrational frequencies
for different compositions (x) of Series-I ferrite
nanoparticles
3.5.2 FTIR analysis of Series-II ferrite nanoparticles
FTIR spectra of Series-II ferrite nanoparticles are shown
in Figure 3.15 and the tetrahedral frequency (1) and
octahedral frequency band (2) values are tabulated in
Table 3.5. It is noticed that the tetrahedral frequency
bands (1) are observed in the range 605 636 cm-1
and octahedral frequency bands (2) are found in the
range 404 - 414 cm-1. These bands are the common
characteristics of spinel cubic ferrite structure. The
similar results are reported by the several researchers
[34, 35].
Figure Error! No text of specified style in document..15:
FTIR spectra of Nix Zn1-x Al1.0 Fe1.0 O4
(x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0)
Table Error! No text of specified style in document..5:
Tetrahedral and octahedral frequencies for different
compositions (x) of Series-II ferrite nanoparticles
3.6 Scanning Electron Microscopy (SEM)
Max knoll [36] invented the Scanning electron
microscopy (SEM) in the year 1935. SEM technique is
used to get an image of a sample by scanning it with a
focused electron beams and used to observe the
surface morphology with high magnification. The high
energy electrons in SEM carry large amounts of kinetic
energy and this energy is dissipated as a wide range of
signals produced by electron-sample interactions when
the incident electrons are decelerated in the sample.
The signals that are obtained from the electron-sample
interactions reveal information about the sample
including external morphology, chemical composition,
crystalline structure and orientation of materials making
up the sample. In several applications, data is collected
over a selected area of the surface of the sample and a
two dimensional image will be generated that displays
spatial variations in these properties. Areas ranging
from approximately few nanometres to micrometers in
width can be imaged in a scanning mode using
conventional SEM techniques of magnification ranging
from 20X to approximately 30,000X, spatial resolution of
50 to 100 nm.
The SEM will be capable of performing analyses of
selected point locations on the surface of the sample,
this approach will be especially useful in qualitatively or
semi-quantitatively determining chemical compositions
with the help of EDX. These signals include secondary
electrons that produce SEM images, backscattered
electrons, diffracted backscattered electrons, photons,
visible light and heat. Secondary electrons and
backscattered electrons will be commonly used for the
Figure Error! No text of specified style in document..16:
Block diagram of SEM
imaging samples. Secondary electrons are most
important for showing morphology and topography on
samples and backscattered electrons are most
important for illustrating contrasts in composition in
multiphase samples. Figure 3.16 shows the block
diagram of scanning electron microscopy (SEM).
3.6.1 SEM analysis of Series-I ferrite nanoparticles
Figure 3.17 shows the SEM micrographs of Series-I
ferrite nanoparticles which are calcinated at 600 0C for 5
hours. It is found that all the samples are formed into
nano sized spherical, uniform and homogenous
crystallite structures. Similar results are investigated by
several researchers [37, 38]. The average particle sizes
of Series-I ferrite nanoparticles are recorded by SEM
morphology and compared with the crystallite sizes
which are calculated by Debye-Scherer formula. The
comparative values are shown in Table 3.6.
Figure Error! No text of specified style in document..17:
SEM micrographs of Ni0.5 Zn0.5 Alx Fe2-x O4
 19
(x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8 and
2.0)
Table Error! No text of specified style in document..6:
Comparative average crystallite sizes of
Series-I ferrite nanoparticles
3.6.2 SEM analysis of Series-II ferrite nanoparticles
Series-II ferrite nanoparticles SEM images are shown in
Figure 3.18 which is calcinated at 600 0C temperatures.
It is observed that morphology of the samples clearly
give the nanoparticles with uniformly distributed,
spherical in size, homogenous and less agglomerated.
Similar results are reported by several investigators [39,
40]. The average particle sizes of Series-II ferrite
nanoparticles are recorded from SEM morphology and
compared with the crystallite sizes which are calculated
by the Debye-Scherer equation. The comparative
average particle and crystallite sizes are shown in Table
3.7.
Figure Error! No text of specified style in document..18:
SEM micrographs of Nix Zn1-x Al1.0 Fe1.0 O4
(x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0)
Table Error! No text of specified style in document..7:
Comparative average crystallite sizes of
Series-II ferrite nanoparticles
3.7 Energy dispersive X-ray spectroscopy (EDX)
Energy dispersive X-ray spectroscopy (EDX) technique
produces the use of X-ray spectrum emitted by a
material stricken with electron beam in order to get the
chemical analysis and thence detect the elements. This
technique is valuable for the qualitative and quantitative
analysis of the sample. Qualitative analysis can be done
on the basis of indentifying spectral lines while
quantitative analysis determines the line intensities of
each element comparable with the standards of known
composition. The incident X-rays, when strike the
detector (lithium-drifted silicon), proportionally generates
a charge pulse that converts into a voltage pulse by a
charge-sensitive pre-amplifier. Then, this signal is
impinged into a multichannel analyzer whence the
pulses sort by voltage. The energy thus produced for
each incident X-ray is digitalized on computer display
for furtherance. The X-ray energy versus counts is
appraised to establish the composition. In a typical EDX
spectrum as a plot of X-ray counts verses energy (KeV),
peaks represent to the constituent elements in the
sample.
3.7.1 EDX analysis of Series-I ferrite nanoparticles
The EDX patterns of Series-I ferrite nanoparticles is
shown in Figure 3.19. EDX study confirmed the
homogeneous mixing of Ni, Zn, Al, Fe and Oxygen.
Composition and mass percentages of constituting
elements have been calculated by EDX analysis and
the calculated atomic weigh percentages of the
synthesized sample are consistent with the composition
of the samples obtained from EDX analysis and
tabulated in Table 3.7. Similarly kind of results are
reported by several researchers [8, 41].
Figure Error! No text of specified style in document..19:
EDX spectra of Ni0.5 Zn0.5 Alx Fe2-x O4
(x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8 and
2.0)
Table Error! No text of specified style in document..8:
Elemental compositions of Ni0.5 Zn0.5 Alx Fe2-x O4
(x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8 and
2.0)
3.7.2 EDX analysis of Series-II ferrite nanoparticles
The EDX patterns of Series-II ferrite nanoparticles are
shown in Figure 3.20. The peaks of the elements Ni, Zn,
Al, Fe and O are observed on the EDX images. Hence
the EDX pattern confirms that the calculated atomic
weight percentages for the synthesized samples are
consistent with the composition of the samples obtained
from EDX analysis and it is tabulated in Table 3.19.
Similar kind of results is reported by several
investigators [30, 42].
Figure Error! No text of specified style in document..20:
EDX spectra of Nix Zn1-x Al1.0 Fe1.0 O4
(x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0)
Table Error! No text of specified style in document..9:
Elemental compositions of Nix Zn1-x Al1.0 Fe1.0 O4
(x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0)

4.1 Introduction
Yogoro Kato and Takeshi Takei of the Tokyo Institute of
Technology discovered ferrites in 1930 [1]. Ferrite is a
material of ceramic compound composed of iron
oxide (Fe2O3) and which can be combined chemically
with one or more metallic elements [2]. Ferrites are
basically very good electrical insulators and have the
ferrimagnetic property. The most commercial
importance [3] of ferrites are Zn2+ substituted Ni and Mn
ferrite represented as Ni Zn Fe2 O4 and Mn Zn Fe2
O4 respectively. The resistivity nature is the key factor
among these two ferrites.
Ferrites exhibit Ferrimagnetic property thus there is a
net magnetic dipole moment present in molecular level.
As a result, the super exchange interaction takes place
in between the metallic and oxygen ions. Bulk ferrites
have the domain structure in which all molecular dipole
movements are aligned in the same direction. Domain
walls or Bloch walls separate the different domains
aligned in random directions. Application of external
magnetic field aligns the dipole moments along the
same direction. In this process some energy has will be
lost and the magnetization always lags behind the
applied magnetic field. This process is called magnetic
hysteresis.
A magnetic hysteresis loop represented by abcdefgb
curve illustrates the change in magnetic induction of a
ferromagnetic material to which an external field is
applied as the intensity of this field vary from +HS to HS
and back again, as shown in Figure 4.1. Hysteresis
curve shows the loss of energy in taking a
ferromagnetic material through a cycle of magnetization
and this is represented by the area enclosed by the
hysteresis loop.
Figure Error! No text of specified style in document..21:
Magnetic Hysteresis loop
In the absence of applied magnetic field (H) at point a it
can be observed that the magnetization is zero, as the
applied magnetic field increases, magnetization also
increases linearly and reaches a highest value known
as saturation magnetization (MS). When the applied
magnetic field is reduced to zero the magnetic induction
of a substance does not come to zero. This value of
magnetic induction is called residual magnetization
(MR). The magnitude of the demagnetizing field required
to reduce the remanent magnetization to zero is
referred as the coercivity (HC).
4.2 Neels theory
This theory is initiated by Louis Neel in the year of 1949.
The magnetic property of ferrites is explained on the
basis of Neels two
sub-lattice model [4]. According to this model the net
magnetic moment of the material is equal to the
difference between the magnetic moment at A and B
sub-lattice (i.e. magnetic moment at B sub-lattice
magnetic moment at A sub-lattice). The magnetic
property of ferrite is explained on the basis of the
distribution of ions in tetrahedral sites (A) and
octahedral sites [B]. It can be observed that there is the
possibility of several interactions between the A and B
sites, as A-A, B-B, A-B and B-A interactions. Neel
suggested that all the interactions in the ferrites are anti-
ferro magnetic in sign. But A-B interaction is
considerably stronger than the A-A or B-B interactions.
Louis Neel experimentally proved that the magnetic
moment of a substance is lesser than that of the
magnetic moment of individual constituent ions.
4.3 Magnetic moment (B)
The magnetic moment of a substance is calculated by
using the Equation 4.1.
B =
M x MS
5585
4.1
Where, B Magnetic moment of the sample, Ms
Saturation magnetization and M Molecular weight of
the sample
4.4 Vibrating Sample Magnetometer (VSM)
Vibrating sample magnetometer is invented by Simon
Forner in the year 1955. It is a common technique which
is used to measure the magnetic nature of the sample
with very high precision changes as small as 10-5 to 10-6
emu. Vibrating sample magnetometer works on the
Faradays law of induction which states that the
changing magnetic field produces an electric field [5].
The principle of the Vibrating sample magnetometer is
that it measures the magnetic moment of a sample
when it vibrates in perpendicular direction with the
applied uniform magnetic field. Normally, the vibrating
sample magnetometer measures the saturation
magnetization, residual magnetization and coercivity
from the hysteresis loops.
Figure Error! No text of specified style in document..22:
Vibrating Sample Magnetometer (Lakeshore model)
The magnetic properties of Series-I and Series-II ferrite
nanoparticles are measured using the vibrating sample
 21

magnetometer (Lakeshore VSM 718 model) in the lattices which reduce the magnetic moment of the
range of -20KOe to +20KOe at room temperature. samples [13, 14, 15].
4.4.1 VSM study of Series-I ferrite nanoparticles
The magnetic properties of Series-I ferrite nanoparticles
are carried using the VSM technique at room
temperature. Figure 4.3 shows the M-H loops of Series-I
ferrite nanoparticles and the calculated magnetic
properties like saturation magnetization, remanent
magnetization, coercivity and magnetic moment values
are tabulated in Table 4.1. As observed from the VSM
results of Series-I ferrite nanoparticles, they typically
represent soft magnetic behaviour [6-8].

Figure Error! No text of specified style in document..23:

M-H loops of Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.0, 0.2, 0.4,
0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8 and 2.0)
As observed from Table 4.1 and Figure 4.3 for Series-I
nanoparticles, saturation magnetization decreased from
35.91 to 0.096 emu/g, remanent magnetization is found
to decrease from 9.15 to 0.035 emu/g and the magnetic
moment values decreased from 1.58 to 0.003 with
increasing Al3+ ion doping substitution. However our
findings about variations in coercive field showed slight
deviation from the findings of Mohd Hashim et. al (9).
Our reported data is for compositions x = 0.0 to 2.0 in
eleven steps. Hence our findings cover extended range
of composition of Al3+ ion substitution. Kumar et. al and
Rajesh Babu et. al [10, 11] reported uniform reduction in
the coercivity but in our case we observed
non-uniformity in coercivity. This may be attributed due
to the asymmetric effect of coercive field on Fe3+ ions
and Al3+ ions.
Reduction in the saturation magnetization and
remanent magnetization is due to the substitution of
non-magnetic Al3+ ions in place of magnetic Fe3+ ions at
A and B sites. This weakens the exchange interactions
between magnetic ions at A and B-sites. As a result the
saturation magnetization and remanent magnetization
decreased with increasing Al3+ ion substitution. Similar
kind of results is reported in the literature [12, 13].
Similarly, decrease in the magnetic moment with
increasing Al3+ substitution is explained according to
Neels two sub-lattice theory. Magnetic moment of a
ferrite arises due to the distribution of Fe3+ ions
between A and B sub-lattices. The doping of Al3+ ions
lead to the decrease in Fe3+ ions over A and B sub-
lattices because, the Al3+ ion is a non magnetic
substance having zero net magnetic moment but the
ferromagnetic Fe3+ ions are having a magnetic moment
of 5B. Hence substituted Al3+ ions occupy the B sub-
 22

Table Error! No text of specified style in document..10:

Saturation magnetization (MS), Remanent
magnetization (MR), Coercivity (HC)
and magnetic moment (B) of Ni0.5 Zn0.5 Alx Fe2-x O4
(x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2,
1.4, 1.6, 1.8 and 2.0

The magnetic properties of ferrites are influenced by
various factors like grain size, density, anisotropy, lattice
defects and
super-exchange interactions between tetrahedral (A-
site) and octahedral (B-site) sub-lattices [16]. The
doping of a non-magnetic ions result in the decrease of
exchange interaction of ions in between A and B sub-
lattices and hence modifies the magnetic behaviour of
the samples. So the net magnetization of the system
can be expressed as the difference in the
magnetizations in the A and B sub-lattices. This can be
explained using Equation 4.2.
M = MB MA
4.2
Where, MA magnetic moment of A sub-lattice, MB -
magnetic moment of B sub-lattice.
But for the sample at x = 2.0 exhibits
superparamagnetic behaviour which is shown in Figure
4.4. The coercivity (Hc) and the remanent magnetization
(MR) values are found nearly zero which may indicate
superparamagnetic behaviour of the prepared
nanoparticles. The superparamagnetic character of the
present nanoparticles may be due to their fine
crystalline size. And it is also evident that a single
domain nature of nanoparticles may exhibit the
superparamagnetic behaviour [17-20].
In single-domain ferrimagnetic particles the
superparamagnetism takes place above the blocking
temperature (TB) due to weak interactions and thermal
fluctuations of magnetic spins of the nanoparticles.
Below blocking temperature (TB) the thermal
fluctuations of superparamagnetic nanoparticles cannot
turn freely but freeze in random orientations leading to
high-coercive fields. Hence in the superparamagnetic
region it can be written as TB < T < TC, the
magnetization response of the nanoparticles under the
applied field H is specified by the Langevin function
(Equation 4.3).
M
= L( )
H interactions, surface to volume ratio and the
MS KB T
4.3
Where, M magnetization, MS - saturation
magnetization,
L Langevins function, - magnetic moment of the
superparamagnetic particles, H applied magnetic field,
KB Boltzmanns constant, TC critical temperature, T
given temperature
23
Figure Error! No text of specified style in document..24:
M-H loop of Ni0.5 Zn0.5 Alx Fe2-x O4 at x = 2.0
4.4.2 VSM study of Series-II ferrite nanoparticles
The magnetic properties of Series-II ferrite
nanoparticles are carried out by VSM technique at room
temperature. Figure 4.5 shows the VSM graphs of
Series-II ferrite nanoparticles and the corresponding
values are presented in Table 4.2. The VSM results of
Series-II ferrite nanoparticles also exhibit the soft
magnetic behaviour.
Figure Error! No text of specified style in document..25:
M-H loops of of Nix Zn1-x Al1.0 Fe1.0 O4
(x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0)
From VSM analysis it is observed that the saturation
magnetization decreased from 10.6 to 4.3 emu/g,
remanent magnetization showed very small values in
the range 0.003 - 0.425 emu/g and magnetic moment
values are decreased from 0.400 to 0.158 by increasing
the Ni2+ ion substitution. It is observed that the
magnetization values of Ni-Zn ferrites in nano powders
are smaller than that of bulk size, this is due to finite
size effects [21-23]. Generally the magnetic properties
of ferrites are highly influenced by the cations
distribution in A and B-sites. It is clear that in Ni-Zn
ferrite Zn2+ ions normally occupy A-sites, Ni2+, Al3+ ions
occupy
B-sites and Fe3+ ions occupy both A and B-sites [24-27].
Present study shows that the saturation magnetization
values are found very small and they decreased from
10.6 to 4.3 emu/g by increasing the Ni2+ ion substitution.
The decreasing in saturation magnetization can be
explained using the canted spin structure at the surface
layers caused by the decrease in exchange coupling,
due to lack of oxygen mediating through super-
exchange mechanism between nearest iron ions at the
surface. It is also explained on the basis of core-shell
enhancement of the surface barrier potential due to
lattice distortion caused by the deviation of the atoms
from their positions on the surface layers [28-30]. The
smaller saturation magnetization values may be
explained due to crystal lattice defects, weak cation
super exchange interactions in between tetrahedral (A)
and octahedral [B] sites and random magnetic spin
orientations on the surface of ferrite nanoparticles [28,
31].
 24

It is the first time to prepare Ni-Zn-Al Ferrites having the

general formula of Nix Zn1-x Al1.0 Fe1.0 O4 (x = 0.0, 0.2,
0.4, 0.6, 0.8 and 1.0) using the sol-gel auto combustion
technique. In this work we focused on the variation of
magnetic properties of prepared ferrite samples with
substitution of Ni2+ ions. It is noticed that the adding of
Al3+ ions lead to the reduction in coercivity and the
saturation magnetization.
The decrease of magnetization is highly expected when
Al3+ ions enter into the ferrite lattice as mentioned in
previous works [32-34]. It is due to the non-magnetic
Al3+ ions which preferably occupy the octahedral sites
[B] and tetrahedral (A) sites. As a result, the density of
ferric ions (Fe3+) at octahedral [B] site decreases
compared to the tetrahedral (A) site. This in turn
reduces the magnetic moment at sub-lattice and
exchange interactions. The replacement of Al3+ ion that
has no magnetic moment (0 B) instead of Fe3+ ion (5
B) will dilute the magnetization at octahedral site and
hence reduces the magnetic moment and consequently
the magnetization in the lattice. Similar kind of
behaviour in the magnetization and coercivity is
observed in Al3+ doped ferrites [3537].
The ferrites having low saturation magnetization and
coercivity may be suitable for applications in high
frequency transformers. It is reported that addition of
trivalent ions like Al3+, substituent(s) for Fe3+ ion to Ni,
Zn, ferrites highly influences their electrical and
magnetic properties [38].
 25

Table Error! No text of specified style in document..11:

Saturation magnetization (MS), Remanent
magnetization (MR), Coercivity (HC) and
magnetic moment (B) of Nix Zn1-x Al1.0 Fe1.0 O4 (x =
0.0, 0.2, 0.4, 0.6, 0.8 and 1.
26
5.1 Introduction
The dielectric measurements of ferrites give the
information about the applicability of the materials in
electronic industry, research and design. The study of
dielectric nature in ferrites is also helpful for modifying
the electrical properties. The dielectric properties of
ferrites have wide applications in the area of medical
industries, aerospace, microwave and automotive. The
dielectric study generally deals with capacitance (C),
dielectric loss (tan ), impedance (Z), permittivity ()
and permeability () of the material. These dielectric
properties of ferrites change with applied frequency,
temperature, sintering conditions, chemical composition,
grain size, method of preparation, ratio of Fe3+/Fe2+ ions
and molecular structure of ferrite material.
The sintered ferrite composition shows good dielectric
properties due to the formation of high conductivity
grains. When the sintered sample is cooled down in
normal atmosphere, it forms low conductivity layers over
the high conductivity grains. As a result the ferrite
structure is the combination of high conductivity grains
separated by low conductivity layers. Hence the ferrite
behaves as inhomogeneous dielectric materials.
5.2 Dielectric parameters
A dielectric material has an ability to store the charge
when an external electric field is applied as observed in
the case of parallel plate capacitor (capacitance
increases when the dielectric material is kept in
between the plates) as shown in the Figure 5.1.
Figure Error! No text of specified style in document..26:
Parallel plate capacitor (with dielectric material)
The related formula is shown in Equation 5.1
A Variation of (a) real part permittivity (b) imaginary
C=
0 d
5.1
Where, C-capacitance of a capacitor, A-area of the
parallel plates,
d-distance between the two parallel plates, 0-
permittivity of free space (8.854x10-12 F/m)
Dielectric behavior of a ferrite material under alternating
electric fields may be explained on the basis of complex
permittivity of the material and it is calculated by using
the Equation 5.2.
= + j frequencies [5]. Hence, ferrites are treated as high-
5.2
Real and imaginary parts of permittivity can be
calculated by Equations (5.3) and (5.4) respectively.
=
Cd
0 A
5.3
= tan
...
5.4
Where, '-real part of permittivity, ''-imaginary part of
permittivity and tan dielectric loss factor
The AC conductivity of the ferrite samples is determined
by using Equation 5.5
AC = 0
5.5
Where, angular frequency
5.3 Experimental study
In the present work the dielectric properties of Ni-Zn-Al
Ferrites of Series-I and II have been studied using the
LCR impedance meter (Model 6500P Precision LCR
Meter, Wayne Kerr-Germany) as a function of
composition with the applied frequency in the range
of 20 Hz - 5 MHz and temperature ranging from 27 0C to
600 0C and their results are discussed in this chapter.
5.4 Dielectric study of Series-I Ferrites
The dielectric response of Series-I Ferrites are carried
using the LCR impedance meter as a function of
frequency, temperature and composition.
5.4.1 Dielectric response with applied frequency
The variation of real and imaginary parts of permittivity
of Series-I Ferrites at room temperature with applied AC
frequency and composition are shown in Figure 5.2.
Figure Error! No text of specified style in document..27:
part permittivity with frequency and composition of
Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0,
1.2, 1.4, 1.6, 1.8 and 2.0) at room temperature
It is observed that the real and imaginary parts of
dielectric permittivity decreased with increasing applied
frequency; which represents the dielectric dispersion
that occurs at lower frequencies [1].This can be
explained by the Maxwell-Wagner polarization [2, 3] in
agreement with Koops theory [4]. In inhomogeneous
dielectric structure, the space charge polarization
reports high dielectric constant values at lower
quality dielectric substances at lower frequencies. At
higher frequency, the real and imaginary part of
dielectric constant becomes very small and almost
independent of applied frequency [6]. The variation of
dielectric constant may be explained in terms of space

charge polarization that is generated due to the
presence of greater conductivity grains and the
insulating grain boundaries. A dielectric material
produces localized accumulation of charge under the
influence of an applied electric field [7]. Similar type of
polarization in ferrites is demonstrated by Rabinkin and
Novikova [8].
The electron exchange between Fe2+ Fe3+ gives the
local displacement of electrons in the direction of
applied AC field which gives the conduction of the
grains. The accumulation of charges at the grain
boundaries results in polarization. It is observed that the
polarization decreases with increased frequency and
then reaches a constant value. This can be explained
that beyond a certain applied frequency, the electron
exchange between Fe2+ Fe3+ does not follow the
alternating field. This is due to the predominance of
species like Fe2+ ions, grain boundary defects, voids,
oxygen vacancies, interfacial dislocation pileups, etc. [9,
10]. Rezlescu model [11] explained that all samples
exhibit the resonance peak with applied frequency.
According to Rezlescu model, when hopping frequency
of charge exchange nearly matches with the applied AC
field then the resonance peak (Debye relaxation)
occurs.
5.4.2 Response of AC conductivity with applied
frequency and composition at room temperature
Figure 5.3 illustrates the variation of AC conductivity with
applied frequency at room temperature for different Al3+
ion substitutions. All the samples showed increasing
trend in the AC conductivity with the increase in applied
frequency. This is a general behaviour of ferrite
materials. The electrical conductivity in ferrites is
explained due to hopping mechanism of electrons
between the ions of the same element present in more
than one valence state.
Grain boundary influence on conduction is more at lower
frequencies as compared to grains which contribute for
higher conductivity at high frequencies. The hopping of
electrons in between Fe3+ and Fe2+ ions is sluggish at
low frequencies but as the applied frequency increases,
the conducting grains stimulate the hopping mechanism,
therefore AC conductivity increases. Figure 5.3 shows
that the AC conductivity increases almost linearly with
applied frequency and decreases with increasing Al3+ ion
substitution.
Figure Error! No text of specified style in document..28:
Variation of AC conductivity with frequency and
composition for Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.0, 0.2,
28
0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8 and 2.0) at room
temperature
The AC conductivity at 1 MHz frequency for Ferrites at
room temperature is shown in Figure 5.4. The decrease
in AC conductivity with composition (x) may be explained
by microstructure, jump length and jumping probability
[12]. Smaller the grain size, greater the insulating grain
boundaries and hence the conductivity of the samples
decrease. As crystallite size decreased from 51.47 to
17.15 nm with the increase of Al3+ ion substitution the AC
conductivity is found to decrease showing the
involvement of small polarons in the conduction process.
Figure Error! No text of specified style in document..29:
Variation of AC conductivity with composition for
Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0,
1.2, 1.4, 1.6, 1.8 and 2.0) at room temperature with
applied frequency of 1MHz
Increasing the Al3+ ion substitution decreased the AC
conductivity of the ferrite samples as shown in Figure
5.4. This may be due to occupancy of Al3+ ions at
octahedral sites for Ni-Zn Ferrites. This reduces the Fe3+
ion quantity and isolates them. Hence a decrease in the
probability of charge hoping causes decrease in the AC
conductivity [13], which can be expressed by the
following electron transport mechanism:
Ni2+ + Fe3+ Ni3+ + Fe2+ and Fe3+ Fe2+ + e
5.4.3 Temperature dependence of dielectric
constant, dielectric loss tangent and AC
Conductivity
There is a strong correlation between the electric
conduction and dielectric behaviour in ferrite systems
[14, 15] and the electric conduction in ferrites is similar to
that of the polarization mechanism [16]. The temperature
dependent dielectric constant (), dielectric loss (tan )
and AC conductivity (AC) of the samples for the selected
compositions (x = 0.8 and x = 2.0) are shown in Figures
5.5, 5.6 and 5.7 respectively. From Figures 5.5, 5.6 and
5.7, it is confirmed that the dielectric constant, dielectric
loss and AC conductivity increase with increasing
temperature. The increase in AC conductivity with
temperature signifies the semiconducting behaviour of
ferrites [17]. By increasing the temperature, the charge
gets thermally activated and that increases the charge
carrier interaction. This improves the AC conductivity of
the ferrite samples [18]. The values observed from
dielectric properties of Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.0,
0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8 and 2.0) Ferrites
are shown in Table 5.1.
 29
Figure Error! No text of specified style in document..30:
Variation of dielectric constant with applied
frequency for Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.8 and 2.0)
at different temperatures

Figure Error! No text of specified style in document..31:

Variation of dielectric loss tangent with applied
frequency for Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.8 and 2.0)
at different temperatures

Figure Error! No text of specified style in document..32:

Variation of AC conductivity with applied frequency
for Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.8 and 2.0) at different
temperatures
 30

Table Error! No text of specified style in document..12:

Crystallite size (t), dielectric constant (), dielectric
loss (tan ), A.C conductivity (AC)
of Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0,
1.2, 1.4, 1.6, 1.8 and 2.0) measured at room
temperature

5.5 Dielectric study of Series-II Ferrites
The dielectric behaviour of Series-II Ferrites are studied
using LCR impedance meter as a function of
composition, applied frequency and temperature.
5.5.1 Dielectric response with applied frequency
Figure 5.8 shows the variations of real and imaginary
parts of dielectric permittivity with applied frequency (20 -
5 MHz) for Series-II Ferrites at room temperature. It is
found that the real and imaginary parts of dielectric
permittivity decreases with increasing applied frequency.
This shows that the dielectric dispersion occurs at lower
frequency, this dispersion mechanism at low frequency
can be explained using
Maxwell-Wagners two-layer model [2, 3, 19] and agrees
with Koops phenomenological theory [4]. The change in
the dielectric constant may be explained in terms of
space charge polarization which is produced due to the
existence of greater conductivity grains in the insulating
grain boundaries [20-25]. The space charge polarization
is formed due to large fine conducting grains separated
by thin and poor conducting intermediate grain
boundaries. The exchange of electron in between Fe2+
and Fe3+ ions gives the local displacement of electrons in
the applied AC field direction which gives the
polarization. It is found that the polarization decreases
with increased frequency and gets a stable value. This
can be explained that beyond a certain applied
frequency the electron exchange between Fe2+ Fe3+
does not follow the AC field
[26, 27].
Figure Error! No text of specified style in document..33:
Variation of (a) real part permittivity (b) imaginary
part permittivity with applied frequency for Nix Zn1-x
Al1.0 Fe1.0 O4
(x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) Ferrites
5.5.2 Response of AC conductivity with frequency
and composition at room temperature
The variation of AC conductivity with applied frequency
at room temperature of Ni2+ ion substitution for a fixed
Al3+ ion substitution is shown in Figure 5.8. Generally the
electrical conductivity in ferrites may be explained on the
basis of Verwey conduction mechanism, where the
electron exchanges between the adjacent Fe2+ and Fe3+
ions which occupies the octahedral sites [34]. From
Figure 5.9 it is found that the AC conductivity increases
linearly with applied frequency, this shows the general
behaviour of ferrite structures. The linear increase in the
electrical conductivity with increasing the applied
frequency may be explained due to increasing frequency
which can improve the electron hopping between the
31
charge carriers and thus increases the conductivity of the
samples [28, 29]. Figure 5.10 shows that the AC
conductivity decreases with increasing the Ni2+ ion
substitution. This can be explained by microstructure,
jump length and the jumping probability of electrons. It is
found that the crystallite size decreased from 45.74 to
14.70 nm with increasing the Ni2+ ion substitution. Hence
it is clear that smaller the grain size larger will be the
insulating grain boundaries and lesser the electrical
conductivity of the material. As grain size decreases with
increasing Ni2+ ion substitution the AC conductivity
decreases almost linearly.
This shows that small polarons are responsible for
conduction mechanism [12]. In another way it may be
explained that the smaller grains offer a large number of
insulating grain boundaries which act as a hurdle for the
electric current hence there is a reduction in the electric
current in the ferrite material [30]. In this composition the
substitution of aluminium ions in place of Fe3+ ions limits
the degree of conduction and polarization by blocking
Verweys hopping mechanism [31, 32] resulting in the
decrease of conductivity, dielectric constant and
dielectric loss. In another way it may be explained that
the addition of aluminium ions reduces electron hopping
thereby decreasing the electronic jumps between Fe2+
and Fe3+ ions [33].
Figure Error! No text of specified style in document..34:
Variation of AC conductivity with applied frequency
and composition for Nix Zn1-x Al1.0 Fe1.0 O4 (x = 0.0,
0.2, 0.4, 0.6, 0.8 and 1.0) Ferrites
Figure Error! No text of specified style in
document..35:Variation of AC conductivity with
composition for
Nix Zn1-x Al1.0 Fe1.0 O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and
1.0) at room temperature with applied frequency of 1
MHz
5.5.3 Temperature dependence of dielectric
constant, dielectric loss tangent and AC
Conductivity
The temperature dependence of dielectric constant (),
dielectric loss tangent (tan ), AC conductivity (ac) for
the compositions of x = 0.4, 0.8 and 1.0 are shown in
Figures 5.11, 5.12 and 5.13 respectively. It is found that
the dielectric constant, dielectric loss tangent and AC
conductivity are observed to increase with increasing the
temperature. The increasing in conductivity with increase
in temperature confirms the semiconductor behaviour of
ferrites samples [17].
 32
This shows that there is a strong association between Nix Zn1-x Al1.0 Fe1.0 O4 (x = 0.4, 0.8 and 1.0) Ferrites at
the conduction mechanism and the dielectric behaviour different temperatures
of ferrites [15, 14]. It can be observed that by increasing
the temperature, electrical conductivity and dielectric loss
tangent of ferrite samples are observed to increase. This
temperature thermally activates the charge carriers that
in turn increase the charge exchange interactions. Hence
the AC conductivity and dielectric loss tangent are Figure Error! No text of specified style in document..37:
observed to increase. The dielectric properties of Nix Zn1- variation of dielectric loss tangent with frequency
x Al Fe O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) are shown for Nix Zn1-x Al1.0 Fe1.0 O4 (x = 0.4, 0.8 and 1.0)
in Table 5.2. Ferrites at different temperatures

Figure Error! No text of specified style in document..38:

Variation of AC conductivity with frequency for
Nix Zn1-x Al1.0 Fe1.0 O4 (x = 0.4, 0.8 and 1.0) Ferrites at
different temperatures

Figure Error! No text of specified style in document..36:

variation of dielectric constant with frequency for

Table Error! No text of specified style in document..13:

Crystallite size (t), dielectric constant constant (),
dielectric loss (tan ), A.C conductivity (AC) of Nix
Zn1-x Al1.0 Fe1.0 O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0)
Ferrites at room temperature
33
 Where, E activation energy, resistivity, T
Introduction temperature,
Resistivity is a key factor to decide the electrical K Boltzmann constant
properties of materials such as conductors, insulators Equation 6.2 states that by increasing the temperature,
and semiconductors. The resistivity of a material is mobility of the charge carriers give rise to hopping of
affected and controlled by temperature, lattice defects, charge carriers. As a result conductivity increases,
mobility of electrons and impurities of a material. hence resistivity decreases. The DC resistivity of the
The electrical resistance of a material is a measurement ferrites generally decreases with increasing the sintering
how difficult to pass an electric current through the temperature and sintering time.
material. 6.3 Activation energy
The resistivity of a substance is expressed as It is defined as the amount of energy required to
=
RA release an electron from the ion to jump from a
L
neighbouring ion, giving rise the electrical conductivity

of the ferrite sample. The slope of the Arrhenius graph
6.1
(log versus 1000/T) gives activation energy by
Where, R - resistance of a substance at a given
considering the difference between paramagnetic and
temperature, A - area of cross section of pallet sample,
ferrimagnetic regions.
L - thickness of the pallet sample
It is found that the activation energy of paramagnetic
For metals, as the temperature increases resistivity also
region (EP) is greater than that of ferrimagnetic region
increases, this is known as positive temperature co-
(EF). In ferrimagnetic region the conduction electrons are
efficient of resistance; whereas, for semiconductors and
very active (hopping) between Fe2+ and Fe3+ ions in B
insulators resistivity decreases as the temperature
sites, which lower the value of activation energy [7].
increases, this is known as negative temperature
6.4 Theories of electrical properties of ferrites
co-efficient of resistance.
The most important models which can explain the
The resistivity of a substance is mostly due to the
electrical properties of ferrites are
following reasons
Hopping model
The thermal vibrations of the lattice ions.
Small polaron model
The impurities and lattice imperfections of
6.4.1. Hopping model
the material.
The conduction mechanism in Ni-Zn ferrite is due to
Due to high electrical resistivity the ferrites have many
hopping of electrons between Fe3+ and Fe2+ ions on
applications in various fields [1-3]. The electrical
octahedral sites (B-sites), as well as the presence of
resistivity of ferrites depends on preparation methods,
small Fe2+ ions in ferrite is due to sintering process and
chemical composition, type of materials, crystallite size,
sintering time and exchange electron interaction
density, porosity and sintering temperature [4].
between Ni2+ and Fe3+ ions explained as
The variation of DC resistivity can be explained with
Ni2++ Fe3+ Ni3++ Fe2+
Verwey hopping mechanism [5]. According to Verwey
In steady state lattice, there is a small interaction
mechanism the electrical conduction in ferrites is
between the ions on adjacent octahedral sites as a
explained due to hopping of electrons in between same
result the charge carriers will not move freely in the
ions of elements in different valance states on
lattice. The conduction mechanism depends on lattice
tetrahedral (A) site and octahedral [B] site [6]. Ferrites
vibrations and mobility of the charge carrier. The
have negative temperature coefficient of resistance like
temperature dependent conductivity is explained on the
semiconductor.
basis of mobility of the charge carriers but not on the
6.2 Temperature dependence of resistivity
density of the charge carriers in the sample.
The electrical resistivity of the ferrite samples with
6.4.2. Small polaron model
temperature can be calculated by using Arrhenius
When a moving charged particle polarizes around the
equation.
E lattice with ionic character then a polaron model forms.
= 0 exp The lattice polarization acts as potential well for charge
KT
6.2 carriers as a result charge carrier and mobility
decreases. Polaron process can be explained by the
displacement of atoms or ions due to incomplete inner
 35
(d or f) shell. Due to this an extremely narrow energy
bands will form by the overlapping of electrons. The
movement of small polarons require hopping of both
electrons and polarized atomic configuration from one
site to adjacent site. If the hopping electrons become
localized due to interaction with phonon then a small
polaron is formed and the conduction is due to hopping
motion of small polaron.
6.5 DC resistivity measurement techniques
DC resistivity of the ferrite samples can be analyze
using two methods two probe method and four probe
method. Two probe experimental method is very simple
to handle and it measures the high electrical resistivity
of ferrites with more accuracy than the four probe
method. Hence the two probe method is sensible to
measure high resistivity of ferrites. Therefore in this
chapter we discussed only two probe method in detail
[8].
6.5.1 Two probe method
The pellet sample is kept in a sample holder and two
good conducting copper wires are used for electrical
connections as two probes. One of the probes is used
for sourcing dc voltage from a constant voltage, which is
capable of measure the voltage from 1V to 211 V with
an accuracy of 0.0001 V and other probe is
connected to same electrometer, which is used to
measure the resulting change in the current across the
surface of the pellet sample.
A temperature controlled furnace along with sample
holder and constant voltage source is connected to dc
power supply in Series connection. Temperature of the
sample is varied from room temperature to 600 0C and
this temperature can be read by using temperature
sensing multimetre. Temperature sensing multimetre is
connected to thermo couple PT 100, the corresponding
change in the current due to temperature can be
measured by source metre, which is capable of
measuring the current from 1A to 400 A. The two
probe experimental set-up and the block diagram of the
sample holder are shown in Figures 6.1 and 6.2
respectively.
6.6 Experimental study
In the present work the DC resistivity () of Ni-Zn-Al
Ferrites of Series-I and Series-II have been studied
using the two probe experimental method in the
temperature range from 294 to
873 K. To study DC resistivity the prepared nanoferrite
samples are silver coated on both the sides for making
good electrical contacts.
Figure Error! No text of specified style in document..39:
Two probe experimental arrangement
Figure Error! No text of specified style in document..40:
Block diagram of sample holder
6.6.1 DC resistivity study of Series-I Ferrites
The present work focuses on the influence of DC
resistivity of
Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0,
1.2, 1.4, 1.6, 1.8 and 2.0) Ferrites. The electrical
resistivity is studied in the temperature range from 294
to 873 K using the Arrhenius equation
(Equation 6.2). It is clear that the electrical resistivity and
drift mobility are inversely related; hence samples have
high electrical resistivity which shows low drift mobility
and vice versa.
Resistivity of the samples and drift mobility of the charge
carriers are calculated by Equations 6.1 and 6.3.
d =
1
ne
6.3
Where, e - charge on electron, DC resistivity, n -
charge substitution can calculate by using Equation 6.4
N P
n = A B Fe
M
6.4
Where, NA Avogadro number, B bulk density, PFe
number of atoms, M molecular weight
Figure Error! No text of specified style in document..41:
Variation of (a) DC resistivity with temperature (b)
drift mobility with temperature for Ni0.5 Zn0.5 Alx Fe2-x
O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8 and
2.0) Ferrites
Figure 6.3 (a) shows that DC resistivity decreases with
increase of temperature showing the semiconductor
nature of the ferrite samples [9] and Figure 6.3 (b)
shows that drift mobility increases with increase of
temperature. This is due to the fact that increasing the
temperature will enhance hopping of charge carriers
from one cationic side to other [10]. It can be observed
from Figure 6.3 (a) that the DC resistivity increased with
increasing the Al3+ ion substitution. As Al3+ ions occupy
the octahedral sites, this decreases the Fe3+ ion
number. Hence, the lesser amount of electron charges
 36

transfer between Fe2+ Fe3+, consequently the

resistivity of the samples increase with increase of Al3+
ion substitution [11].
Activation energy and Curie temperature
Figure 6.4 shows log with 1000/T graphs of Ni0.5 Zn0.5
Alx Fe2-x O4
(x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8 and 2.0)
Ferrites. A kink in the graph is observed at a particular
temperature indicating that the sample changes from
ferrimagnetism to paramagnetism and this temperature
is known as Curie temperature (TC). From Table 6.1, it
is observed that the Curie temperature decreases from
677 to 636 K with increasing Al3+ ion substitution. These
values are in agreement with Curie temperature
calculated by Lorie-Sinha technique. It is observed that
the activation energy of the paramagnetic region is
greater than ferrimagnetic region.
In ferrimagnetic region the conduction electrons are
very active (hopping) between Fe2+ and Fe3+ ions in
octahedral [B] sites, which lowers the value of activation
energy. The activation energy is measured from the
slope of the Arrhenius plots and tabulated in
Table 6.1. It is observed that the activation energy
increases from 0.315 to 0.346 eV. This may be
explained due to the presence of large number of
oxygen vacancies and enhanced electrical resistivity
with increasing Al3+ ions substitution [12, 13].

Figure Error! No text of specified style in document..42:

Variation of log () with 1000/T and composition for
Ni0.5 Zn0.5 Alx Fe2-x O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0,
1.2, 1.4, 1.6, 1.8 and 2.0) Ferrites
6.6.2 DC resistivity study of Series-II Ferrites
The DC resistivity of the ferrite samples can be decided
with the chemical composition, type of materials used,
preparation method, sintering temperature and time,
crystallite size, density, porosity, of the samples and type
of cations substituted in the ferrite lattice [4]. Ferrites
electrical resistivity may be altered with the substitution
of suitable divalent or trivalent ions occupying at the
tetrahedral or octahedral sites.
 37

Table Error! No text of specified style in document..14:

Curie temperature, DC resistivity, activation energy
of Ni0.5 Zn0.5 Alx Fe2-x O4
(x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8 and
2.0) Ferrites
 38

The present work will discuss about the influence of DC
resistivity of Series-II Ferrites. The DC resistivity and drift
mobility with temperature for the ferrite samples are
shown in Figures 6.5 (a) and (b) respectively. It is clear
from the Figures 6.5 (a) and (b) that the DC resistivity of
the ferrite samples decreases with increasing the
temperature whereas the drift mobility increased with
increasing the temperature. The increase in electrical
resistivity of the ferrite samples may be explained based
on the Ni2+ and Al3+ ions which preferably occupy the
octahedral sites [14, 15]. Hence increasing the Ni2+ ion
substitution may cause to shift the Fe3+ ions from
octahedral sites to tetrahedral site. Therefore the
decrease in electron transfer between Fe2+ Fe3+
consequently increases the resistivity of the ferrite
samples.
Figure Error! No text of specified style in document..43:
Variation of (a) DC resistivity with temperature (b)
drift mobility with temperature for Nix Zn1-x Al1.0 Fe1.0
O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) Ferrites at room
temperature
The Curie temperature values obtained from the
Arrhenius plots and that from the Lorie-Sinha method
nearly agrees with each other.
6.6.3 Lorie Sinha method
The Lorie - Sinha technique [17] is an easy technique to
determine Curie temperature of the magnetic
substances. The electromagnet along with the soft iron
pieces are well insulated using porcelain sheet. The soft
iron at middle of the furnace gets magnetized under the
influence of electromagnetic field. The ferrite sample
pellet is placed on the soft iron and kept in the furnace
whose position can be adjusted with the help of a
mirror. The temperature of the samples is slowly
increased by heating coil using dimmer-stat, which is
measured with a Cr-Al thermo couple.
At a certain temperature, called Curie temperature the
ferrite sample loses its magnetization and falls down.
Curie temperature for all the samples are measured and
presented in Table 6.2. Observed values are quite
encouraging and are in good agreement with the values
of Curie temperature found with the help of slope of
Arrhenius plots (Figure 6.4 and 6.6).

It is noticed from Figure 6.6 that the electrical resistivity

of ferrite samples decrease with increasing the
temperature showing the semiconducting behaviour of
ferrite samples. Decrease in the electrical resistivity with
increasing temperature can be explained due to
thermally activated drift mobility of charge carriers
according to hopping conduction mechanism [10, 16] of
electrons between multivalent cations like Fe2+ and Fe3+
located at octahedral sites as Fe3+ + e- Fe2+.

Figure Error! No text of specified style in document..44:

Variation of log () with 1000/T and composition for
Nix Zn1-x Al1.0 Fe1.0 O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and
1.0)
Activation energy and Curie temperature
Figure 6.6 shows the Arrhenius plot of Nix Zn1-x Al1.0 Fe1.0
O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) Ferrites. The
activation energy values are obtained from the slopes of
ferrimagnetic (EF) and paramagnetic regions (EP). Table
6.2 reveals that the activation energy increased from
0.223 to 0.250 eV with increasing the Ni2+ ion
substitution. This is due to the existence of a large
number of oxygen vacancies and increased trend in
electrical resistivity of the ferrite samples. From Table 6.2
it is observed that the Curie temperature decreases from
671 to 647 K with increasing the Ni2+ ion substitution.
 39

Table Error! No text of specified style in document..15:

Curie temperature, DC resistivity, activation energy
of
Nix Zn1-x Al Fe O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0)
Ferrites
40

7.1 Introduction
The current-voltage (I-V) characteristics play an
important role in electronic engineering for designing,
testing and characterization [1-4] materials for practical
applications. Memory storage and switching properties
of mixed oxide ferrites are used in making the digital
computers and data processing circuits. Electrical
switching concept is initially reported in CuFe2O4 ferrite
by Yamashiro [5]. Later report is on thermally treated
CuFe2O4 by Vaingankar et al. [6]. Electrical switching in
Lithium ferrite is reported by Histake et al. [7] by
considering the latest developments in the resistance
switching in mixed oxides. In the present work we have
tried to revisit the classic ferrite system to understand
the high field instability causing resistance switching in
cationic spinel ferrite system.
7.2 Experimental study
Current-Voltage (I-V) characteristics are evaluated by
using Keithley 4200 semiconductor system as shown in
the Figure 7.1. The system can characterize DC I-V,
C-V, pulse devices, with real time plotting and analysis
with high precession and measures up-to femto-amp
(fA=10-15 level) resolution. This system is embodied with
a digital computer supported by windows operating
system. The 4200-SCS is configured to support up to 8
source-measure units, including up to 4 high power
SMU with 1A/20 W capability. An optional remote pre-
Amp extends the system resolution from 100 - 0.1 fA by
adding five current ranges to SMU models including I-V
package, dual-channel pulse generator and dual
channel digital oscilloscope.
Figure Error! No text of specified style in document..45:
Block diagram of Keithley 4200
characterization system
Figure Error! No text of specified style in document..46:
Typical Ag/Ni-Zn/Ag planner geometry used
to record I-V curves
For I-V characteristic study a 5 mm long electrodes of
copper wires are pressed directly on the pellet, which
acts as electrodes. Four probe technique is used for the
study of I-V characteristics as shown in Figure 7.2.
Typical current-voltage (I-V) curves are taken at room
42
temperature in the voltage range of -2V to +2V applied
through the electrodes and the corresponding current is
measured.
7.3 Current-Voltage (I-V) characteristics of SeriesI
Ferrites
Voltage - Current (I-V) loops for different compositions
of Ni0.5 Zn0.5
Alx Fe2-x O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6,
1.8 and 2.0) Ferrites are measured by Keithley 4200
semiconductor system and shown in Figure 7.3.
Figure Error! No text of specified style in document..47:
Current-Voltage (I-V) characteristics of Ni0.5 Zn0.5 Alx
Fe2-x O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8
and 2.0)
7.4 Current-Voltage (I-V) characteristics of SeriesII
Ferrites
Voltage-Current (I-V) loops for different compositions of
Nix Zn1-x
Al1.0 Fe1.0 O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0)
nanoferrite are measured by Keithley 4200
semiconductor system as shown in the Figure 7.4.
Figure Error! No text of specified style in document..48:
Current-Voltage (I-V) characteristics of Nix Zn1-x Al1.0
Fe1.0 O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) Ferrites
Figure 7.3 and 7.4 shows typical I-V characteristics
curves for ferrites in the form of hysteresis loops. The
prime idea of this study is to check whether these
samples are suitable for switches or not? From Figures
7.3 and 7.4 it is found that I-V characteristics of the
samples show a non-linear behaviour which means
different currents at different biasing voltages. I-V
characteristic of the samples show semiconductor diode
like dynamic properties.

The ferrite nanoparticles of Series-I: Ni0.5 Zn0.5 Alx Fe2-x
O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8 and
2.0) and Series-II:
Nix Zn1-x Al1.0 Fe1.0 O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0)
are prepared by using sol-gel auto combustion
technique. Structural, magnetic, dielectric, electrical and
I-V characteristics are studied by using various
techniques. The prepared ferrite nanopowders are
sintered at 600 0C for 5 hours and the obtained powder
is pressed into pellets by applying hydraulic pressure of
5 tons for about 15 minutes to get circular shaped
pellets with dimensions of 10 mm in diameter and
2 mm thickness. These pellets are again sintered at 600
0C for 5 hour and coated with silver paint for better
making electrical contacts to investigate the dielectric,
electrical properties and I-V characteristics. The
structural properties such as lattice constant, crystallite
size, X-ray density, bulk density and porosity are
calculated from the X-ray diffraction analysis.
For Series-I, it is observed that the lattice constant
decreased from 8.472 to 8.205 as Al3+ ion substitution
increased. Similarly the crystallite size also decreased
from 51.47 to 17.15 nm. The linear variation of lattice
constant with composition obeyed the Vegards law. The
behaviour of decrease in the lattice constant and
crystallite size with Al3+ ion substitution may be
attributed due to the larger Fe3+ (0.645 ) ions being
replaced by smaller Al3+ (0.55 ) ions. The
X-ray density decreased from 5.373 to 4.328 g/cm3 with
increasing Al3+ ion substitution. This is due to the
replacement of Al3+ ions (lower molar mass: 26.98
g/mol) in the place of Fe3+ ions (higher molar mass:
55.85 g/mol). It is observed that the bulk density
increased from 4.072 to 4.152 g/cm3 and porosity
decreased from 24.21 to 4.06 % with increasing Al3+ ion
substitution. The jump lengths LA and LB found to
decrease from 3.668 to 3.552 and 2.994 to 2.900
respectively with increasing the Al3+ ion substitution.
The jump length is directly proportional to lattice
constant, hence it is understood that as the lattice
constant decreases the jump length also decreases in
case of Series-I ferrite nanoparticles.
For Series-II, it is observed that the lattice constant
decreased from 8.334 to 8.281 as Ni2+ ion substitution
increases. Similarly the crystallite size also decreased
from 45.74 to 14.70 nm. The linear variation of lattice
constant with composition obeyed the Vegards law. The
behaviour of decrease in the lattice constant and
crystallite size with Ni2+ ion substitution may be
attributed to the larger Zn2+
(0.84 ) ions being replaced by smaller Ni2+ (0.74 )
ions. The
44
X-ray density decreased from 4.869 to 4.807 g/cm3 with
increasing Ni2+ ion substitution. This is attributed due to
the replacements of higher atomic mass of zinc (68.38
amu) by lower atomic mass of nickel (58.69 amu). It is
observed that the bulk density increased from 3.784 to
3.997 g/cm3 and porosity is decreased from
22.28 to 16.85 % with increasing Ni2+ ion substitution.
The jump lengths LA and LB found to decrease from
3.609 to 3.586 and 2.946 to 2.927 respectively with
increasing the Ni2+ ion substitution.
The jump length is directly proportional to lattice
constant, hence it is understood that as the lattice
constant decreases the jump length also decreases in
the case of Series-II ferrite nanoparticles.
FTIR spectra of the synthesized ferrite nanoparticles of
Series-I and Series-II confirm the ferrite structure. For
the Series-I, the high frequency bands (1) is observed
in the range of 624 - 635 cm-1 and low frequency bands
(2) in the range of 417 - 420 cm-1. For Series-II, the
high frequency bands (1) are observed in the range of
605 636 cm-1 and low frequency bands (2) are
observed in the range of 404 414 cm-1. The IR
analysis confirms the characteristic of ferrite.
The SEM images showed the morphology of the Series-
I and
Series-II prepared ferrite nanoparticles. Well defined
spherical, uniform, homogenous and less agglomerated
nanoparticles are observed in prepared nanoferrite
samples. EDX pattern for Series-I and Series-II ferrite
nanoparticles confirms the homogeneous mixing of the
Ni, Zn, Fe, Al and O atoms in pure and doped ferrite
samples. Hence, the observed composition from EDX is
almost equal to that of the sample produced by sol-gel
method.
The magnetic properties are carried by using the VSM
technique at room temperature for the Series-I and
Series-II ferrite nanoparticles. Series-I ferrite
nanoparticles show the soft magnetic behaviour and it is
found that the saturation magnetization and remanent
magnetization decreased from 35.91 to 0.096 emu/g
and
9.15 to 0.035 emu/g respectively with increasing the Al3+
ions substitution. Similarly, the coercive field and
magnetic moment also decreased from 242 to 0.5 KOe
and 1.528 to 0.003 respectively by increasing the Al3+
ion substitution. But the composition at x = 2.0 the
nanoferrite particles showed the superparamagnetic
behaviour. Series-II ferrite nanoparticles also showed
the soft magnetic behaviour. Their saturation
magnetization, remanent magnetization values are
found to decrease from 10.6 to 4.3 emu/g and

0.271 to 0.425 emu/g respectively with increasing the
Ni2+ ion substitution.
For Series-I nanoferrite samples the dielectric properties
such as dielectric constant and dielectric loss values are
calculated and it is found to decrease from 87.9 to 21.1
and 1.47 to 0.77 with the applied frequency of 1 MHz at
room temperature. It can be observed that AC
conductivity decreased from 0.78x10-6 to 0.12x10-6 /-
cm with increasing the Al3+ ion substitution. Increasing
the Al3+ ion substitution will decrease the AC
conductivity of the prepared nanoferrite samples due to
occupying of Al3+ ions at octahedral sites in the Ni-Zn
nanoferrite samples. This can reduce the Fe3+ ion
quantity thereby decreasing the probability of charge
hopping, hence a decrease in the AC conductivity is
observed. This can be explained with the following
mechanism:
Ni2+ + Fe3+ Ni3+ + Fe2+, Fe3+ Fe2+ + e
The dielectric constant, dielectric loss tangent and AC
conductivity values are observed to increase with
increasing temperature thus verifying the
semiconducting behaviour of ferrites. This is due to the
excess temperature that thermally activates the charge
carriers. As a result the charge carrier interaction
increases so that it improves the AC conductivity,
dielectric constant and dielectric loss tangent of the
prepared nanoferrite samples.
Similarly for Series-II nanoferrite samples, dielectric
constant and dielectric loss found to decrease from 92.2
to 19.6 and 1.06 to 0.82 respectively with increasing the
Ni2+ ion substitution at room temperature with applied
frequency of 1 MHz. AC conductivity is found to
decrease with Ni2+ ion substitution from 0.70x10-6
to 0.11x 10-6/-cm at room temperature with applied
frequency of
1 MHz.
DC resistivity, activation energy and Curie temperatures
are calculated by using two-probe method in
temperature range 294- 873 K. It is observed that by
increasing the temperature, DC resistivity decreases,
which shows the semiconductor nature of the prepared
nanoferrite samples. Similarly by increasing the
temperature, drift mobility also increases due to the
excess temperature which enhances the hopping of
charge carriers from one cationic site to other. It is
obvious that electrical resistivity and drift mobility are
inversely related, hence samples having high electrical
resistivity show low drift mobility and vice-versa.
For Series-I nanoferrite samples, it is observed that the
DC resistivity at room temperature increased from
45
0.087x106 to 0.850x106 -cm with increasing the Al3+
ion substitution. This is because Al3+ ions occupy the
octahedral sites which decrease the Fe3+ ions. Hence,
lesser amount of electron charges transfer takes place
between Fe2+ Fe3+, therefore the resistivity of the
samples increased by increasing the Al3+ ion
substitution. It is noticed that the activation energy
increased from 0.315 to 0.346 eV with increasing Al3+
ion substitution, this is due to the increase of resistivity
in the prepared nanoferrite samples. The activation
energy and resistivity are directly proportional to each
other. The Curie temperature decreased from 674 to
635 K due to decreasing of grain size with Al3+ doping
substitution. It is found that the Curie temperature
depends on the grain size, which decreases with
decrease in the grain size. The Curie temperature
values calculated by Loria-Sinha method found to
decrease from 677 to 634 K. The Curie temperature
values measured by Lorie-Sinha method agreed very
well with the values calculated by two-probe method.
For Series-II nanoferrite samples the DC resistivity
found to increase from 0.083x106 to 0.151x106 -cm by
increasing the Ni2+ ion substitution at room temperature.
This is due to the occupying of Ni2+ ions at B-sites which
in turn reduces the Fe3+ ions substitution thereby
decreasing the electron transfer between Fe2+ Fe3+.
Hence, the resistivity increases by increasing the Ni2+
ion substitution. It is observed that the activation energy
increases slightly from 0.223 to 0.250 eV with Ni2+ ion
substitution due to increase in the resistivity of the
prepared nanoferrite samples. The Curie temperature
found to decrease in two-probe experimental method
from 671 to 647 K due to decrease in the grain size. The
activation energy and grain size are directly proportional
to each other. The Curie temperature values calculated
using the Lorie-Sinha method is found to decrease from
678 to 643 K. Finally, it is noticed that the Curie
temperature values calculated by both the methods are
in good agreement with each other.
I-V characteristics are studied for Series-I and Series-II
Ferrites using the Keithely 4200 model at room
temperature by applying -2 volt to +2 volts. It is
observed that all the samples showed the typical
hysteresis nature of magnetic behaviour. The prime idea
of this study is to examine whether the prepared ferrite
samples are suitable for switches or not.
Outcome of the Thesis
Based on our results and observations from the present
thesis work, herewith we are briefly presenting the
outcomes from our thesis,
 46

All the synthesized nanoferrite samples

showed soft magnetic behaviour. These Ferrites find
wide applications in high performance microwave
devices.
Ferrites with composition Ni0.5Zn0.5Al2.0O4
showed superparamagnetism property. Therefore these
Ferrites may be used in applications like MRI scanning,
cell and DNA separation, drug delivery, hyperthermia,
ferrofluids, heating transfer and sensors etc.
Series-I and Series-II Ferrites showed
excellent dielectric behavior, hence they may be used in
wide frequency ranges from microwave frequency to
radio frequency.
Due to low dielectric values and high Curie
temperature values for Series-I and Series-II samples,
this nanoferrite may be used both at low and high
frequency devices.
In Series-I and Series-II, the high DC
resistivity is reported for Ni0.5Zn0.5Al2.0O4 and NiAlFeO4
samples. Therefore these Ferrites are highly suitable for
high frequency applications such as in electromagnetic
wave absorbing devices and telecommunications.