General Introduction

Chapter 1 .

GENERAL INTRODUCTION

1.1 Nanomaterials and Nanotechnology

Material science and research is evolving in great phase with the aid
of nanoscale material development with wide variety of applications.
Nanoscience can be considered as ubiquitous in technology which has
relevance in many fields of research including condensed matter physics,
biology, medicine, electronics etc. Basically it is a multidisciplinary
subject which essentially requires contributions from physicists, chemists,
material scientists, engineers, molecular biologists, pharmacologists for the
proper development. Nanomaterials are materials with morphological
features on the nanoscale which is usually defined as smaller than a one
tenth of a micrometer in at least one dimension. The demand for smaller
particles for use in high density storage media is one of the fundamental
motivations for the fabrication of ultra-small nanoscale magnetic materials.
When particle sizes incorporated into devices become smaller and smaller,
the dimensionality of the particle approaches that of a molecule. A
nanoscale material is a physical object differing appreciably in properties
from its bulk counterpart. When dealing with nanoparticles, its physical
properties depend on size to a large extent.

1
Chapter -1

Nanotechnology is the technology dealing with both single

nanoobjects of materials, devices based on them and with processes that
take place in the nanometer range. Nanomaterials are those materials
whose key physical characteristics are dictated by the nanoobjects they
contain. They are classified into compact materials and nano dispersions.
Materials isotropic in the macroscopic composition and consisting of
incorporated nanometer-sized units as repeating structural elements are
called nanostrucutred materials that comes under first type of
nanomateials. Nanodispersions include a homogeneous dispersion medium
like gas, vacuum, liquid, and nanosized inclusions dispersed in this
medium which is isolated from each other [1, 2]. Nanoparticles with a
clearly ordered arrangement of atoms or ions are called nanocrystallites.

Nanoscience and nanotechnology mainly covers the length scale

from 1nm to 100nm. The transition from microparticles to nanoparticles
can lead to modifications in the physical and chemical properties. In the
nanometer dimensions, a large fraction of the atoms are at or near the
surface resulting in a large surface to volume ratio. This results in
increasing dominance of the behaviour of atoms on the surface of the
particle over that of those in the interior of the particle. This affects the
properties of the particles on isolation and its interaction with other
particles. This is where quantum size effects starts playing its role [3, 4].
At nanolevel, materials exhibit superlative physico-chemical properties
when compared to their microsized counterparts. With the emergence of
nanotechnology in the horizon of research, magnetism at the nanoscale is
being probed deeply from a fundamental perspective [5].

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 General Introduction

1.2 Magnetism in macroscopic materials

Magnetic materials are all around us whose properties and
applications underlie much of todays scientific and engineering works.
Despite its century old history, magnetism is still a scientific field with
great deal of puzzles. Most of the pure stable chemical elements carry an
atomic moment in the atomic ground state. However among pure elements
in polyatomic state, only O, Cr, Fe, Mn, Co, Ni and some rare earth
elements show magnetic ordering. In the case of substances consisting of
more than one type of atom, no simple approach allows to predict whether
a given substance is magnetic or not [1]. The fundamental source of
material magnetism is magnetic moments of electrons which constitute
electron shells of atoms and form electron structure of molecules and
crystals [6]. If the electron shell of an isolated atom is not closed, the atom
has nonzero magnetic moment. In molecules and in condensed matter,
interatomic interactions have significant action upon electron and magnetic
properties. If magnetism of individual atoms is preserved, interactions
between localized magnetic moments can result in magnetic ordering. In
metals, like Fe, Co, Ni, the magnetic moment of delocalized electrons can
also be a reason of magnetic ordering. It is a standard practice to analyze
magnetic properties of solids in terms of these two approaches models of
localized moments and itinerant (wandering) electrons [7]. In real
materials, both mechanisms can be important to a greater or lesser extent.
Another approach is spin fluctuation theory which tries to create unified
picture of magnetism [8]. Magnetism essentially results from two
electronic motion associated with the atom; the orbital motion of the
electron and the spin motion of the electron. For macroscopic purposes the
tiny currents due to these motions can be treated as magnetic dipoles.
Ordinarily they cancel each other because of the random orientation of the

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Chapter -1

atoms. When a magnetic field is applied, a net alignment of these magnetic

dipoles occur and the medium become magnetically polarized [9, 10]. The
magnetization M is the sum of the magnetic moments mi per unit volume

M m
volume
i
(1.1)

The magnetic properties of magnetic materials are characterized not

only by the magnitude and sign of M, but also the way in which M varies
with H. The ratio of these two quantities is called magnetic susceptibility.
M
F (1.2)
H
The magnetization M of a material is defined by the relation
B P 0 H  M  = P r P 0 H = PH (1.3)

where P 0 = 4S u107 Hm-1 is the permeability of free space and B and H are

measured in Tesla (T) and Am-1 respectively. P r is termed as the relative

permeability of the material.
Hence from the relations (1.2) and (1.4), it can be shown that
P P 0 1  F  (1.4)

The value of F and P r characterizes the magnetic properties of a

material Typical curves of M vs H called magnetization curves are
characterized by phenomena like saturation magnetization and hysteresis
(Figure1.1). At higher values of H, the magnetization becomes constant at
its saturation value Ms. After saturation, a decrease in H to zero does not
reduce M to zero which is termed as hysteresis. Mr is the remanent
magnetization and Hc is the coercive field or coercivity of the material.

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 General Introduction

M(emu/g)
Ms

Mr

Hc H (Oe)

Figure 1.1 Typical Hysteresis Curve

A classification of substances by their magnetic properties includes

weak- magnetic (diamagnetic and paramagnetic) and strong-
magnetic (ferromagnetic, ferrimagnetic, antiferromagnetic etc.) materials.
The carriers of magnetic moment are usually sketched out as magnetic
dipoles.
The diamagnetic and paramagnetic materials have zero
magnetization at any temperature in the absence of the external magnetic
field. Zero-field (spontaneous) magnetization takes place only in
strong- magnetic materials below the Curie (or Neel) temperature due
to long-range ordering of magnetic dipoles. The origin of this ordering lies
in the quantum-mechanical exchange forces. While ferromagnetic has only
one magnetic lattice composed of parallel dipoles, antiferromagnetics and
ferrimagnetics can be considered as superposition of two oppositely
directed magnetic sublattices (Figure 1.2). Since the sublattices in
antiferromagnetic crystals are identical, then their total magnetic moment
vanishes. As it seems from Figure 1.2, ferro and ferrimagnetic specimens
should have very large total magnetic moment even in the absence of an
external magnetic field. Note that such arrangements take place below the

5
Chapter -1

ordering temperature regardless of the absence or presence of an external

magnetic field (H).

Figure 1.2 Alignments of atomic magnets in different

types of magnetic materials

Actually the reason for spontaneous magnetization is the so-called

domain structure of ferromagnets. Weiss first proposed that a ferromagnet
contains a number of small regions called domains. Ferromagnetic
domains are small regions in ferromagnetic materials within which all the
magnetic dipoles are aligned parallel to each other. When a ferromagnetic
material is in its demagnetized state, the magnetization averages to zero.
The process of magnetization causes all the domains to orient in the same
direction. Domains are separated by domain walls. The formation of
domains allows ferromagnetic materials to minimize its total magnetic
energy. The main contributions to the magnetic energy are magnetostatic
energy, magnetocrystalline energy and magnetostrictive energy which

6
 General Introduction

influence the shape and size of the domains. The magnetization and
hysteresis occurring in a ferromagnetic material can be suitably explained
by domain theory [10, 11].

Figure 1.3 Schematic of multidomains in a ferromagnetic material

Figure 1.4 Schematic monodomain after the application of the field

In the initial demagnetized state, the domains are arranged such that
the magnetization averages to zero. When the field is applied, the domain
whose magnetization is nearest to the field direction starts to grow at the
expense of other domains. The growth occurs by domain wall motion that
is provided by the external magnetic field. Eventually the applied filed is
sufficient to eliminate all domain walls from the sample, leaving a single
domain with its magnetization pointing along the easy axis, oriented
closely to the external magnetic field. Further increase in magnetization
can occur only by rotating the magnetic dipoles from the easy axis of
magnetization into the direction of the applied field. In crystals with large
magnetocrystalline anisotropy, large fields can be required to reach

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Chapter -1

saturation magnetization. So we will now discuss the magnetocrystalline

anisotropy associated with magnetic materials.

The magnetization directions of domains are determined mainly by

the so-called crystalline anisotropy. The energy of atom in crystals depends
on orientation of the magnetic moment with respect to crystallographic
axis. The directions for which the energy has minimum (maximum) value
are called directions (axes) of easy (hard) magnetization. As a result, the
saturation magnetization in bulk ferromagnets like Fe, Co, Ni is not a
simple scalar magnitude but depends on the orientation of their
crystallographic axes in the external magnetic field.

The explanation of the molecular field in terms of exchange forces

was contributed by Heisenberg [12], and the explanation of the origin of
domains in terms of magnetic field energy was given by Landau and
Lifshitz [13]. As the specimen is subjected to larger and larger fields, at
first the magnetization remains along directions of easy magnetization, but
domains magnetized close to the field direction grow at the expense of
those magnetized away from the field direction (domain walls
displacement). Eventually, only the directions of easy magnetization near
the field direction are occupied. At still higher fields, the magnetization
rotates toward the field direction and the magnetic saturation can be
reached after all. When at extremely high applied fields, the magnetization
approaches the saturation magnetization value Ms and the field is
decreased, then the magnetization does not follow, in general, the initial
magnetization curve obtained during the increase. When the field is
decreased to zero, in general, a nonzero (remanent) magnetization Mr
survives. If the field is applied in the reverse direction, the magnetization is
equal to zero at a field (HC), where HC is called the coercive force. When

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 General Introduction

the negative field increases still further, the magnetization reaches the
saturation value again. This irreversible behavior of magnetization versus
external magnetic field is called hysteresis. In general, experimentally
observed hysteresis is a nonequilibrium (in thermodynamical sense)
phenomenon complicated by the influence of the ferromagnets real
structure (e.g., defects in single crystals, morphology in polycrystals and
composites, etc.). The realization of a specific domain pattern depends
essentially on the magnetic history. Due to impurities (or defects)
acting as pinning centers, at temperatures much below the Curie
temperature, domain walls propagate very slowly and the equilibrium
distribution of domains can only be reached in very long period. Naturally,
domain wall dynamics becomes faster at temperatures near the Curie
temperature. The coercive force is the most sensitive property of
ferromagnetic materials which is subject to control, and is one of the most
important criteria in the selection of ferromagnetic materials for practical
applications.

1.3 Magnetism in ultrafine nanoparticles: Nanomagnetism

Among many of the known nanomaterials, nanomagnetic materials

have a special position due to its modified magnetic properties and
applications in different fields. Advances in new area of nanomagnetism
include superparamagnetism [14], ultrahigh magnetic anisotropy and
coercive force, and giant magnetic resistance (GMR). Currently a special
place belongs to the magnetic properties in which the difference between a
massive (bulk) and a nanomaterial is especially pronounced. Recent studies
shows that magnetization and the magnetic anisotropy of the nanomaterials
could be much greater than that of a bulk specimen, while difference in
Curie or Neel temperatures, nanoparticle and the corresponding

9
Chapter -1

microscopic phase reach hundreds of degrees. The magnetic properties of

nanoparticles depend upon many factors like the chemical composition, the
type and degree of defectiveness of the crystal lattice, the particle size and
shape, the morphology, the interaction of the particles with surrounding
matrix and the neighboring particles etc. By changing the nanoparticle size,
shape, composition and structure, one can control to an extent the magnetic
characteristics of the materials based on them. In addition, magnetic
nanomaterials were found to possess a number of unusual properties like
giant magnetoresistance, abnormally high magnetocaloric effect and so on.

Nanoscale magnetic materials are of interest for applications in

ferrofluids, high density magnetic storage, high frequency electronics,
high-performance permanent magnets, magnetic refrigerants etc. Magnetic
nanoparticles exhibit many unique phenomena such as
superparamagnetism [14], quantum tunneling of magnetization [15],
enhanced magnetic coercivity [16] etc. In case of bulk materials, their
intrinsic magnetic properties like saturation magnetization (Ms), coercive
force (HC) and Curie temperature (TC) depend only on chemical and
crystallographic structure. The size and shape of bulk samples are not
crucially important. Magnetic nanoparticles show a wide variety of unusual
magnetic properties as compared to the respective bulk materials. Magnetic
characteristics of nanoparticles are strongly influenced by so-called
finite-size and surface effects. Their relevance increases with decreasing
particle size. Finite-size effect results from quantum confinement of the
electrons. Surface effects is related to the symmetry breaking of the crystal
structure at the boundary of each particle and the different chemical and
magnetic structures in internal (core) and surface (shell) parts of a
nanoparticle [1].

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 General Introduction

1.3.1 Single Domain Particles

Nanomagnetism usually considers so called single domain particles.
Typical values of single domain size range from 15 to 150 nm. Recently
the researchers focused their attention on the particles whose sizes are
smaller than the domain size range; a single particle of size comparable to
the minimum domain size would not break up into domains. These
particles are called domain free magnetic nanoparticles (DFMN) which
behaves like giant paramagnetic atom and shows superparamagnetic
behaviour when the temperature is above the so-called blocking
temperature. In the view of the condensed matter physics, finite-size
effects [17] are originated due to cutting off of characteristic length
(exchange length, domain size, etc.) [18], resulting from the geometric
limitation of particle volume. For example, macroscopic ferromagnetic
single-crystal materials have well defined TC values depending exclusively
on their composition [19]. As a specimen characteristic dimension d
approach nano size values and since the magnetic correlation length
diverges at TC, the correlated fluctuating magnetic moments in a volume
are influenced by the finite size of the specimen. The TC is then reduced as

>TC d   TC f@ r d
O
(1.5)
TC f  d0

where, TC() is the bulk Curie temperature,  is related to a correlation

length exponent, and d0 is an order of the characteristic microscopic
dimension [20]. Hence, if the particle size decreases, we can anticipate that
the Curie temperature should also decrease. However, changing of
crystallographic parameters or composition, either in the particle core or its
surface layer, can mask or even inverse this effect [21, 22].

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Chapter -1

Surface effects are due to the lack of translational symmetry at outer

boundaries of a particle, reduced coordination number, and broken
magnetic exchange bonds of surface atoms [23]. Decreasing the particle
size gradually increases the ratio of surface spins to the total number of
spins and hence increases spin disorder. For instance, in a maghemite
( -Fe2O3) particle of radius about 4 nm, 50% of atoms lie on the surface
[24]. Thus due to surface effects saturation magnetization value generally
decrease with decrease in particle size. The coercive force of nanoparticles
is observed to increase with decrease in particle size, until extremely small
dimensions are reached. This has been considered as a substantial evidence
for the existence of single domain particles.

Shape of the nanoparticle also can influence its magnetic

properties. According to classical Electrodynamics, homogeneous
magnetization is achievable only for ellipsoidal bodies and so ideal single
domain particle must be ellipsoidal. Distortion in particle shape can induce
additional anisotropy, stabilizing or destabilizing the single domain state.
Small deviations from uniformity in the magnetization field within the
nanoparticles can play a crucial role in determining its magnetic properties.
In addition to this, the surface effects can be shape dependent since the
relative number of surface atoms depends on the particle shape [25].

Macroscopic magnetic materials consist of a large number of

magnetic domain - groups of spins all pointing in the same direction and
acting cooperatively - that form in an effort to minimize the magnetostatic
energy of the material. Domains are separated by domain walls, which
have a characteristic width and energy associated with their formation and
existence. The motion of domain walls is a primary means of reversing
magnetization. Experimental investigation on the dependence of coercivity

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 General Introduction

on particle size showed behaviour similar to that schematically illustrated

in Figure 1.5. In large particles, energetic considerations favour the
formation of domain walls. As the particle size decreases towards some
critical particle diameter DC, the formation of domain walls becomes
energetically unfavourable and the particles are of single domain. Changes
in the magnetization can no longer occur through domain wall motion and
instead require the coherent rotation of spins, resulting in larger
coercivities. As the particle size continues to decrease below single domain
value, the spins are increasingly affected by thermal fluctuations and the
system becomes super paramagnetic.

Figure 1.5 Qualitative illustration of the behaviour of the coercivity in ultra

fine particle systems as the particle size changes

1.3.2 Superparamagnetism

Consider an assembly of identical single domain particles with

uniaxial anisotropy. The energy per particle is
U  KV sin 2 T (1.6)

13
Chapter -1

where, T is the angle between the single particle magnetic moment P and
the easy axis, K is the magnetic anisotropy constant and V is the volume of
the particle. If single domain particles become small enough that, KV
would become so small that the thermal energy fluctuations could
overcome the anisotropy forces and spontaneously reverse the
magnetization of a particle from one easy direction to another even in the
absence of an applied field. As a result of the competition between
anisotropy and thermal energies, assemblies of small particles show
behaviour similar to paramagnetic materials, but with much larger
magnetic moment. This moment is the moment of the particle and is equal
to m=MsV. It can be quite large thousands of Bohr Magnetons. An applied
field would tend to align this giant moment, but kBT would fight the
alignment just as it does in paramagnet. Thus this phenomenon is called
superparamagnetism [14]. At high enough temperature, kBT >>K1V, the
anisotropy energy can be neglected and the assembly magnetization can be
described by the well-known Langevin function M = nMsL(x), where n is
the particle number density and x = 0H/kBT. Thus, the features of
superparamagnetism are the scaling of magnetization curves with H/T, as
dictated by the Langevin function, and the lack of hysteresis, that is,
vanishing remanence and coercivity. Moreover, the major difference
between classical paramagnetism of bulk materials and
superparamagnetism is the weak fields (H= 0.1 T) required to achieve the
saturation of nanoparticle assembly magnetisation M. This occurs because
of the large particle moment ( P | 10 4 P B ) compared to the atomic moments
( P at | P B ). At low temperatures, kBT << K1V, the anisotropy barriers are
very rarely overcome (weak thermal fluctuations), the assembly shows
hysteresis, and this is called the blocked state. Following Neels arguments,

14
 General Introduction

we assume that thermal activation over the anisotropy barrier can be

described within the relaxation time approximation (or Arrhenius law) as

K1V
W W 0 exp (1.7)
K BT

The intrinsic time 0 depends on the material parameters

(magnetostriction constant, Youngs modulus, anisotropy constant, and
saturation magnetization). Typical values are 0 = 1010 to 109 s as
obtained by Neel. If m is the measuring time window, the condition for
superparamagnetic behaviour is m >> . The strong dependence of  on
temperature permits us to define a temperature above which the relaxation
time is so small that superparamagnetic behaviour is observed. This is
called the blocking temperature (Tb) of the assembly, and is given by

K1V W m
Tb ln (1.8)
K B W

For T < Tb, the particle moments fluctuate without switching direction (on
average) and the assembly is in the blocked state exhibiting hysteresis. For
T > Tb, the assembly is in the superparamagnetic state, hysteresis
disappears, and thermal equilibrium is established. It is remarkable that the
value of Tb depends on m, which is a characteristic of the experimental
technique adopted. Below Tb, the free movement of the magnetic moment
is blocked by the anisotropy. Above Tb the system appears
superparamagnetic. The blocking temperature can be easily measured
FC-ZFC measurements [Chapter 2] using a SQUID magnetometer.

15
Chapter -1

1.3.3 Frustration

Consider a lattice in which only nearest antiferromagnetic

interactions operate. On the square lattice it is possible to satisfy the
requirement that nearest neighbour spins must be antiparallel. However on
a triangular lattice, if two adjacent spins are placed parallel, naturally there
is a dilemma for the third spin. The system cannot achieve a state that
entirely satisfies its microscopic state, but does possess a multiplicity of
equally unsatisfied states, hence under frustration. Frustrated systems
hence show metastability, hysteresis effects and time dependent relaxation
towards equilibrium. In some systems, geometry of the lattice can frustrate
the ordering of the spins [9].

1.3.4 Spin glass

Spin glass can be considered as a random yet co-operative freezing

of spins at a well defined temperature Tf below which metastable frozen
state appears without usual magnetic long range ordering. This behaviour
is normally exhibited in a nonmagnetic lattice populated within a dilute
random distribution of magnetic atoms. The phase transition at the freezing
temperature (glass transition) shows a transition to a disordered state which
is distinctly different from the high temperature disordered state. The
distribution of distances between moments in a random site spin glass
leads to competing interaction of RKKY type and therefore the sign
depends on the distance between the ions [26, 27].

The competing interaction leads to frustration leading a

multi-degenerate ground state, which also shows a co-operative freezing
transition. As a spin glass is cooled from high temperature, the independent
spins slow down and build up into locally correlated unit known as

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 General Introduction

clusters. As the temperature cools to Tf (Tg), the fluctuation in the clusters

progressively slow down. The interactions between spins become more
long range so that each spin becomes more aware of spin in a progressively
gray region that amends it. At Tf, the system finds one of its ground states
and freezes. Below Tf the ground state appears to be glassy possessing
metastability and slow relaxation behaviour. A wide range of relaxation
times is also observed below Tf, showing that some free spins of small
superparamagnetic clusters are still there. The co-operative spin freezing in
spin glasses is still not yet fully understood.

1.3.5 Finite Size effects and Surface effects

The magnetic properties of fine particles are strongly influenced by

finite size and surface effects. Their relevance increases as the particle size
decreases. Finite size effects are due to the nanometric size of the particles,
while surface effects are related to the symmetry breaking of the crystal
structure at the boundary of each particle. These effects are manifested in
nanometric particles through a wide variety of anomalous magnetic
properties with respect to those of bulk materials. The nanoparticles are
found to exhibit anomalous magnetic properties like enhancement in Curie
temperature, change in coercivity, strong decrease in saturation
magnetization etc. These properties are explained on the basis of finite size
effect and surface effect. By finite size scaling theory the different
magnetic characteristics like Tc, Hc, Ms etc. can be assumed to be varying
as a function of particle size and the variations can be theoretically
modeled through equations. For example the finite scaling theory predicts
a shift in transition temperature from that of a bulk, should depend on the
size of the system in the following manner

17
Chapter -1
1
TC (D )  TC ( D) D v
(1.9)
TC (D ) Do

where TC() is the bulk curie temperature, TC(D) is the curie temperature as
a function of particle size D and n the initial exponent of the correlation
length. In order to study finite scaling effect, the samples of different sizes
should have the same microstructure [27, 28].

Like all the magnetic properties TC can also be affected by surface

effect at the nanoregime. For nanoparticles a significant fraction of atoms
is on the surface and it is reasonable to expect their magnetic interaction to
be different from the core atoms and hence a different average of the
magnetic properties results. Early models postulated the presence of a so
called dead magnetic layer induced by the demagnetization of the surface
spins, which causes a reduction in Ms because of its paramagnetic
response. In more recent works devoted to the study of different
ferrimagnetic oxides: -Fe2O3, NiFe2O4, CoFe2O4, CuFe2O4, in the form of
nanometric particles, a random spin canting at the surface, caused by
competing antiferromagnetic interactions was observed [29]. The origin of
this noncollinear arrangement of the spins is attributed to the surface
effects occurring in magnetic nanoparticle surfaces.

1.4 Ferrites

Microcrystalline ferrites form the basis of materials currently used

for magnetic information recording and storage. Nanocrystalline ferrites
and magnetic carriers based on them will increase the recorded information
density. The general chemical formula of ferrites possessing the structure
of the mineral spinel MgAl2O4 is MFe2O4, where M represents a divalent
metal ion with an ionic radius approximately between 0.6 and 1 . In the

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 General Introduction

case of simple ferrites, M is one of the divalent ions of the transition

elements Mn, Fe, Co, Ni, Cu and Zn, or Mg and Cd. The presence of Fe2+,
Ni2+, Co2+ and Mn2+ can provide unpaired electron spins and therefore
contribute to the magnetic moment of spinel. Other divalent ions such as
Mg2+, Zn2+or Cd2+ do not have unpaired electrons but they disproportionate
the Fe3+ ions on the crystal lattice sites to increase the magnetic moment.
We can also go for solid solutions of two ferrites, i.e., combinations of
these ions are possible to form mixed ferrites. Moreover, M can represent a
combination of which has an average valency of two. The trivalent ferric
ions in MFe2O4 can completely or partly be replaced by another trivalent
ion which gives rise to mixed crystals. If the non-magnetic ions present are
not large in concentration, these compounds will be magnetic. So a great
variety of ferromagnetic oxides with spinel structure with different
chemical composition is possible.

Spinel ferrites shows interesting structural, electrical and magnetic

properties which vary with the nature of ions and crystal structure. Its
characteristics widely vary with the method and the conditions of
preparation. Diverge practical application of spinel ferrites has attracted the
attention of researchers for decades. The properties of the ferrites in the
nanoregime differ much from the bulk. The study of spinel ferrites in the
nanoregime is significant because of their interesting magnetic and
electrical properties with chemical and thermal stabilities. Ferrites
substituted with different cations prepared by various techniques exhibit
interesting applications and involve exciting Physics in them.
Nanoparticles of spinel ferrites are of practical interest for a wide range of
applications like high density magnetic information storage, magnetic
resonance imaging, targeted drug delivery etc.

19
Chapter -1

1.4.1 Crystal Structure of Spinel Ferrite

Ferrites are mixed metal oxides with iron (III) oxides as their main
component. Ferrites crystallize in three crystal types [30, 31, 32]

1. Spinel type with cubic crystal structure and general formula

M2+Fe2O4 where M = Fe, Mn, Mg, Ni, Zn, Cd, Co, Cu, Al or a
mixture of these.

2. Garnet type with cubic crystal structure and general formula

Ln33+Fe5O12 where Ln = Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, or Lu.

3. Magnetoplumbite type with hexagonal crystal structure and

2+
general formula M Fe12 O19 where M = Ba or Sr.

Spinel ferrites are the simplest of these three groups. A detailed

picture of the spinel ferrites are shown below. Spinel ferrites crystallize
into the spinel structure, which is named after the mineral spinel, MgAl2O4.
This structure was first determined by Bragg and Nishikawa. Spinel
structure is determined primarily by the oxygen ion lattice. The oxygen
anions are packed in a face centered cubic arrangement such that there are
two kinds of interstitial space between the anions-tetrahedrally co-
ordinated A sites and octahedrally co-ordinated B sites. There are eight
formula units of MFe2O4 in a unit cell. Thus in a unit cell of 32 oxygen
anions, there are 64 tetrahedral sites and 32 octahedral sites. It turns out
that of the 64 tetrahedral sites only 8 are occupied and out of 32 octahedral
sites, only 16 are occupied.

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 General Introduction

Figure 1.6 Unit cell of spinel structure

Figure 1.7 Tetrahedral Coordination Figure 1.8 Octahedral Coordination

Factors like ionic radii of the cations, preference of ions to specific

sites, Madelung energy, crystal field effects determine the distribution of
cations in spinel ferrites. The interesting and useful magnetic and electrical
properties of the spinel are governed by the distribution of the iron and the
divalent metal ions among the octahedral and tetrahedral sites of the spinel
lattice. The general cation distribution can be represented as
> @
M G2 Fe13G M 12G Fe13G O4 , where the cations inside brackets are located in

octahedral sites and the other outside brackets in tetrahedral sites. For  =1,
the ferrite form the normal spinel which has A-sites occupied by divalent

21
Chapter -1

cations, while B-sites by trivalent cations. When  =0 it is called inverse

spinel in which divalent cations occupy B-sites, while the trivalent cations
are being distributed among A and B sites. In a mixed spinel structure with
 between 0 and 1, both the tetrahedral and octahedral sublattice sites are
occupied by divalent and trivalent ions. Neutron diffraction examinations
of MgFe2O4 have yielded a value of  approximately equal to 0.1 [40].
Magnesium ferrite is a typical spinel in which the cation distribution in the
crystal lattice site is very much sensitive to heat treatment due to high
diffusibility of Mg2+ions [38, 39]. ZnFe2O4 and CdFe2O4 are normal spinels
with all the divalent metal cation distributed in the tetrahedral sites. In
inverse spinels like NiFe2O4 and CoFe2O4, the metallic cation occupies the
octahedral sites only with ferric ions equally distributed in the two sites
[32, 33].

Coming to the nanolevel a disordered cation distribution compared

with the bulk has been observed in a number of ferrite systems. An
inversion of degree of 60% was reported in manganese ferrite compared
with 20% inversion in bulk. Also in Nickel ferrite and cobalt ferrite
nanoparticles Ni2+/Co2+ ions were experimentally observed in the
tetrahedral sites. Most interesting is the cation distribution found in
nanoparticles of zinc ferrite, where zinc ions with the highest preference
for tetrahedral sites is found in the octahedral sites also. All these
redistribution of cations will lead to unexpected properties in ferrites at the
nanoregime [34, 35, 36, 37].

Grinding of microcrystalline ferrite powders to reach the nanosize of

grains is inefficient because this gives particles with a broad size
distribution. Different preparation techniques for nano-ferrites is discussed
in next section

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 General Introduction

1.4.2 Synthesis techniques for ferrite nanoparticles.

Ferrites in bulk are usually manufactured using ceramic processing

techniques. Since we are particularly interested in nanoparticles of ferrites,
the important synthesis techniques are detailed here.

The challenge is to control the nanoparticles size, shape and

properties, to assemble the nanoparticles for a given purpose and to make
them from a variety of nanomaterials. Generally two main approaches are
adapted for the synthesis of nanoparticles: bottom-up method and top-
down method. In bottom-up approach the nanoparticles are built up from
atom by atom, or molecule by molecule levels by controlling the reaction
parameters. Top-down method is most applied in the traditional particle
making process. Here the nanoparticles are synthesized by breaking down
bulk materials gradually into smaller sizes until they are nanosized.
Mechanical breakdown such as high energy ball milling is a simple case of
the top down strategy. But as already mentioned in previous section, this is
inefficient because the resulting particles will be with a broad size
distribution. So the physical methods like high energy ball milling [41],
lithography or patterning etc are examples of top down method. Most of
the chemical synthesis methods can be included in the bottom-up method.
Most popular methods are co-precipitation [42], sol-gel method [43],
microemulsion method [44], hydrothermal [45], spray pyrolysis [46],
reverse micelle [47], precursor [48], etc. Complex schedules and low
production rate are common problems of the wet-chemical methods
[49, 51].

Sol-gel auto-combustion synthesis is a method where the chemical

sol-gel and combustion process is combined that has shown great potential
in the preparation of spinel type ferrite nanomaterials. Generally, this

23
Chapter -1

method can be considered as solution combustion technique. This method

involves exothermic and self-sustaining thermally induced anionic redox
reaction of xerogel, which is obtained from aqueous solution containing
desired metal salts (oxidizer) and organic complexant (reductant) [50, 51].
The nitrate salts are favoured as precursors because they serve as water-
soluble low temperature NO3 oxidant source for synthesis. The method
employed in present study is flash-combustion method in which metal
nitrates and complexant are directly mixed together by intensive stirring
and heating without adding water. Metal nitrates are hygroscopic and so
easily become slurry. The complexant selected is ethylene glycol of which
the decomposition temperature is 1630C. Rapid evolution of a large
volume of gasses accompanied by a great mass loss during xerogel
combustion leads to the formation of ferrite nanopowders. Evolution of gas
limits the occurrence of agglomeration [52]. Good chemical homogeneity,
high product purity, high crystallinity and narrow particle size distribution
are some of the advantages of this preparation technique. Moreover
dopants can be easily introduced into the final product. Simple preparation
process and low processing time also adds to this.

Another method employed to produce ferrite nanoparticles is co-

precipitation. In this chemical method various salts (nitrates, sulphates,
chlorides, perchlorates etc.) are co-precipitated under a fine control of pH
by using NaOH or NH4OH solutions. Particle size of the co-precipitated
material is strongly dependent on the pH of the precipitation medium and
molarity of the starting precursors. Consequently, control over the particle
size can be easily achieved. The reaction and transport rates are affected by
the concentration of reactants, temperature, pH, the order in which the
reagents are added to the solution and mixing. The structure and
crystallinity of the particles can be influenced by reaction rates and
24
 General Introduction

impurities. Particle morphology is influenced by factors such as

supersaturation, nucleation and growth rates. At low supersaturation, the
particles are small, compact and well formed; and the shape depends on
crystal structure and surface energies. The detailed discussion of two
preparation steps of ferrite nanoparticles used in the laboratory (sol-gel
synthesis and chemical co-precipitation techniques) is given in Chapter 2.

1.4.3 Magnetic Properties of Ferrites

As the name suggests, ferrites exhibit a ferrimagnetic ordering. Neel

explained the spontaneous magnetization of these ferrites on the basis of
Heisenbergs exchange forces. The exchange energy in ferrites is of the
indirect super-exchange type. The predominating exchange energies
between the magnetic ions in the ferrites are negative, as would follow
from the theory of half-filled or more than half-filled 3d shells. These ions
include the ferric ions as well as the divalent metal ions which can be
substituted in ferrites with spinel structure [30]. In ferrites three kinds of
magnetic interactions are possible between magnetic ions, which are
occupied in the two crystallographically distinct lattice sites. These
interactions are possible through the intermediate O2+ ions by super-
exchange mechanism. The three possible interactions are A-A interaction,
B-B interaction and A-B interaction [32, 33].

The strength in interaction between moments on various sites

depends on the distances between the metal ions and the oxygen anions
that links them and also on the angle between the three ions. The
interaction is greatest for an angle of 1800 and also where the interatomic
distances are the shortest. In A-A and B-B cases the angles are too small or
the distances between the metal ions and oxygen ions are too large. For an
undistorted spinel, the A-O-B angles are about 1250 and 1540. The B-O-B

25
Chapter -1

angles are 900 and 1250. In the A-A interaction the angle is about 80.
Therefore, the interaction between moments on the A and B sites is the
strongest. The B-B interaction is much weaker and most unfavourable
situation occurs in A-A interaction. Thus with A-O-B interaction
predominating the spins will be oppositely magnetized in the sublattices A
and B, with a resultant magnetic moment equal to the difference between
those of A and B site ions.

In developing his theory of ferrimagnetism, Neel postulated two

separate sublattice magnetization corresponding to the two sublattices. In
general, the value of saturation magnetization based on Neels two
sublattice model is that the resultant saturation magnetization may be
written as Ms= IMB-MAI. The variation of magnetization with temperature
in ferrites depends on the magnitude of sublattice magnetizations at 0K and
the ratios of the magnitudes of exchange interactions between the
sublattices. There can be deviations in the net magnetization which can be
attributed to several factors: (i) The cation distribution on various sites may
not be as perfect as predicted (eg. MnFe2O4) (ii) The orbital moment may
not be quenched (eg. CoFe2O4) (iii) The direction of the spins may not be
antiparallel in the interactions. They may be canted. Ferrites exhibit
hysteresis phenomenon during the magnetization cycle. The shape of the
loops varies with respect to individual ferrites.

When the particle size is reduced to a few tens of nanometers, ferrite

materials exhibit high coercive field, high Curie temperature and low
saturation magnetization as compared to their corresponding bulk values.
This phenomenon has been explained on the basis of finite size scaling
effects and surface effects occurring in the nanoregime. In addition to this,
the presence of a different cation distribution in the nano regime leading to

26
 General Introduction

different type of interactions play a significant role in deciding the

magnetic properties [6].

1.4.4 Electrical Properties

Studies of electrical properties of dielectric crystals are required not

only for the practical applications, but also for the interpretation of various
physical phenomena. Ferrites can be included in the class somewhere
between semiconductors and insulators. Spinel ferrites have high electrical
resistivity, low eddy currents and dielectric losses. This is a major
advantage over ferromagnetic materials.

1.4.5 D C Resistivity

For ferrites the resistivity at room temperature can vary, depending

on the chemical composition between 10-2ohm-cm and 1011ohm-cm. The
low resistivity is caused in particular by the simultaneous presence of
ferrous and ferric ions on equivalent lattice sites (octahedral sites) [53].
The temperature dependence of resistivity of ferrites follows Arrhenius
relation [30]

U 
U 0 exp 'E kT  (1.10)

where U is the resistivity and 'E is the activation energy required for the
hopping of an electron from one lattice site to another. According to this
relation, resistivity of ferrites decreases with increase in temperature. The
relationship between log U and 1T is found to be linear, however, breaks

occur in these curves at temperatures which correspond closely with the

observed ferromagnetic Curie temperature [55]. Such linear relationship is
not always observed and sometimes the graph may be slightly curved [54].

27
Chapter -1

Thus, it is clear that high activation energy is associated with high

resistivity at room temperature. Although the stoichiometry of the material
determines the resistivity of ferrites [56], presence of impurities can
influence resistivity [57].

1.4.6 Conduction Mechanism

Although ferrites show semiconducting properties, the conduction

mechanism is quite different than that of semiconductors. In ferrites, the
carrier concentration is almost constant but mobility of carriers is affected
by temperature. Conventional band theory and free electron theory fails to
explain conduction in ferrites as there are no Bloch type of wave as well as
no free electrons [33]. Band theory is in accordance with increase in carrier
concentration with temperature whereas hopping model considers that
conductivity is due to change in mobility of charge carriers with
temperature. Similarly, ferrites display a number of properties not inherent
in common semiconductors owing to the spontaneous polarization and to
the phase transition at Curie temperature [58]. One of this property is the
posistor effect (PTC effect) that shows a growth in resistivity of a
ferroelectric material with temperature when it passes from the
ferroelectric phase into paraelectric phase. The PTC effect underlines the
operating principle of posistors (thermally sensitive resistors). In
semiconductor based thermistor, the resistance diminishes with
temperature. For ferrites, the PTC region lies within the temperature
interval of crystal lattice rearrangement during phase transition and hence
with a diffused phase transition shows a smooth increase in resistivity over
the entire temperature interval where the diffused phase transition takes
place [58]. The conduction in ferrites can be explained in terms of electron
hopping and polaron models, which is discussed in next section.

28
 General Introduction

1.4.7 Hopping model of Electrons and Small Polaron Model

An electron in crystal lattice interacts through its electrical charge

with the ions or atoms of the lattice and creates a local deformation of the
lattice. The deformation further follows the electron as it moves through
the lattice. The electron coupled with this strain field is called a polaron. If
the polaron or its strain field spreads beyond lattice constant, it is called
large polaron and if the strain field extends over a distance less than a
lattice constant it is called a small polaron. An electron associated with
large polaron moves in a band and electron associated with small polaron
is trapped on a single ion. Thus the interaction between the conduction
electron or a hole with nearby ions may result in the displacement of the
ion and hence in the polarization of the surrounding region. So a carrier
becomes situated at the centre of the polarization potential well. If the
potential well is deep enough, the carrier may be trapped at the lattice site
and its transition to the neighbouring site can be determined by the thermal
activation. This process is called hopping of electron.

If the size of the potential well is comparable to the ionic volume,

interaction between nearest neighbour is important, and then small polaron
model is used. Small polaron formation is favoured in solids, which at low
temperature behaves like particle moving in a narrow conduction band. At
elevated temperature, small polaron may absorb one or more phonons
resulting in hopping mechanism. When the tunnelling time is less than the
time for successive hopping transition, conduction by small polaron
becomes prominent. Bosman and Van Daal [59] have given the detailed
analysis of conduction due to polaron hopping. Many researchers
[60, 61, 62] have reported that the conduction in ferrites is mainly due to
small polaron hopping.

29
Chapter -1

1.5 Applications of Ferrites

Ferrites in the bulk have many applications in high frequency devices

as an AC field does not induce undesirable eddy currents in insulating
materials. Nickel zinc ferrites are used as deflection yoke core in a
television picture tube. Since ferrites have high resistivity and low eddy
current loss, ferrite cores are used for fly-back transformers in television
sets. This greatly increases the energy received by a receiving antenna. The
ferrites combined with their high permeability also make them suitable for
filter inductor applications. Ferrites are used in cores for magnetic
memories [63, 64]. Ferrites are used at microwave frequencies for
somewhat different reasons [65, 66, 67]. At these frequencies, they exhibit
non-reciprocal properties, i.e., the attenuation and phase shift of
microwaves propagating through them have different values for the two
opposite directions of propagation in a waveguide. Power applications of
ferrite cores cover a wide energy range, from milliWatt to kiloWatt. The
square loop characteristic along with the fast switching time t, minimal
temperature variation, mechanical strength and low magnetostriction make
them ideal for memory applications.

Spinel ferrite of chemical formula (MFe2O4) plays a significant role

in microwave control components such as circulators, isolators and phase
shifters [68]. Among different ferrites, magnesium ferrite (MgFe2O4)
enjoys a special attention because of its vast applications in high density
recording media, heterogeneous catalysis, adsorption, sensors and
magnetic technologies. Nano particles of MgFe2O4 have good photo
electrical properties [69, 70, 71]. .

The broad applications of ferrite nanoparticles include high density

information storage, ferrofluid technology, magnetic resonance imaging

30
 General Introduction

enhancement, magnetically guided drug delivery and magnetocaloric

refrigeration. Using a combination of ferrite nanoparticles as contrast
enhancement agents, harmless radio waves and computer technology,
Magnetic Resonance Imaging (MRI) creates detailed images of the soft
tissue morphology. Powdered nanoferrites are successfully used for the
design of magnetic storage and recording devices. An enhanced magneto-
optical effect and large magnetoelastic effect in cobalt ferrite are really
promising. The magnetostrictive properties of cobalt ferrite nanoparticles
are tailored for stress sensor applications. Ferrofluids are stable colloidal
suspensions composed of magnetic nanoparticles in organic or inorganic
liquid carriers. The biocompatible ferrofluids based on ferrites are really
promising for biomedical applications like cell separation and purification
and magneto hyperthermia of tumor cells. Most of the biocompatible fluids
are based on magnetite and maghemite. Zinc ferrite nanoparticles have
generated a lot of interest owing to their potential applications in gas
sensor and semiconductor photocatalysis [72, 73].

1.5.1 Catalytic wet peroxide oxidation of 4-chlrophenol

Catalysis involves the modification of a chemical reaction rate,

mostly speeding up or accelerating the reaction rate by a substance called
catalyst that is not consumed throughout the reaction. Usually, the catalyst
participates in the reaction by interacting with one or more of the reactants
and is regenerated without any change at the end of process. There are two
main kinds of catalysts, homogeneous and heterogeneous. The
homogeneous type is dispersed in the same phase as the reactants. The
dispersal is ordinarily in a gas or a liquid solution. Heterogeneous catalyst
is in a different phase from the reactants and is separated by a phase
boundary. Heterogeneous catalytic reactions typically take place on the

31
Chapter -1

surface of a solid support, e.g. silica or alumina. These solid materials have
very high surface areas that usually arise from their impregnation with
acids or coating with catalytically active material e.g. platinum-coated
surfaces. Catalysts usually have two principal roles in nanotechnology
areas: (1) In macro quantities, they can be involved in some processes for
the preparation of a variety of other nanostructures like quantum dots,
nanotubes etc. (2) Some nanostructures themselves can serve as catalysts
for certain chemical reactions. The chemical activity of a conventional
heterogeneous catalyst is proportional to its overall specific surface area
per unit volume, which is customarily reported in the unit of square meters
per grams, with typical values for commercial catalysts in the range of
100 m2/g to 400 m2/g. There are different procedures to enhance the
surface area of the catalyst, which result in voids or empty spaces within
the material. It is quite common for these materials to have pores with
diameters in the nanometer range. The pore surface areas are usually
determined by the Brunauer-Emmett-Teller (BET) method.

Chlorophenols (CPs) can be found in many ecosystems: surface and

ground waters, bottom sediments, atmospheric air, and soils [74]. Most of
them have been listed as priority pollutants due to the toxicity and hard
biodegradability. Therefore, safe disposal of these compounds is emerging
as an important area of research with increasing concern about the
environment. Various abatement techniques including biological, thermal,
and chemical treatments have been developed in the last few years for the
detoxification of organic pollutants [75, 76]. Among these techniques,
catalytic wet peroxide oxidation (CWPO) appears to be a promising field
of study, which has been reported to be effective for the near ambient
degradation of soluble organic pollutants, because it can provide a nearly
complete degradation [77-82]. Active, economical and stable catalysts

32
 General Introduction

would play a critical role in the degradation of organic pollutants in

CWPO. In the past 10 years, the attention has been focused on different
kinds of supported transition metal ion (iron or copper) catalysts such as
metal-exchanged zeolites, metal-exchanged clays, metal-exchanged resins,
and hydrotalcite-like compounds [81, 82]. Compared with iron-based
catalysts, copper-based catalysts show higher resistance to leaching and
better catalytic performance and wider range of pH operations [83]. Thus,
there has been a considerable interest in the development of copper-based
heterogeneous catalysts especially hydrotalcites and pillared clays (PILCs)
in recent years. Although they have been widely employed into the
peroxide oxidation of phenol, the catalytic oxidation of CPs over these
catalysts at ambient temperature and pressure has not been reported.
Reports on ferrites as catalysts to catalyze the peroxide oxidation of CPs is
not yet reported.

1.6 Motivation of the present work

Spinel ferrites in microscale have been widely investigated from

early days due to its application as switching devices and memory devices
in computers. Recently, nanostructures of magnetic materials have
received more and more attention due to their novel material properties
that are significantly different from those of their bulk counterparts
[85-89]. Large surface-to-volume ratio is an attractive characteristic that
can be achieved from nanoscaling of magnetic materials. With such
feature, their technological application should be introduced into many
areas including nanocomposites, nanocatalysts, nanosensors, nano-
electronics, and photonics. Magnesium ferrite (MgFe2O4) is one of the
most important ferrite with a partially inverse cubic spinel structure and it
can be considered as a collinear ferrimagnet whose degree of inversion is

33
Chapter -1

sensitive to the sample preparation history. Magnetic properties of ferrites

are strongly dependent on their chemical compositions and additives or
substitutions. Small amount of foreign ions in the ferrite can dramatically
change the properties of ferrites. Magnesium ferrite is a soft magnetic n-
type semiconducting material, which finds a number of applications in
heterogeneous catalysis, adsorption, sensors, and in magnetic technologies
[84]. Apart from its magnetic application in the area of memory and
switching circuits of digital computers and microwave devices, Mg ferrite
is used as a catalyst in dehydrogenation of butene, humidity sensor and
recently is more applicable in achieving local hyperthermia when
compared with other ferrites [9096].

Increase in resistivity and reduced dielectric loss attained by rare

earth doping is promising as it is desirable for high frequency applications.
In electronic equipments like computers, microprocessors, video recorders
etc. power supplies with ferrite core is an integral part. Soft ferrite
materials is extensively used in inductors, transformers, antenna rods,
loading coils, choke coils, recording heads, magnetic amplifiers and power
transformer applications. So rare earth doped magnesium ferrite adequately
suit these demands.
Rare earth ions have unpaired 4f electrons that have a role to
originate magnetic anisotropy due to their orbital shape. The
magnetocrystalline anisotropy in ferrite is related to 4f3d coupling
between transition metal and rare earth ions, thereby doping rare into
spinel Mg ferrite can improve their electrical and magnetic properties.
Research on different rare earth substituted ferrites has revealed to improve
its properties [97-99]. But an investigation on structural, magnetic and
electrical properties of rare earth doped magnesium ferrite has not done
much. So in the present study, influence of rare earth ions - samarium,

34
 General Introduction

dysprosium and neodymium - in magnesium ferrite nanoparticles are

explored. Structural, magnetic and electrical properties are examined in
detail. An investigation on the transport characteristics of these series will
be in the right direction in order to develop an insight into the different
mechanism that operates at nanodimensions. Also nanosized magnesium
ferrite doped with rare earth ions is a system where the magnetic properties
can be tuned considerably by manipulating the concentration of doping.

Advanced oxidation processes (AOPs) have been successful in

treating most of the refractory organic compounds present in polluted
water. One of the most important members of pollutant from
environmental and health view, is chlorophenols (CP) [100]. This pollutant
is introduced into the environment through various human activities such
as waste incineration, uncontrolled use of wood preservatives, pesticides,
fungicides and herbicides, as well as via bleaching of pulp with chlorine,
chlorination of drinking water and wastewater and from break down of
phenoxy herbicides such as 2, 4-dichlorophenoxyacetic acid. Possibility of
using ferrite in water treatment is discussed in Chapter 7. Oxidation of
chlorophenols using ferrite as catalyst is not yet been reported. In present
study an innovative use of active, economical and stable magnesium ferrite
as catalyst for degradation of organic pollutants like 4-chlorophenols is
invoked. Catalytic wet peroxide oxidation (CWPO) appears to be a
promising field of study, which has been reported to be effective for the
near ambient degradation of soluble organic pollutants, because it can
provide a nearly complete degradation. But no work has been reported with
ferrites as catalyst in peroxide oxidation of chlorophenols. So a scope of
using magnesium ferrite as catalyst in CWPO of chlorophenols exists.

35
Chapter -1

1.7 Objectives of the work

Study the influence of preparation method on structural, magnetic

and electrical properties.
Synthesis of magnesium ferrite (MgFe2O4) by chemical co-
precipitation technique and sol-gel method
High temperature and low temperature magnetic studies of sol-gel
derived MgFe2O4
Partial replacement of Fe3+ ions in sol-gel derived nanocrystalline
MgFe2O4 by rare earth ions Nd3+, Dy3+ and Sm3+ and to study the
modifications in structural, magnetic and electrical properties in
each case.
Synthesis of three series MgRxFe2-xO4 where R= Sm, Nd, Dy and
x=0.05, 0.1, 0.15, 0.2, 0.25, 0.3- by sol-gel method.
Study the impact of particle size on magnetic properties of samples
and to tune magnetic properties by manipulating dopant
concentration.
DC conductivity and AC conductivity study on the transport
characteristics of these series to procure an insight into the different
mechanism that operate at nano-dimensions.
Wet peroxide oxidation of 4-chlorophenol over magnesium ferrite
as catalyst at room temperature
Find optimum condition for complete oxidation of 4-chlorophenol
from water by varying the reaction temperature (T), quantity of
catalyst and amount of hydrogen peroxide for different
concentration of 4-CP.
Compare the impact of Nd3+, Dy3+ and Sm3+ doping in oxidation of
4-chlorophenol.
Correlation of results

36
 General Introduction

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FG

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