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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.

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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].

2

General Introduction

1.2 Magnetism in macroscopic materials
Magnetic materials are all around us whose properties and
applications underlie much of today’s 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

3

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

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.2) and (1. it can be shown that P P 0 1  F . = P r P 0 H = PH (1. Hence from the relations (1.4).

At higher values of H. the magnetization becomes constant at its saturation value Ms. (1. After saturation.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). 4 . 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.

magnetic materials below the Curie (or Neel) temperature due to long-range ordering of magnetic dipoles.magnetic (diamagnetic and paramagnetic) and ‘‘strong’’- magnetic (ferromagnetic. The diamagnetic and paramagnetic materials have zero magnetization at any temperature in the absence of the external magnetic field. General Introduction M(emu/g) Ms Mr Hc H (Oe) Figure 1.2. The carriers of magnetic moment are usually sketched out as magnetic dipoles.) materials. ferrimagnetic.2). antiferromagnetic etc. then their total magnetic moment vanishes. Zero-field (spontaneous) magnetization takes place only in ‘‘strong’’. Note that such arrangements take place below the 5 . While ferromagnetic has only one magnetic lattice composed of parallel dipoles. As it seems from Figure 1. Since the sublattices in antiferromagnetic crystals are identical. The origin of this ordering lies in the quantum-mechanical exchange forces. ferro and ferrimagnetic specimens should have very large total magnetic moment even in the absence of an external magnetic field.1 Typical Hysteresis Curve A classification of substances by their magnetic properties includes ‘‘weak’’. antiferromagnetics and ferrimagnetics can be considered as superposition of two oppositely directed magnetic sublattices (Figure 1.

Domains are separated by domain walls. The main contributions to the magnetic energy are magnetostatic energy. The process of magnetization causes all the domains to orient in the same direction. The formation of domains allows ferromagnetic materials to minimize its total magnetic energy.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. the magnetization averages to zero. Figure 1. Weiss first proposed that a ferromagnet contains a number of small regions called domains. magnetocrystalline energy and magnetostrictive energy which 6 .Chapter -1 ordering temperature regardless of the absence or presence of an external magnetic field (H). When a ferromagnetic material is in its demagnetized state. Ferromagnetic domains are small regions in ferromagnetic materials within which all the magnetic dipoles are aligned parallel to each other.

In crystals with large magnetocrystalline anisotropy. the domains are arranged such that the magnetization averages to zero. 11]. Eventually the applied filed is sufficient to eliminate all domain walls from the sample. large fields can be required to reach 7 . The growth occurs by domain wall motion that is provided by the external magnetic field. leaving a single domain with its magnetization pointing along the easy axis. The magnetization and hysteresis occurring in a ferromagnetic material can be suitably explained by domain theory [10. Figure 1. the domain whose magnetization is nearest to the field direction starts to grow at the expense of other domains. General Introduction influence the shape and size of the domains. When the field is applied.4 Schematic monodomain after the application of the field In the initial demagnetized state. 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.3 Schematic of multidomains in a ferromagnetic material Figure 1.

When at extremely high applied fields. Eventually. The magnetization directions of domains are determined mainly by the so-called crystalline anisotropy. When 8 . At still higher fields. the initial magnetization curve obtained during the increase. in general. The energy of atom in crystals depends on orientation of the magnetic moment with respect to crystallographic axis. and the explanation of the origin of domains in terms of magnetic field energy was given by Landau and Lifshitz [13].Chapter -1 saturation magnetization. the magnetization is equal to zero at a field (HC). only the directions of easy magnetization near the field direction are occupied. the magnetization rotates toward the field direction and the magnetic saturation can be reached after all. but domains magnetized close to the field direction grow at the expense of those magnetized away from the field direction (domain walls displacement). where HC is called the coercive force. The explanation of the molecular field in terms of exchange forces was contributed by Heisenberg [12]. a nonzero (remanent) magnetization Mr survives. Co. the magnetization approaches the saturation magnetization value Ms and the field is decreased. The directions for which the energy has minimum (maximum) value are called directions (axes) of easy (hard) magnetization. As a result. then the magnetization does not follow. When the field is decreased to zero. at first the magnetization remains along directions of easy magnetization. Ni is not a simple scalar magnitude but depends on the orientation of their crystallographic axes in the external magnetic field. in general. As the specimen is subjected to larger and larger fields. the saturation magnetization in bulk ferromagnets like Fe. So we will now discuss the magnetocrystalline anisotropy associated with magnetic materials. If the field is applied in the reverse direction.

Advances in new area of nanomagnetism include superparamagnetism [14]. Due to ‘‘impurities’’ (or defects) acting as pinning centers. 1.. ultrahigh magnetic anisotropy and coercive force. The realization of a specific domain pattern depends essentially on the magnetic history. experimentally observed hysteresis is a nonequilibrium (in thermodynamical sense) phenomenon complicated by the influence of the ferromagnet’s real structure (e.3 Magnetism in ultrafine nanoparticles: Nanomagnetism Among many of the known nanomaterials. nanoparticle and the corresponding 9 . morphology in polycrystals and composites. nanomagnetic materials have a special position due to its modified magnetic properties and applications in different fields. General Introduction the negative field increases still further.).g. defects in single crystals. etc. This irreversible behavior of magnetization versus external magnetic field is called hysteresis. the magnetization reaches the saturation value again. 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. Recent studies shows that magnetization and the magnetic anisotropy of the nanomaterials could be much greater than that of a bulk specimen. and is one of the most important criteria in the selection of ferromagnetic materials for practical applications. Naturally. domain wall dynamics becomes faster at temperatures near the Curie temperature. In general. and giant magnetic resistance (GMR). while difference in Curie or Neel temperatures. Currently a special place belongs to the magnetic properties in which the difference between a massive (bulk) and a nanomaterial is especially pronounced. The coercive force is the most sensitive property of ferromagnetic materials which is subject to control.

magnetic nanomaterials were found to possess a number of unusual properties like giant magnetoresistance. enhanced magnetic coercivity [16] etc.Chapter -1 microscopic phase reach hundreds of degrees. high density magnetic storage. their intrinsic magnetic properties like saturation magnetization (Ms). By changing the nanoparticle size. shape. one can control to an extent the magnetic characteristics of the materials based on them. quantum tunneling of magnetization [15]. the type and degree of defectiveness of the crystal lattice. Magnetic characteristics of nanoparticles are strongly influenced by so-called finite-size and surface effects. Finite-size effect results from quantum confinement of the electrons. magnetic refrigerants etc. the morphology. In addition. 10 . 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]. The size and shape of bulk samples are not crucially important. the interaction of the particles with surrounding matrix and the neighboring particles etc. high frequency electronics. Magnetic nanoparticles show a wide variety of unusual magnetic properties as compared to the respective bulk materials. Magnetic nanoparticles exhibit many unique phenomena such as superparamagnetism [14]. coercive force (HC) and Curie temperature (TC) depend only on chemical and crystallographic structure. Nanoscale magnetic materials are of interest for applications in ferrofluids. composition and structure. the particle size and shape. In case of bulk materials. Their relevance increases with decreasing particle size. high-performance permanent magnets. The magnetic properties of nanoparticles depend upon many factors like the chemical composition. abnormally high magnetocaloric effect and so on.

etc. For example. Recently the researchers focused their attention on the particles whose sizes are smaller than the domain size range. Typical values of single domain size range from 15 to 150 nm. General Introduction 1. domain size. macroscopic ferromagnetic single-crystal materials have well defined TC values depending exclusively on their composition [19]. In the view of the condensed matter physics.) [18].3. the correlated fluctuating magnetic moments in a volume are influenced by the finite size of the specimen. a single particle of size comparable to the minimum domain size would not break up into domains.1 Single Domain Particles Nanomagnetism usually considers so called single domain particles. As a specimen characteristic dimension d approach nano size values and since the magnetic correlation length diverges at TC. 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. The TC is then reduced as >TC d . finite-size effects [17] are originated due to cutting off of characteristic length (exchange length. resulting from the geometric limitation of particle volume.

 TC f.

5) TC f .@ r§¨ d ·¸ O (1.

if the particle size decreases. and d0 is an order of the characteristic microscopic dimension [20]. TC() is the bulk Curie temperature.  is related to a correlation length exponent. changing of crystallographic parameters or composition. either in the particle core or its surface layer. we can anticipate that the Curie temperature should also decrease. Hence. can mask or even inverse this effect [21. 11 . © d0 ¹ where. However. 22].

Thus due to surface effects saturation magnetization value generally decrease with decrease in particle size.that form in an effort to minimize the magnetostatic energy of the material. The motion of domain walls is a primary means of reversing magnetization. reduced coordination number. Small deviations from uniformity in the magnetization field within the nanoparticles can play a crucial role in determining its magnetic properties. This has been considered as a substantial evidence for the existence of single domain particles.Chapter -1 Surface effects are due to the lack of translational symmetry at outer boundaries of a particle. Experimental investigation on the dependence of coercivity 12 . until extremely small dimensions are reached. In addition to this. the surface effects can be shape dependent since the relative number of surface atoms depends on the particle shape [25]. Domains are separated by domain walls. in a maghemite ( -Fe2O3) particle of radius about 4 nm. homogeneous magnetization is achievable only for ellipsoidal bodies and so ideal single domain particle must be ellipsoidal. 50% of atoms lie on the surface [24]. Decreasing the particle size gradually increases the ratio of surface spins to the total number of spins and hence increases spin disorder. Distortion in particle shape can induce additional anisotropy. Shape of the nanoparticle also can influence its magnetic properties. which have a characteristic width and energy associated with their formation and existence. and broken magnetic exchange bonds of surface atoms [23]. According to classical Electrodynamics. The coercive force of nanoparticles is observed to increase with decrease in particle size. Macroscopic magnetic materials consist of a large number of magnetic domain .groups of spins all pointing in the same direction and acting cooperatively . stabilizing or destabilizing the single domain state. For instance.

5. The energy per particle is U  KV sin 2 T (1. Changes in the magnetization can no longer occur through domain wall motion and instead require the coherent rotation of spins.2 Superparamagnetism Consider an assembly of identical single domain particles with uniaxial anisotropy. the formation of domain walls becomes energetically unfavourable and the particles are of single domain. 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. In large particles. As the particle size decreases towards some critical particle diameter DC. General Introduction on particle size showed behaviour similar to that schematically illustrated in Figure 1.6) 13 . energetic considerations favour the formation of domain walls.3. Figure 1.5 Qualitative illustration of the behaviour of the coercivity in ultra fine particle systems as the particle size changes 1. resulting in larger coercivities.

K is the magnetic anisotropy constant and V is the volume of the particle. kBT << K1V. Thus this phenomenon is called superparamagnetism [14]. 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. the anisotropy energy can be neglected and the assembly magnetization can be described by the well-known Langevin function M = nMsL(x). It can be quite large thousands of Bohr Magnetons. At high enough temperature.1 T) required to achieve the saturation of nanoparticle assembly magnetisation M. At low temperatures. as dictated by the Langevin function. but with much larger magnetic moment. where n is the particle number density and x = 0H/kBT. but kBT would fight the alignment just as it does in paramagnet. kBT >>K1V. and the lack of hysteresis. Thus. the features of superparamagnetism are the scaling of magnetization curves with H/T. Moreover. the assembly shows hysteresis. that is. vanishing remanence and coercivity. An applied field would tend to align this giant moment. As a result of the competition between anisotropy and thermal energies. If single domain particles become small enough that.Chapter -1 where. T is the angle between the single particle magnetic moment P and the easy axis. the anisotropy barriers are very rarely overcome (weak thermal fluctuations). Following Neel’s arguments. This occurs because of the large particle moment ( P | 10 4 P B ) compared to the atomic moments ( P at | P B ). This moment is the moment of the particle and is equal to m=MsV. and this is called the blocked state. 14 . assemblies of small particles show behaviour similar to paramagnetic materials. the major difference between classical paramagnetism of bulk materials and superparamagnetism is the weak fields (H= 0.

the particle moments fluctuate without switching direction (on average) and the assembly is in the blocked state exhibiting hysteresis. hysteresis disappears. The blocking temperature can be easily measured FC-ZFC measurements [Chapter 2] using a SQUID magnetometer. Youngs modulus. anisotropy constant. For T > Tb.7) ¬ K BT ¼ The intrinsic time 0 depends on the material parameters (magnetostriction constant. the assembly is in the superparamagnetic state.8) K B «¬ W »¼ For T < Tb. Above Tb the system appears superparamagnetic. and thermal equilibrium is established. Below Tb. which is a characteristic of the experimental technique adopted. and saturation magnetization). It is remarkable that the value of Tb depends on 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. Typical values are 0 = 1010 to 109 s as obtained by Neel. General Introduction we assume that thermal activation over the anisotropy barrier can be described within the relaxation time approximation (or Arrhenius law) as ª K1V º W W 0 exp« » (1. and is given by K1V ªW m º Tb ln (1. This is called the blocking temperature (Tb) of the assembly. the condition for superparamagnetic behaviour is m >> . If m is the measuring time window. the free movement of the magnetic moment is blocked by the anisotropy. 15 .

Chapter -1 1.3. the independent spins slow down and build up into locally correlated unit known as 16 .3.3 Frustration Consider a lattice in which only nearest antiferromagnetic interactions operate. 27]. if two adjacent spins are placed parallel. which also shows a co-operative freezing transition. naturally there is a dilemma for the third spin. The system cannot achieve a state that entirely satisfies its microscopic state. hysteresis effects and time dependent relaxation towards equilibrium. 1. However on a triangular lattice. 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 [26.4 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. As a spin glass is cooled from high temperature. hence under frustration. In some systems. 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 competing interaction leads to frustration leading a multi-degenerate ground state. On the square lattice it is possible to satisfy the requirement that nearest neighbour spins must be antiparallel. but does possess a multiplicity of equally unsatisfied states. geometry of the lattice can frustrate the ordering of the spins [9]. This behaviour is normally exhibited in a nonmagnetic lattice populated within a dilute random distribution of magnetic atoms. Frustrated systems hence show metastability.

should depend on the size of the system in the following manner 17 . At Tf. change in coercivity. Their relevance increases as the particle size decreases. For example the finite scaling theory predicts a shift in transition temperature from that of a bulk. Finite size effects are due to the nanometric size of the particles. By finite size scaling theory the different magnetic characteristics like Tc. These properties are explained on the basis of finite size effect and surface effect. General Introduction clusters. Below Tf the ground state appears to be glassy possessing metastability and slow relaxation behaviour. The co-operative spin freezing in spin glasses is still not yet fully understood.3. strong decrease in saturation magnetization etc. A wide range of relaxation times is also observed below Tf. the fluctuation in the clusters progressively slow down. Hc. can be assumed to be varying as a function of particle size and the variations can be theoretically modeled through equations. These effects are manifested in nanometric particles through a wide variety of anomalous magnetic properties with respect to those of bulk materials. while surface effects are related to the symmetry breaking of the crystal structure at the boundary of each particle. 1. The nanoparticles are found to exhibit anomalous magnetic properties like enhancement in Curie temperature. the system finds one of its ground states and freezes.5 Finite Size effects and Surface effects The magnetic properties of fine particles are strongly influenced by finite size and surface effects. Ms etc. 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. showing that some free spins of small superparamagnetic clusters are still there. As the temperature cools to Tf (Tg).

in the form of nanometric particles. NiFe2O4. a random spin canting at the surface. In the 18 . Early models postulated the presence of a so called dead magnetic layer induced by the demagnetization of the surface spins. The general chemical formula of ferrites possessing the structure of the mineral spinel MgAl2O4 is MFe2O4.6 Å and 1 Å. Like all the magnetic properties TC can also be affected by surface effect at the nanoregime.4 Ferrites Microcrystalline ferrites form the basis of materials currently used for magnetic information recording and storage. In order to study finite scaling effect. 1. Nanocrystalline ferrites and magnetic carriers based on them will increase the recorded information density. the samples of different sizes should have the same microstructure [27. CoFe2O4. 28]. CuFe2O4. where M represents a divalent metal ion with an ionic radius approximately between 0.Chapter -1 1 TC (D )  TC ( D) § D · v ¨¨ ¸¸ (1. The origin of this noncollinear arrangement of the spins is attributed to the surface effects occurring in magnetic nanoparticle surfaces. 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. TC(D) is the curie temperature as a function of particle size D and n the initial exponent of the correlation length.9) TC (D ) © Do ¹ where TC() is the bulk curie temperature. caused by competing antiferromagnetic interactions was observed [29]. which causes a reduction in Ms because of its paramagnetic response. In more recent works devoted to the study of different ferrimagnetic oxides: -Fe2O3.

Zn2+or Cd2+ do not have unpaired electrons but they disproportionate the Fe3+ ions on the crystal lattice sites to increase the magnetic moment. Ferrites substituted with different cations prepared by various techniques exhibit interesting applications and involve exciting Physics in them. magnetic resonance imaging. M can represent a combination of which has an average valency of two. Other divalent ions such as Mg2+. Ni2+. If the non-magnetic ions present are not large in concentration. Cu and Zn. Nanoparticles of spinel ferrites are of practical interest for a wide range of applications like high density magnetic information storage. i. The properties of the ferrites in the nanoregime differ much from the bulk. combinations of these ions are possible to form mixed ferrites. The study of spinel ferrites in the nanoregime is significant because of their interesting magnetic and electrical properties with chemical and thermal stabilities. 19 . Ni. Diverge practical application of spinel ferrites has attracted the attention of researchers for decades. or Mg and Cd. targeted drug delivery etc. The trivalent ferric ions in MFe2O4 can completely or partly be replaced by another trivalent ion which gives rise to mixed crystals. these compounds will be magnetic. The presence of Fe2+.e. General Introduction case of simple ferrites. We can also go for solid solutions of two ferrites. Spinel ferrites shows interesting structural. Its characteristics widely vary with the method and the conditions of preparation. So a great variety of ferromagnetic oxides with spinel structure with different chemical composition is possible. Fe.. Co2+ and Mn2+ can provide unpaired electron spins and therefore contribute to the magnetic moment of spinel. Moreover. electrical and magnetic properties which vary with the nature of ions and crystal structure. M is one of the divalent ions of the transition elements Mn. Co.

Cd. Co. Cu. which is named after the mineral spinel. It turns out that of the 64 tetrahedral sites only 8 are occupied and out of 32 octahedral sites. Al or a mixture of these. There are eight formula units of MFe2O4 in a unit cell. 20 . 3. Gd. 31. Spinel ferrites are the simplest of these three groups. Spinel structure is determined primarily by the oxygen ion lattice.4. Ni. 32] 1. Sm. there are 64 tetrahedral sites and 32 octahedral sites. Spinel type with cubic crystal structure and general formula M2+Fe2O4 where M = Fe. 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. only 16 are occupied. Zn. MgAl2O4. Eu. Ferrites crystallize in three crystal types [30. Tb. Spinel ferrites crystallize into the spinel structure.Chapter -1 1. or Lu. A detailed picture of the spinel ferrites are shown below. Tm.1 Crystal Structure of Spinel Ferrite Ferrites are mixed metal oxides with iron (III) oxides as their main component. Magnetoplumbite type with hexagonal crystal structure and 2+ general formula M Fe12 O19 where M = Ba or Sr. Dy. Thus in a unit cell of 32 oxygen anions. This structure was first determined by Bragg and Nishikawa. Garnet type with cubic crystal structure and general formula Ln33+Fe5O12 where Ln = Y. Mg. Ho. Er. Mn. 2.

where the cations inside brackets are located in octahedral sites and the other outside brackets in tetrahedral sites. General Introduction Figure 1.6 Unit cell of spinel structure Figure 1. crystal field effects determine the distribution of cations in spinel ferrites.8 Octahedral Coordination Factors like ionic radii of the cations. For  =1. 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 . preference of ions to specific sites. Madelung energy. the ferrite form the normal spinel which has A-sites occupied by divalent 21 .7 Tetrahedral Coordination Figure 1.

Also in Nickel ferrite and cobalt ferrite nanoparticles Ni2+/Co2+ ions were experimentally observed in the tetrahedral sites. 36. where zinc ions with the highest preference for tetrahedral sites is found in the octahedral sites also. Different preparation techniques for nano-ferrites is discussed in next section 22 . both the tetrahedral and octahedral sublattice sites are occupied by divalent and trivalent ions. An inversion of degree of 60% was reported in manganese ferrite compared with 20% inversion in bulk. Grinding of microcrystalline ferrite powders to reach the nanosize of grains is inefficient because this gives particles with a broad size distribution. In a mixed spinel structure with  between 0 and 1. In inverse spinels like NiFe2O4 and CoFe2O4. while B-sites by trivalent cations. the metallic cation occupies the octahedral sites only with ferric ions equally distributed in the two sites [32. while the trivalent cations are being distributed among A and B sites. When  =0 it is called inverse spinel in which divalent cations occupy B-sites. 35. Most interesting is the cation distribution found in nanoparticles of zinc ferrite.Chapter -1 cations. Coming to the nanolevel a disordered cation distribution compared with the bulk has been observed in a number of ferrite systems. ZnFe2O4 and CdFe2O4 are normal spinels with all the divalent metal cation distributed in the tetrahedral sites. 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. All these redistribution of cations will lead to unexpected properties in ferrites at the nanoregime [34. 37]. 39]. 33].1 [40]. Neutron diffraction examinations of MgFe2O4 have yielded a value of  approximately equal to 0.

shape and properties. But as already mentioned in previous section. sol-gel method [43]. this 23 . Here the nanoparticles are synthesized by breaking down bulk materials gradually into smaller sizes until they are nanosized. Ferrites in bulk are usually manufactured using ceramic processing techniques.2 Synthesis techniques for ferrite nanoparticles. The challenge is to control the nanoparticle’s size. Mechanical breakdown such as high energy ball milling is a simple case of the top down strategy. In bottom-up approach the nanoparticles are built up from atom by atom. Generally two main approaches are adapted for the synthesis of nanoparticles: bottom-up method and top- down method. General Introduction 1. Generally. reverse micelle [47]. microemulsion method [44]. Most of the chemical synthesis methods can be included in the bottom-up method. Most popular methods are co-precipitation [42]. to assemble the nanoparticles for a given purpose and to make them from a variety of nanomaterials.4. this is inefficient because the resulting particles will be with a broad size distribution. Since we are particularly interested in nanoparticles of ferrites. 51]. Complex schedules and low production rate are common problems of the wet-chemical methods [49. 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. hydrothermal [45]. or molecule by molecule levels by controlling the reaction parameters. Top-down method is most applied in the traditional particle making process. precursor [48]. lithography or patterning etc are examples of top down method. spray pyrolysis [46]. etc. the important synthesis techniques are detailed here. So the physical methods like high energy ball milling [41].

Evolution of gas limits the occurrence of agglomeration [52]. The complexant selected is ethylene glycol of which the decomposition temperature is 1630C. the order in which the reagents are added to the solution and mixing. high crystallinity and narrow particle size distribution are some of the advantages of this preparation technique. Metal nitrates are hygroscopic and so easily become slurry.Chapter -1 method can be considered as solution combustion technique.) are co-precipitated under a fine control of pH by using NaOH or NH4OH solutions. Rapid evolution of a large volume of gasses accompanied by a great mass loss during xerogel combustion leads to the formation of ferrite nanopowders. sulphates. This method involves exothermic and self-sustaining thermally induced anionic redox reaction of xerogel. In this chemical method various salts (nitrates. The structure and crystallinity of the particles can be influenced by reaction rates and 24 . Particle size of the co-precipitated material is strongly dependent on the pH of the precipitation medium and molarity of the starting precursors. 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. Moreover dopants can be easily introduced into the final product. 51]. Good chemical homogeneity. high product purity. control over the particle size can be easily achieved. perchlorates etc. pH. Simple preparation process and low processing time also adds to this. temperature. The reaction and transport rates are affected by the concentration of reactants. which is obtained from aqueous solution containing desired metal salts (oxidizer) and organic complexant (reductant) [50. The nitrate salts are favoured as precursors because they serve as water- soluble low temperature NO3 oxidant source for synthesis. Consequently. Another method employed to produce ferrite nanoparticles is co- precipitation. chlorides.

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 A-O-B angles are about 1250 and 1540. compact and well formed. The B-O-B 25 . The three possible interactions are A-A interaction. These interactions are possible through the intermediate O2+ ions by super- exchange mechanism. nucleation and growth rates. 1. 33]. 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. Neel explained the spontaneous magnetization of these ferrites on the basis of Heisenberg’s exchange forces.4. as would follow from the theory of half-filled or more than half-filled 3d shells. B-B interaction and A-B interaction [32. 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. Particle morphology is influenced by factors such as supersaturation. General Introduction impurities. and the shape depends on crystal structure and surface energies.3 Magnetic Properties of Ferrites As the name suggests. For an undistorted spinel. The interaction is greatest for an angle of 1800 and also where the interatomic distances are the shortest. which are occupied in the two crystallographically distinct lattice sites. the particles are small. These ions include the ferric ions as well as the divalent metal ions which can be substituted in ferrites with spinel structure [30]. The exchange energy in ferrites is of the indirect super-exchange type. In ferrites three kinds of magnetic interactions are possible between magnetic ions. At low supersaturation. The predominating exchange energies between the magnetic ions in the ferrites are negative. ferrites exhibit a ferrimagnetic ordering.

The shape of the loops varies with respect to individual ferrites. In addition to this. 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. In developing his theory of ferrimagnetism. In general. They may be canted. When the particle size is reduced to a few tens of nanometers. the presence of a different cation distribution in the nano regime leading to 26 . In the A-A interaction the angle is about 80°. The B-B interaction is much weaker and most unfavourable situation occurs in A-A interaction. Therefore. the interaction between moments on the A and B sites is the strongest. 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. MnFe2O4) (ii) The orbital moment may not be quenched (eg.Chapter -1 angles are 900 and 1250. the value of saturation magnetization based on Neel’s two sublattice model is that the resultant saturation magnetization may be written as Ms= IMB-MAI. Thus with A-O-B interaction predominating the spins will be oppositely magnetized in the sublattices A and B. 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. ferrite materials exhibit high coercive field. with a resultant magnetic moment equal to the difference between those of A and B site ions. Ferrites exhibit hysteresis phenomenon during the magnetization cycle. CoFe2O4) (iii) The direction of the spins may not be antiparallel in the interactions. Neel postulated two separate sublattice magnetization corresponding to the two sublattices.

4. 1. but also for the interpretation of various physical phenomena. The low resistivity is caused in particular by the simultaneous presence of ferrous and ferric ions on equivalent lattice sites (octahedral sites) [53].4.5 D C Resistivity For ferrites the resistivity at room temperature can vary. The temperature dependence of resistivity of ferrites follows Arrhenius relation [30] U U 0 exp 'E kT . Spinel ferrites have high electrical resistivity. General Introduction different type of interactions play a significant role in deciding the magnetic properties [6].4 Electrical Properties Studies of electrical properties of dielectric crystals are required not only for the practical applications. low eddy currents and dielectric losses. depending on the chemical composition between 10-2ohm-cm and 1011ohm-cm. 1. Ferrites can be included in the class somewhere between semiconductors and insulators. This is a major advantage over ferromagnetic materials.

According to this relation. resistivity of ferrites decreases with increase in temperature. Such linear relationship is not always observed and sometimes the graph may be slightly curved [54]. (1. breaks occur in these curves at temperatures which correspond closely with the observed ferromagnetic Curie temperature [55]. The relationship between log U and 1T is found to be linear. 27 . however.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.

Similarly. 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]. The conduction in ferrites can be explained in terms of electron hopping and polaron models.4. 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].Chapter -1 Thus. 28 . In semiconductor based thermistor. which is discussed in next section. 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. 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. it is clear that high activation energy is associated with high resistivity at room temperature. the resistance diminishes with temperature. In ferrites. 1. 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]. the conduction mechanism is quite different than that of semiconductors. The PTC effect underlines the operating principle of posistors (thermally sensitive resistors).6 Conduction Mechanism Although ferrites show semiconducting properties. presence of impurities can influence resistivity [57]. For ferrites. Although the stoichiometry of the material determines the resistivity of ferrites [56]. the carrier concentration is almost constant but mobility of carriers is affected by temperature.

This process is called hopping of electron. the carrier may be trapped at the lattice site and its transition to the neighbouring site can be determined by the thermal activation. The electron coupled with this strain field is called a polaron. Small polaron formation is favoured in solids.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. General Introduction 1. Bosman and Van Daal [59] have given the detailed analysis of conduction due to polaron hopping. small polaron may absorb one or more phonons resulting in hopping mechanism. At elevated temperature. Many researchers [60. which at low temperature behaves like particle moving in a narrow conduction band. interaction between nearest neighbour is important. If the potential well is deep enough. conduction by small polaron becomes prominent. 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. An electron associated with large polaron moves in a band and electron associated with small polaron is trapped on a single ion. So a carrier becomes situated at the centre of the polarization potential well. 62] have reported that the conduction in ferrites is mainly due to small polaron hopping. The deformation further follows the electron as it moves through the lattice. If the size of the potential well is comparable to the ionic volume. When the tunnelling time is less than the time for successive hopping transition. 29 . 61. 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. and then small polaron model is used. If the polaron or its strain field spreads beyond lattice constant.4.

Ferrites are used at microwave frequencies for somewhat different reasons [65. The ferrites combined with their high permeability also make them suitable for filter inductor applications. The broad applications of ferrite nanoparticles include high density information storage.. the attenuation and phase shift of microwaves propagating through them have different values for the two opposite directions of propagation in a waveguide. minimal temperature variation. from milliWatt to kiloWatt. Ferrites are used in cores for magnetic memories [63. . 66.5 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. isolators and phase shifters [68]. ferrofluid technology. adsorption. 70.e. they exhibit non-reciprocal properties. Nano particles of MgFe2O4 have good photo electrical properties [69. The square loop characteristic along with the fast switching time t. ferrite cores are used for fly-back transformers in television sets. 64]. Spinel ferrite of chemical formula (MFe2O4) plays a significant role in microwave control components such as circulators. Power applications of ferrite cores cover a wide energy range.Chapter -1 1. Nickel zinc ferrites are used as deflection yoke core in a television picture tube. i. magnesium ferrite (MgFe2O4) enjoys a special attention because of its vast applications in high density recording media. Among different ferrites. heterogeneous catalysis. This greatly increases the energy received by a receiving antenna. At these frequencies. magnetic resonance imaging 30 . sensors and magnetic technologies. mechanical strength and low magnetostriction make them ideal for memory applications. Since ferrites have high resistivity and low eddy current loss. 71]. 67].

There are two main kinds of catalysts. The dispersal is ordinarily in a gas or a liquid solution. Using a combination of ferrite nanoparticles as contrast enhancement agents. Powdered nanoferrites are successfully used for the design of magnetic storage and recording devices. 1. Magnetic Resonance Imaging (MRI) creates detailed images of the soft tissue morphology.5.1 Catalytic wet peroxide oxidation of 4-chlrophenol Catalysis involves the modification of a chemical reaction rate. General Introduction enhancement. Heterogeneous catalyst is in a different phase from the reactants and is separated by a phase boundary. The magnetostrictive properties of cobalt ferrite nanoparticles are tailored for stress sensor applications. The homogeneous type is dispersed in the same phase as the reactants. The biocompatible ferrofluids based on ferrites are really promising for biomedical applications like cell separation and purification and magneto hyperthermia of tumor cells. homogeneous and heterogeneous. An enhanced magneto- optical effect and large magnetoelastic effect in cobalt ferrite are really promising. Zinc ferrite nanoparticles have generated a lot of interest owing to their potential applications in gas sensor and semiconductor photocatalysis [72. Usually. magnetically guided drug delivery and magnetocaloric refrigeration. Heterogeneous catalytic reactions typically take place on the 31 . Ferrofluids are stable colloidal suspensions composed of magnetic nanoparticles in organic or inorganic liquid carriers. 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. Most of the biocompatible fluids are based on magnetite and maghemite. 73]. mostly speeding up or accelerating the reaction rate by a substance called catalyst that is not consumed throughout the reaction. harmless radio waves and computer technology.

they can be involved in some processes for the preparation of a variety of other nanostructures like quantum dots. 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. Therefore. which is customarily reported in the unit of square meters per grams. There are different procedures to enhance the surface area of the catalyst. atmospheric air.Chapter -1 surface of a solid support. Various abatement techniques including biological. because it can provide a nearly complete degradation [77-82]. Active. (2) Some nanostructures themselves can serve as catalysts for certain chemical reactions. economical and stable catalysts 32 . The chemical activity of a conventional heterogeneous catalyst is proportional to its overall specific surface area per unit volume. These solid materials have very high surface areas that usually arise from their impregnation with acids or coating with catalytically active material e. 76]. bottom sediments. It is quite common for these materials to have pores with diameters in the nanometer range. silica or alumina. e. with typical values for commercial catalysts in the range of 100 m2/g to 400 m2/g. Among these techniques. thermal. and chemical treatments have been developed in the last few years for the detoxification of organic pollutants [75.g. which has been reported to be effective for the near ambient degradation of soluble organic pollutants.g. safe disposal of these compounds is emerging as an important area of research with increasing concern about the environment. Catalysts usually have two principal roles in nanotechnology areas: (1) In macro quantities. and soils [74]. nanotubes etc. catalytic wet peroxide oxidation (CWPO) appears to be a promising field of study. which result in voids or empty spaces within the material. platinum-coated surfaces. Most of them have been listed as priority pollutants due to the toxicity and hard biodegradability.

1. Large surface-to-volume ratio is an attractive characteristic that can be achieved from nanoscaling of magnetic materials. and hydrotalcite-like compounds [81. Thus. copper-based catalysts show higher resistance to leaching and better catalytic performance and wider range of pH operations [83]. nanosensors. there has been a considerable interest in the development of copper-based heterogeneous catalysts especially hydrotalcites and pillared clays (PILCs) in recent years. General Introduction would play a critical role in the degradation of organic pollutants in CWPO. metal-exchanged clays. 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]. the attention has been focused on different kinds of supported transition metal ion (iron or copper) catalysts such as metal-exchanged zeolites. 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 . Although they have been widely employed into the peroxide oxidation of phenol. their technological application should be introduced into many areas including nanocomposites. metal-exchanged resins. With such feature.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. Compared with iron-based catalysts. 82]. Reports on ferrites as catalysts to catalyze the peroxide oxidation of CPs is not yet reported. and photonics. nano- electronics. Recently. nanocatalysts. the catalytic oxidation of CPs over these catalysts at ambient temperature and pressure has not been reported. In the past 10 years.

and in magnetic technologies [84]. 34 . Apart from its magnetic application in the area of memory and switching circuits of digital computers and microwave devices. transformers. Research on different rare earth substituted ferrites has revealed to improve its properties [97-99]. Mg ferrite is used as a catalyst in dehydrogenation of butene. Magnetic properties of ferrites are strongly dependent on their chemical compositions and additives or substitutions. Magnesium ferrite is a soft magnetic n- type semiconducting material. So rare earth doped magnesium ferrite adequately suit these demands. choke coils. Small amount of foreign ions in the ferrite can dramatically change the properties of ferrites. antenna rods. influence of rare earth ions . Increase in resistivity and reduced dielectric loss attained by rare earth doping is promising as it is desirable for high frequency applications. which finds a number of applications in heterogeneous catalysis. Soft ferrite materials is extensively used in inductors. The magnetocrystalline anisotropy in ferrite is related to 4f–3d coupling between transition metal and rare earth ions.samarium. thereby doping rare into spinel Mg ferrite can improve their electrical and magnetic properties. Rare earth ions have unpaired 4f electrons that have a role to originate magnetic anisotropy due to their orbital shape. adsorption. power supplies with ferrite core is an integral part. video recorders etc. sensors. recording heads. microprocessors. So in the present study. But an investigation on structural. In electronic equipments like computers. magnetic and electrical properties of rare earth doped magnesium ferrite has not done much.Chapter -1 sensitive to the sample preparation history. humidity sensor and recently is more applicable in achieving local hyperthermia when compared with other ferrites [90–96]. loading coils. magnetic amplifiers and power transformer applications.

is chlorophenols (CP) [100]. fungicides and herbicides. economical and stable magnesium ferrite as catalyst for degradation of organic pollutants like 4-chlorophenols is invoked. uncontrolled use of wood preservatives. as well as via bleaching of pulp with chlorine. Oxidation of chlorophenols using ferrite as catalyst is not yet been reported. 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. which has been reported to be effective for the near ambient degradation of soluble organic pollutants. 35 . This pollutant is introduced into the environment through various human activities such as waste incineration. 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. Possibility of using ferrite in water treatment is discussed in Chapter 7. chlorination of drinking water and wastewater and from break down of phenoxy herbicides such as 2. magnetic and electrical properties are examined in detail. One of the most important members of pollutant from environmental and health view. Catalytic wet peroxide oxidation (CWPO) appears to be a promising field of study. pesticides. In present study an innovative use of active. So a scope of using magnesium ferrite as catalyst in CWPO of chlorophenols exists. 4-dichlorophenoxyacetic acid. General Introduction dysprosium and neodymium .in magnesium ferrite nanoparticles are explored. because it can provide a nearly complete degradation. But no work has been reported with ferrites as catalyst in peroxide oxidation of chlorophenols. Structural. Advanced oxidation processes (AOPs) have been successful in treating most of the refractory organic compounds present in polluted water.

3. Dy and x=0. Dy3+ and Sm3+ and to study the modifications in structural. quantity of catalyst and amount of hydrogen peroxide for different concentration of 4-CP. 0. magnetic and electrical properties. 0. Dy3+ and Sm3+ doping in oxidation of 4-chlorophenol.7 Objectives of the work ¾ Study the influence of preparation method on structural.by sol-gel method.Chapter -1 1. ¾ Study the impact of particle size on magnetic properties of samples and to tune magnetic properties by manipulating dopant concentration. 0. ¾ 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.2. ¾ Synthesis of magnesium ferrite (MgFe2O4) by chemical co- precipitation technique and sol-gel method ¾ High temperature and low temperature magnetic studies of sol-gel derived MgFe2O4 ¾ Partial replacement of Fe3+ ions in sol-gel derived nanocrystalline MgFe2O4 by rare earth ions Nd3+. ¾ Wet peroxide oxidation of 4-chlorophenol over magnesium ferrite as catalyst at room temperature ¾ Find optimum condition for complete oxidation of 4-chlorophenol from water by varying the reaction temperature (T).15.05. 0.1. ¾ Synthesis of three series – MgRxFe2-xO4 where R= Sm. 0. Nd. ¾ Correlation of results 36 . magnetic and electrical properties in each case.25. ¾ Compare the impact of Nd3+.

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