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2.1.

Nanoparticles
Nanoparticles are generally considered to be a number of atoms or molecules bonded together
with radious <100nm. A nanoparticles is 10-a or 10Ao, So Particle having radius ≤ 1000Ao can
be considered to be nanoparticle themselves had been around and studied long before the words
were coined.

For Example:- Many of the beautiful calors of stained glass windows are result of small metal
oxide clusters in the glass, having a size comparable to wavelength of light Particle of different
sizes scatter different clors to the glass. small colloidal particles of silver are a part of the process
of image formation in photography.

Nanotechnology.
Nanotechnology is called technology of the next century, coming after microtechnology
Nanotechnology unfortunately also becomes a catchword for people with ambitions in science
fiction Nanotechnology becomes a key word of public interest.
Ferrites
Ferrites may be defined as magnetic materials composed of oxides containing ferric ions as the
main constituent (The word ferrites comes from Latin "ferrum" for iron) and classified as
magnetic materials because they exhibit ferrimagnetic behaviour. The ferrites, in powder or thin
film forms, can be prepared by high temperature solid state reaction method. sol-gel method. Co-
Precipitation, Pulsed laster deposition, high energ ball milling and hydrothermal technique.

Classification and Types of ferrites


Ferrites are composed of iron oxide as their main constituent and metal oxides. Depending upon
the crystal structure, ferrites are of following types.

1) Spinel ferrite, 2) Garnet

3) Ortho-ferrite and 4) Hexagonal ferrites

Spinel ferrite

Spinel ferrites are described by the chemical formula MFe2O4 where M stands for
divalent metal ions. The crystal structure of spinel ferrite possess two interstitial sties namely
tetrahedral (A) and octahedral [B]. A variety of cations can accommodate at tetrahedral A site
and octahedral B site enabling wide variation in the properties of ferrites. M can be replaced by
other divalent metal ions and we can have number of spinel ferrites. Fe3+ ions can be replaced by
other trivalent ions like Al3+, Cr3+, Ga3+ etc. Fe3+ ions can also be replaced by compination of
divalent and tetravalent ions.

Garnet

The chemical formula for ferrimagnetic garnet is Me3Fe5O12 where, Me is a trivalent ion such as
rare earth or yttrium. The unit cell is cubic and contians eight molecules of Me3Fe5O12 i.e. (160
atoms). The metal ions are distributed over three types of sites. The Me ions occupy the
dodechedral sites (called c sites), where they are surrounded by eight oxygen ions, the Fe3+ ions
distributed over the tetrahedral and octhedral sites in the ratio 3:2. Thus, the cation distribution of
Me3Fe5O12 can be written as M e 𝑐3 Fe 𝑎2 Fe 𝑑3 O12.

As in the case of spinels, the magnetic alignment results from super exchange interaction via the
intervening oxygen ions, and the interaction is expected to be greater for the shorter the Me-O
distance and closer the Me-O-Me angle is to 180O.

Ortho-ferrites

Ortho-ferrites have the general formula MeFeO3, where, Me is a large trivalent metal ion, such as
rare-earth ion or Y. They crystallize in a distorted pervoskite structure with an orthorhombic unit
cell. These ortho-ferrites show a weak ferromagnetism, which has been attributed to the small
canting angle is of the order of 10-2 radian but is sufficient to introduce a small net ferromagnetic
moment perpendicular to the anti-ferromagnetic axis.

Hexagonal ferrites

There are a number of ferrites that crystallize in hexagonal structure, and some of them have
gained considerable technological importance in recent years. These ferrites are further sub-
classified into M, W, Y, Z and U compounds. All these have different, though related, crystal
structures. The M compounds have the simplest structure. Barium ferrite, the well known hard
ferrites, belongs to this class. These compounds have the general formula MeFe12O19 where Me
is a divalent ion of a large ionic radius, such as Ba2+, Sr2+, or Pb2+. Some compounds with
trivalent Me (e.g. La3+, Al, Ga, Cr, Fe) are also known. In these, one iron per formula unit is
present as Fe2+ to allow for the charge compensation.

The crystal structure of barium ferrite is hexagonal with the unit cell made up of two unit
formula. The structure is related to the spinel structure in which the oxygen lattice, f.c.c., consist
of a series of hexagonal laryers of oxygen lying prependicular to the (111) direction.

Types of ferrites are given in Table 1.1.

Table 1.1: Types of ferrites.

Applications of ferrites

Ferrites are regarded as better magnetic materials than pure metals because of their high
resistivity, lower cost, easier manufacture and superior magnetization properties. Ferrites are
extensively used in radar, audio-video and digital recording, bubble devices, memory rores of
computers, satellite communication and microwave devices [1-3]. Ferrite has a vast application
from microwave to radio frequencies. It is used for antenna cores in radio receivers, fly back
transformer in TV picture tube, broad band transformer, mechanical filter, ultrasonic generator,
moderators, phase shift, isolators.

Now a day ferrite is used in telephone exchange, computers, and control equipment. Ferrite is a
magnetic material of two types one is soft ferrite and second is the hard ferrite. Soft ferrite is
class of magnetic material used as transformer core mainly for television, telecommunication
computer, medical and other industrial electronic system. Hard ferrites are used for permanent
magnets mainly in loud speakers, micro motors, Ferrites is a ferromagnetic material also ferrites
is an inverse spinel taken to be collinear ferrimagnet. The low loss polycrystalline ferrites should
be used in a high frequency range. For the good performance in application and classified by the
initial permeability, for the low and high frequency applications, the most important
technological properties are saturation magnetization (Ms), coercive force (Hc) initial
permeability (𝜇𝑖) and losses. It is not possible generally to obtain the best combination of thsese
properties for any specific application. By verying the compositions or adding additives of by
varying the preparation technique, one can, to a large extent control most parameters for any
particular applications. The other applications of ferrites are as under;

High-Density Write-Once Optical Recording

Thin films of defect spinel ferrites can be used as write-once read-many media working with
blue wavelengths. In fact, because these non-stoichiometric ferrites are metastable, they can be
transformed into corundum phases as moderate temperatures by a laser spot. The transformed
regions have different optical indices form the starting ferrite film, making the readout process
possible [4].

Magnetic sensors

These are used for temperature control and these can be made using ferrite with sharp and
definite Curie temperature. Postion and rotational angle sensors (proximity switches) have also
been designed using ferrites.

Magnetic Shielding.

A radar absorbing paint containing ferrite has been developed to render an aircraft of submarine
invisible to radar.
Pollution Control

There are several Japanese installations which use precipitation of ferrite precursors to scavenge
pollutant materials such as mercury from waste streams. The ferrites produced subsequently can
be separated magnetically along with the pollutant.

Ferrite electrodes

Because of their high corrosion resistance, ferrites having the appropriate conductivities have
been used as electrode in applications such as chromium plating.

Entertainment ferrites

Ferrites are widely used in radio and television circuits. Typically applications include deflection
Yokes, fly back transformers and SMPS transformer for power applications.

Some of the recent applications of ferrites are listed below:

 Power transformer and chokes: HF Power supplies and lighting balasts.


 Inductors and tuned transformers: Frequency selective circuits
 Pulse and wideband transformers: Matching devices
 Magnetic deflection structures: TV sets and monitors
 Recording heads: Storage devices
 Rotating transformers: VCR's
 Shield beads and chokes: Interference suppresion
 Transducers: Vending machines and ultrasonic cleaners
 Catalysis: high surface area, controlled crystal surfaces
 Optical properties: sun screen, hyperthermic cancer treatment, flourescent tags
 Light scattering: smoke/fog screens
 Drug delivery: inhalation asthma, timed drug relase
 Pesticide delivery: fogging and fumigation
 Magnetic recording: orient magnetic domain axis, improtant for hard drive, video &
audio taps
 Pigments, inks, paints: coloring and opacity
Scanning Electron Microscopy (SEM)

This electron microscopy based technique determines the size, shape and surface morphology
with direct visualization of the nanoparticles. Therefore scanning electron microscopy offer
several advantages in morphological and sizing analysis. However the provide limited
information about the size distribution and true population average. During the process of SEM
characterization, solution of nanoparticles should be initially converted into a dry powder. This
dry powder is then further mounted on a sample holder followed by coating with a conductive
metal (e.g. gold) using a sputter coater. Whole sample is then analyzed by scanning with a
focused fine beam of electrons [20]. Secondary electrons emitted from the sample surface
determine the surface characteristics of the sample. This electron beam can often damage the
polymer of the nanoparticles which must be able to withstand vacuum. Average mean size
evaluated by SEM is comparable with results obtained by dynamic light scattering. In addition
these techniques are time consuming, costly and frequently need complementary information
about sizing distribution [21].

Transmission Electron Microscope

Experimental difficulties in studying nanostructures stem from their small size, which limits the
use of traditional techniques for measuring their physical properties. Transmission electron
microscopy techniques can provide imaging, diffraction and spectroscopic information, either
simultaneously or in a serial manner, of the specimen with an atomic or a sub-nanometer spatial
resolution. TEM operates on different principle than SEM, yet if often brings same type of data.
The sample preparation for TEM is complex and time consuming because of its requirement to
be ultra thin for the electron transmittance. High-resolution TEM imaging, when combined with
nanodiffraction, atomic resolution electron energy-loss spectroscopy and nanometer resolution
X-ray energy dispersive spectroscopy techniques, is critial to the fundamental studies of
importance to nanoscience and nanotechnology. During the TEM characterization nanoparticles
dispersion is deposited onto support grids of films. After dispersion they are fixed using either a
negative staining material (phosphotungstic acid or derivatives, uranyl acetate, etc., or by plastic
embedding). This is done to make nanoparticles withstand against the instrument vacuum and
facilitate handling.

Nanoparticles can be prepared from a variety of materials such as proteins, polyscchardes and
synthetic polymers.

Spinel Ferrites Structure


Properties of spinel ferrite

Magnetic Hysteresis

Figure 4.5: Variation of Magnetic field (B) with applied field (H).

A typical M (magnetization) verses H(field) graph for a magnetic material is shown in fig. 4.5.
Graph exhibits typical curve known as hysteresis. Starting from a demagnetized sample, if field
H is increases then magnetization M also increases and reaches a maximum value known as
sturation magnetization (Ms). If field is decreased and brought to zero, the magnetization
decreases without following the original path. The value of magnetization at which field is zero
is called remanence magnetization (Mr). With further decrease in field magnetization decreases
and reaches zero value.

Classification of Spinel Ferrite

In spinel lattice, the cations are distributed at tetrahedral (A) and octahedral [B] site dependng
upon their ionic radii, their electronic configuration and the electrostitic energy of the lattice. On
the basis of the occupancy of the cations at tetrahedral (A) and octahedral [B] sites,

The spinel ferrite is classified as normal, inverse and random spinel ferrite.
Normal Spinel Ferrite

In this type of spinel ferrite the davalent metal ions are totally occupied at tetrahedral A site and
the trivalent ferric ions are totally occupited at octahedral B site. The distribution of cations for
spinel ferrite represented by Mfe2O4 can be written as (M)A [Fe2]B O4. Zinc and cadmium ions
occupy tetrahedral A site and therefore zinc ferrite and cadmium ferrite are the best examples of
normal spinel ferrite.

Inverse Spinel Ferrite

In this type of spinel ferrite the divalent metal ions totally occupy octhedral [B] site where as the
trivalent ferric ions equally occupy tetrahedral (A) and octahedral [B] site. The distribution of
cations can be written as (Fe)A[MFe]BO4. The examples of inverse spinel ferrite are cobalt ferrite
and nickel ferrite.

Random spinel Ferrite

When the divalent metal ions and trivalent ferric ions occupy both tetrahedral and octahedral [B]
site, the spinel ferrite is called as random spinel ferrite. The distribution in such type of spinel
ferrite can be represented by (M1-xFex)[Fe2-xMx]O4, where x is distribution parameter and can
very between 0 and 1. Magnesium and copper ferrite is an example of random spinel ferrite.
these magnetic nano-particles of ferrite are used for drug taregeting and hyperthermia, separation
and magnetic resonance imaging. In environmental, separation and magnetic resonance imaging.
In environmental science ferrite nano-particles are used in treating polluted waste water from
industry. The recent application also includes high density information storage, ferro-fluids,
catalyst, sensors etc [16]. The following chart illustrates the applications of ferrite material.
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