[CHAPTER 1] A. A.

Birajdar

CHAPTER 1

Introduction, types and applications of ferrites

1.1 Introduction

Several years of worldwide revolutionary developments in

nanoscience, combining physics, chemistry, material science, theory and

even biosciences, have brought us to another level of understanding.

Nanotechnology becomes a key word of public interest, since even

politician and economists realized the social power of nanotechnological

development. Nanotechnology is called the technology of the next

century, coming after microtechnology. Nanotechnology unfortunately

also becomes a catchword for people with ambitions in science fiction.

Nanoparticles themselves had been around and studied long

before the words were coined. For example, many of the beautiful colors

of stained glass windows are result of the presence of small metal oxide

1
[CHAPTER 1] A. A. Birajdar

clusters in the glass, having a size comparable to the wavelength of light.

Particle of different sizes scatter different wavelength of light, imparting

different colors to the glass. Small colloidal particles of silver are a part of

the process of image formation in photography. Water at ambient

temperature consists of clusters of hydrogen-bonded water molecules.

Nanoparticles are generally considered to be a number of atoms or

molecules bonded together with a radius of <100nm. A nanoparticles is 10-

9
m or 10Å, so particles having a radius of about ≤1000Å can be considered

to be nanoparticles.

The history of ferrites (magnetic oxides) and their applications

have been known for several centuries ago. The loadstone (magnetite,

Fe3O4), a natural non-metallic solid, may attract iron was first described

in known Greek writings about 800 B.C. Much later, the first application

of magnetite was as 'Lodestones' used by early navigators to locate

magnetic North. That is the first scientific significance was appreciated,

after the first technical magnetic material because it formed the first

compass (Crangle, 1977). The first scientific study of magnetism named

De Magnete was published by William Gilbert in 1600. Later, in 1819 Hans

Christian Oersted observed that an electric current in a wire affected a

magnetic compass needle. Naturally occurring magnetite is a weak 'hard'

ferrite. 'Hard' ferrites possess a magnetism which is essentially

permanent. Originally manufactured in a few select shapes and sizes,

2
[CHAPTER 1] A. A. Birajdar

primarily for inductor and antenna applications, 'soft' ferrite has

proliferated into countless sizes and shapes for a multitude of uses.

Furthermore, ferrites are used predominately in three areas of electronics:

low level applications, power applications, and Electro-Magnetic

Interference (EMI) suppression. The breadth of application of ferrites in

electronic circuitry continues to grow. The wide range of possible

geometries, the continuing improvements in material characteristics and

their relative cost-effectiveness make ferrite components the choice for

both conventional and innovative applications.

Basically, ferrites are ceramic materials, dark grey or black in

appearance and very hard and brittle. Ferrites may be defined as magnetic

materials composed of oxides containing ferric ions as the main

constituent (the word ferrite comes from the Latin “ferrum” for iron) and

classified as magnetic materials because they exhibit ferrimagnetic

behavior. The ferrites, in powder or thin film forms, can be prepared by

high-temperature solid-state reaction method, sol–gel method,

coprecipitation, pulsed laser deposition, high-energy ball milling and

hydrothermal technique.

A ferrite core is made by pressing a mixture of powders containing

the constituent raw materials to obtain the required shape and then

converting it into a ceramic component by sintering. The magnetic

properties arise from interactions between metallic ions occupying

3
[CHAPTER 1] A. A. Birajdar

particular positions relative to the oxygen ions in the crystal structure of

the oxide. In the commercial ferrites, they can be divided into three

important classes, with each one having a specific crystal structure,

namely:

1. Soft ferrite with the garnet structure such as the microwave ferrites

(e.g: YIG).

2. Soft ferrites with the cubic spinel structure such as NiZn-, MnZn-,

and MgMnZn ferrites.

3. Hard ferrites with the magnetoplumbite (hexagonal) structure

such as Ba and Sr hexaferrites.

Ferrites are widely used in transformer and inductors for

telecommunications, power conversion and interference suppression.

Much of the ferrite-related research took place after the 1950s, thanks to a

technology expansion in various fields.

1.2 Classification and Types of ferrite

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

4
[CHAPTER 1] A. A. Birajdar

1.2.1 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 sites 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 combination of divalent

and tetravalent ions.

1.2.2 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 contains eight molecules of Me3Fe5O12 i.e. (160 atoms). The metal ions

are distributed over three types of sites. The Me ions occupy the

dodecahedral sites (called c sites), where they are surrounded by eight

oxygen ions, the Fe3+ ions distributed over the tetrahedral and octahedral

sites in the ratio 3:2. Thus, the cation distribution of Me3Fe5O12 can be

written as M e c3 F e a2 F e d3 O 1 2 .

As in the case of spinels, the magnetic alignment results from

super exchange interaction via the intervening oxygen ions, and the

5
[CHAPTER 1] A. A. Birajdar

interaction is expected to be greater for the shorter the Me-O distance

and closer the Me-O-Me angle is to 1800. On this basis it is concluded that

the interaction between the d and a cations are relatively strong (both

negative). These interactions control the magnetic alignments in the

solid, resulting in the following spin arrangement.

c a d
Me
uur 3 Fe
r 2 Fe
s 3 O12 for magnetic Me ion

Mec3 Fe a
ur 2 sFe
d
u 3O12 for non-magnetic Me ion

The total magnetic moments on ‘a’ and ‘d’ ions are aligned

antiparallel and the moments on the c-ions are antiparallel to those on

the d-ion. Thus for the formula (3M2O3)c(2Fe2O3)a (2Fe2O3)d the

arrangement is 6Fed, 4Fed, 6Mc. The net magnetic moment m (in Bohr

magneton per unit formula) is

m = 6mc - (6md-4ma) = 6mc -10 µB 1.1

Assuming a magnetic moment of 5µB per Fe ion, in terms of the unit

formula M3Fe5O12 equation 1.1 becomes

m = (3mC - 5µB) 1.2

where,

mc is the magnetic moment per Me ion.

1.2.3 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

6
[CHAPTER 1] A. A. Birajdar

distorted pervoskite structure with an orthorhombic unit cell. These

ortho-ferrites show a weak ferromagnetism, which has been attributed to

the small canting in the alignment of two anti-ferromagnetically coupled

lattices. The 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. The direction of spin orientation of the Fe ion in

HOFeO3 and ErFeO3 has been experimentally determined (9) at room

temperature and found to be parallel to the (100) axis on lowering the

temperature the spin axis rotates, and at 1.25K the direction is (001) for

HOFeO3 and (110) for ErFeO3. The spin moment on the rare earth ion gets

ordered at a much lower Neel temperature [6.5 K for HO Fe O3 and 4.3 K

for ErFeO3].

1.2.4 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

7
[CHAPTER 1] A. A. Birajdar

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 formulae. The structure is related to the spinel

structure in which the oxygen lattice, f.c.c., consist of a series of

hexagonal layers of oxygen lying perpendicular to the (111) direction.

Types of ferrites are given in Table 1.1.

Table 1.1: Types of ferrites

General
Type Structure Examples
Formula
Π AΠ=Cd,Co,Mg, Zn
Spinel Ferrites Cubic A Fe2O4
etc.
LnIII=Y,Sm,Eu,
Garnet Cubic Ln3IIIFe5O12 Gd,Tb,Dy,Ho,Er,Tm
and Lu
Magneto-
Hexagonal AΠFe12O19 AΠ=BaF12O19
plumbite

1.3 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 cores of

computers, satellite communication and microwave devices [1-3]. Ferrite

has a vast application from microwave to radio frequencies. It is used for

8
[CHAPTER 1] A. A. Birajdar

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. Ferrite is a ferromagnetic material also ferrite 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 these properties for any specific

application. By varying the compositions or adding additives or 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;

9
[CHAPTER 1] A. A. Birajdar

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 at moderate temperatures by a

laser spot. The transformed regions have different optical indices

from 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. Position

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.

10
[CHAPTER 1] A. A. Birajdar

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,

fluorescent tags

Light scattering: smoke/fog screens

11
[CHAPTER 1] A. A. Birajdar

Drug delivery: inhalation asthma, timed drug release

Pesticide delivery: fogging and fumigation

Magnetic recording: orient magnetic domain axis, important for

hard drives, video & audio tapes

Pigments, inks, paints: coloring and opacity

1.4 Literature review and aim of the present work:

With the boom in the synthesis and characterization techniques in

nanometric range, the research activities in the field of ferrites got a

surge. Superparamagnetism, collective magnetic excitations, low

saturation magnetization, enhanced coercivity, metastable cation

distributions, etc., are some of the phenomena which have been observed

in nanoparticles of various ferrites [5-9].

Synthesis of magnetic material has been an interesting area of

study for a long time. Studies shown that the physical properties of

ferrites depend on the processing, preparation condition and methods.

Ferrites are mostly prepared via conventional ceramic processing involves

commercially both long and high temperature treatments for the oxides

used in their preparation.

Ni–Zn ferrites having spinel crystal structure are extensively used

in a number of electronic devices because of their high permeability at

high frequency, remarkably high electrical resistivity, mechanical

12
[CHAPTER 1] A. A. Birajdar

hardness, chemical stability, and reasonable cost [10]. Zn and Ni are

known to have very strong preferences for the tetrahedral and octahedral

sites, respectively, making Ni–ferrite a model inverse ferrite and Zn–

ferrite a model normal ferrite [11]. Ni–Zn ferrite is thus expected to have a

cation distribution represented by (ZnxFe1-x)[Ni1-xFe1+x]O4. This system has

been extensively studied for various properties as well as for structural

issues.

The studies on magnetic and dielectric properties in Ni-Zn ferrites

synthesized by conventional technique have been reported by so many

workers [12-16]. The conventional method is the most common method

for preparing ferrites for so decades. Mohan et al., [17] studied the

dielectric properties of nickel zinc ferrites NixZn1-xFe2O4, where x changed

from 0.2 to 1.0 and synthesized by standard ceramic technique. They

investigated the frequency, temperature and composition dependence of

NiZn ferrites. They found the dielectric constant and loss tangent

decrease with increasing of zinc content up to x=0.4. Beyond x=0.4, they

observed these parameters increased progressively. They suggested the

variation of dielectric constant depends linearly on the variation of

available ferrous ions on octahedral sites. Dielectric constant declined

with increasing frequency. The maximum dielectric dispersion was seen

for x=0.8 which be explained on the basis of available ferrous ions on

octahedral sites. The variation of the dispersion with composition for

13
[CHAPTER 1] A. A. Birajdar

mixed nickel–zinc ferrites was explained by the fact the electron exchange

between Fe2+ and Fe3+ in an n-type semiconducting ferrite and hole

exchange between Ni3+ and Ni2+ in a p-type semiconducting. They

measured resistivity and dielectric constant was inversely proportional to

the square root of resistivity. Additionally, the dielectric loss reflected in

resistivity that the lower loss exhibited higher resistivity and vice versa. In

their research the dielectric constant increased gradually with increasing

temperature up to the particular temperature, which is designated as the

dielectric transition temperature Ts. However, beyond this temperature

the values of the dielectric constant for all the samples were found to

decrease continuously. In a later paper, Ranga and Revinder [18]

discussed the conductivity of Ni1-xZnxFe2O4 as a function of composition

and temperature. They observed conductivity increase with zinc content

and temperature. They calculated the charge carrier concentration and

observed the higher charge carrier in higher temperature up to magnetic

transition temperature. Beyond this temperature the concentration of

charge carrier decreased.

Further research was also done by El-Sayed [19] on the electrical

conductivity of Ni1-xZnxFe2O4 (x = 0.1, 0.3, 0.5, 0.7 and 0.9) which were

prepared by the ceramic processing technique. They found the lowest

conductivity and higher activation energy for x=0.3 in nickel zinc ferrite.

Ajmal and Maqsood [20] investigated the substitution of Zn in the Ni1-

14
[CHAPTER 1] A. A. Birajdar

xZnxFe2O4 system and checked the effect on the physical properties. They

studied the variation of zinc content on DC resistivity, dielectric constant

and loss factor. It was observed that dielectric constant increased with the

increase in Zn concentration. The resistivity values was in the range of

1.629×106 to 3.0×103 Ωcm. Loss factor remained in the range of 9.057–

0.456 with the variation in frequency from 80 Hz to 1 MHz, respectively.

It is observed by various workers that the magnetization having the

highest values for x =0.3 /0.4 in Ni1-xZnxFe2O4 [13, 14, 21-23]. So it was

decided that it will be very interesting to conduct the further research

with different ion substitution by keeping Ni0.7Zn0.3Fe2O4 as a parent

compound.

In conventional methods, there are some inherent drawbacks such

as poor compositional control, chemical inhomogenity, coarser particle

and introduction of some impurities during milling. Thus, the coarser and

non-uinform particles cause the formation of some voids and low-density

areas in the green compact [24].

However, the variety wet methods such as ball milling,

hydrothermal, sol-gel, microemulsions, and co-precipitation have been

used to synthesize ferrite materials. Each method has unique advantages.

But trying to improve the physical properties of ferrites by new designing

in synthesize is still a matter of primary interest. Recently sol-gel

methods have been used to prepare ultrafine, homogenous and

15
[CHAPTER 1] A. A. Birajdar

reproducible powder [25-29]. In the recent past, the sol-gel method has

been found to have distinct advantages over the conventional dry

processing. The final goal is to fabricate the ferrites with better physical

and magnetic properties that are useful in a variety of industrial

applications.

16
[CHAPTER 1] A. A. Birajdar

References

[1] A. Hagfeldth, M. Gratzel, Chem. Rev. 95 (1995) 49.

[2] S. Prasad, N. S. Gajbhiye, J. Alloys Compd. 265 (1998) 87.

[3] B. Viswanathan, V.R.K. Murthy: Ferrite Materials. Springer Verlag,

Berlin (1990)

[4] Laurence Bouet, Philippe Tailhades, Isabelle Pasquet, Corine

Bonningue, Stéphane Le Brun, Abel Rousset, Jpn. J. Appl. Phys. 38

(1999) pp. 1826-1828

[5] A. S. Albuquerque, J. D. Ardisson, W. A. A. Macedo, M. C. M.

Alves, J. Appl. Phys. 87 (2000) 4352.

[6] P. J. van der Zaag, P. J. van der Valk, M. T. Rekveldt, Appl. Phys.

Lett. 69 (1996) 2927.

[7] P. C. Fannin, S. W. Charles, J. L. Dormann, J. Magn. Magn. Mater.

201 (1999) 98.

[8] P. G. Bercoff and H. R. Bertorello, J. Magn. Magn. Mater. 213 (2000)

56.

[9] K. Haneda, Can. J. Phys. 65 (1987) 1233.

[10] K. Ishino and Y. Narumiya, Ceram. Bull. 66 (1987) 1469.

[11] J. Smit and H. P. J. Wijn, Ferrites-Physical Properties of

Ferrimagnetic Oxides in Relation to Their Technical Applications

(N. V. Philip’s Gloeilampenfabrieken, Eindhoven, Holland, 1959),

Chap. VIII, pp. 136–176.

17
[CHAPTER 1] A. A. Birajdar

[12] S. R. Murthy, B. Ramaiah, J. Mater. Sci. Lett. 19 (2000) 703.

[13] M. Ajmal, A. Maqsood, Mater. Lett. 62 (2008) 2077.

[14] P. Yadoji, R. Peelamedu, D. Agrawal, R. Roy, Mater. Sci. Engg. B 98

(2003) 269.

[15] A.K.M. Akther Hossaina, S.T. Mahmuda, M. Sekib, T. Kawaib, H.

Tabata, J. Magn. Magn. Mater. 312 (2007) 210.

[16] A.M. Abdeen, J. Magn. Magn. Mater. 185 (1998) 199.

[17] Mohan, G.R., D. Ravinder, A.V. Reddy, B.S. Boyanov, Mater. Lett.,

40 (1999) 39.

[18] G. Ranga Mohan, D. Ravinder, A.V. Ramana Reddy,B.S. Boyanov,

Mater. Lett. 40 (1999) 39.

[19] A. M. El-Sayed, Mater. Chem. Phys. 82 (2003) 583

[20] Muhammad Ajmal, Asghari Maqsood, Mater. Sci. Engg: B, 139 (

2007) 164.

[21] Santosh S. Jadhav, Sagar E. Shirsath, B. G. Toksha, S. J. Shukla, K.

M. Jadhav, Chin. J. Chem. Phys. 21 (2008) 381.

[22] S. V. Kakatkar, S. S. Kakatkar, R. S. Patil, A. M. Sankpal, S. S.

Suryawanshi, D. N. Bhosale, S. R. Sawant, Phys. Stat. Sol (b). 198

(1996) 853.

[23] Wang Li, Li Fa-Shen, Zhou Qing-Guo, Chin. Phys. 9 (2000) 685

[24] Gagan Kumar, Jagdish Chand, Satish Verma, M Singh, J. Phys. D:

Appl. Phys. 42 (2009) 155001

18
[CHAPTER 1] A. A. Birajdar

[25] Kashinath C. Patil, S.T. Aruna, Tanu Mimani, Curr. Opi. Solid State

and Mater. Sci. 6 (2002) 507.

[26] M. Popovici, C. Savii, D. Niznanskya, J. Subrta, J. Bohaceka, D.

Becherescub, C. Caizerc,C. Enache, C. Ionescu, J. Opto. Adv. Mater.

5 (2003) 251.

[27] P. Vijaya Bhasker Reddy, B. Ramesh, Ch. Gopal Reddy, Physica B:

Cond. Matter 405 (2010) 1852.

[28] Sagar E. Shirsath, B.G. Toksha, R.H. Kadam, S.M. Patange, D.R.

Mane, Ganesh S. Jangam, Ali Ghasemi, J. Phys. Chem. Solids 71

(2010) 1669.

[29] D. R. Mane, D. D. Birajdar, Swati Patil, Sagar E. Shirsath, R. H.

Kadam, J. Sol-Gel Sci. Tech. (Published Online) DOI:

10.1007/s10971-010-2357-8

19