FABRICATION, CHARACTERIZATION AND

MICROWAVE ABSORPTION STUDIES OF

HEXAGONAL FERRITES

Thesis Submitted in Partial Fulfillment of the requirement for the Degree

of
DOCTOR OF PHILOSOPHY (PhD)

by

FAIZA AEN
REGISTRATION NO. 96-im-159

Supervisor:
Prof Dr. Mazhar-Ud-Din Rana

DEPARTMENT OF PHYSICS
BAHAUDDIN ZAKARIYA UNIVERSITY
MULTAN-PAKISTAN

DEDICATED to
54
My Parents: Mr. M. Hanif Qadri & Mrs Khurshid Begum
Brothers, Sister and Husband

DECLARATION

I hereby declare that I have not submitted this research work titled “Fabrication,
Characterization and Microwave Absorption Studies of Hexagonal Ferrites” to the
degree of Ph.D. in Physics to other university within the Pakistan or outside Pakistan. I
also promise not to submit the same thesis for the degree of Ph.D. to any other university

55
in future if I am awarded Doctorate in this regard. Research work on the same topic has
never been submitted before to the best of my knowledge. The responsibility of the
contents solely lies to me.

Faiza Aen

The Controller of Examination,

Bahauddin Zakariya University,
Multan.

We, the Supervisory Committee, certify that the contents and form of thesis titled
“Fabrication, Characterization and Microwave Absorption Studies of Hexagonal
Ferrites” submitted by Mrs. Faiza Aen is fully adequate in scope and quality for the
award of PhD degree in Physics.

SUPERVISORY COMMITTEE

56
--------------------------------------
Dr. Anis ur Rehman (Examiner)
Associate Professor,
Department of Physics,
COMSATS Institute of Information Technology
Islamabad.

-----------------------------------------
Dr. Mazhar ud Din Rana (Supervisor)
Professor,
Department of Physics,
Bahauddin Zakariya, University, Multan.

---------------------------------------
Dr. Ejaz Ahmad (Chairman)
Professor,
Department of Physics,
Bahauddin Zakariya, University, Multan.

ACKNOWLEDGEMENTS

All praises and blessings to the most Gracious and Merciful, Allah. It is with great

submission that I bow my head before Him for giving me the courage to complete this

work.

With deep regards and profound respect, I avail this opportunity to express my deep

sense of gratitude and indebtedness to Prof. Dr. Mazhar-Ud-Din Rana, for introducing

the present research topic and for inspiring guidance, constructive criticism and valuable

suggestion throughout this research work.

I would like to express my gratitude to Prof. Dr. Ejaz Ahmad, Head of Physics

Department, for his cooperation in one way or the other. I wish to record my thanks and

57
gratitude to Prof Dr. Shahida B.Niazi, Dr. Misbah-ul-Islam for their valuable suggestions

and encouragements at various stages of the work. It would have not been possible for

me to bring out this thesis without their help and constant encouragement.

My special thanks to my husband Mr Muhammad FarooqWasiq for the completion of

thesis.

I wish to thanks Mr. Anwar Manzoor Rana, Mr.Asim Javed, Dr. Muhamamd Ishaque.

Mukhtar Ahmad, Imran khan, Imran Saddiq, Khalid Nadeem (PhD Fellows) for their

guidance and consistent encouragement for the completion of this work.

It was a nice and memorable association with all the stuff of my department. Iwish to

give them my heartfelt thanks for their constant help.

Many thanks to my friends, Ayesha Iftikhar, Sadia Khalid, Malaika Rani (PhD Fellows),

for encouraging during research work. I would also like to thanks to all my teachers and

professors, form academic and nonacademic levels, who inspire me to be wise and

knowledge.

I would like to thank my parents, Mr. Mohammad Hanif Qadri and Mrs Khurshid

Begum, who formed a part of my vision and taught me the good things that really matter

in my life, sister, Zeerak Maliha, brothers, Mohsin Zia, H.M. Khawar Usman, Ubada

huzaifa, Bilal Hasan and other family members, for their support for choices in all my

life and their love, which has been a constant source of strength for everything I do.

Above all, I thank to my Allah for giving me all these people to help and encourage me,

and for the skills and opportunity to complete this thesis.

Special thanks to Higher Education Commission (HEC) of Pakistan for the financial

assistance under PhD Indigenous Fellowship Program to complete my PhD studies.

FaizaAen

58
 ABSTRACT
W-type hexagonal ferrite is the most important magnetic materials used for the

manufacturing of microwave absorbers. The present work is focused on the influence of

divalent, trivalent cations substitutions on physical, electrical, magnetic and

electromagnetic properties of these hexagonal ferrites.

This dissertation presents a systematic study on four series namely, BaHoxZ n2Fe16-xO27

(x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0), Ba1-xHoxCo2Fe16O27(x= 0.0, 0.02, 0.04, 0.06, 0.08, 0.1),

SrGaxZn2Fe16-xO27 (x=0.0, 0.1, 0.2, 0.3, 0.4), SrNdxZn2Fe16-xO27 (x=0.0, 0.05, 0.1, 0.15,

0.2, 0.25) hexagonal ferrites.

A series of BaHoxZn2Fe16-xO27 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) W-Type hexagonal ferrites

were prepared by co-precipitation technique at high annealing temperature of 1320 ºC.

XRD reveals single W-type hexagonal phase in these ferrites. The grain size is measured

by SEM analysis using line intercept method. Saturation magnetization, retentivity and

59
coercivity were measured from MH-loops taken on VSM. It was observed that

magnetization increases with the increase of Ho content due to difference in ionic radii

of Ho3+ (0.901Å) and Fe3+ (0.67Å) ions. Room temperature dc resistivity increases as a

function of Ho3+ that may be due to separation between grains. The dc electrical

resistivity decreases as a function of temperature which indicates the semi-conducting

behavior of the samples.

Ba-based W-type hexagonal ferrite with composition Ba1-xHoxCo2Fe16O27(x= 0.0, 0.02,

0.04, 0.06, 0.08, 0.1) were prepared by sol gel auto-combustion technique. The

precursors were prepared by Ba2+, Fe3+ nitrates solutions with citric acid as chelating

agent. The as-prepared powder was sintered at 950 0C for 8 hrs to produce a single phase

of W-type hexaferrite with corresponding crystallite size ranging from 34nm to 44nm.

The thermal decomposition of nitrate-citrate gel of as-prepared powder was investigated

by TG/DTA. The FTIR spectral study reveals the presence of two absorption bands

which are characteristics of hexaferrites. DC electrical resistivity increases from

3.01×109 to 5.69× 1010 (ohm-cm).The real and imaginary parts of dielectric constant (έ,

ε‫ )״‬and dielectric loss tangent (tan δ) are determined in the frequency range of 20Hz to

1MHz. It is observed that both real and imaginary parts of the dielectric constant and

tanδ decrease with the increase of frequency on the basis of Wagner and Koop‟s theory.

A series of nano-sized single phase W-type SrGaxZn2Fe16-xO27 (x=0.0, 0.1, 0.2, 0.3, 0.4)

hexaferrites prepared by sol gel technique and sintered at 950 0C have been investigated.

The thermal decomposition behavior of nitrate-citrate gel of as prepared powder was

investigated by means of DTA/TGA analysis. The sintered powders were characterized

by FTIR, XRD, SEM, VSM and vector network analyzer (VNA). X-ray diffraction

patterns for pure and substituted W-type hexaferrites show the single phase structure

with no impurity phase. The lattice parameters (a and c) decrease with the increase of Ga

contents (x). The grain size estimated from SEM images is in the range of 139-76 nm

60
which confirms the nanocrystalline nature of the investigated samples. The saturation

magnetization (Ms) decreases whereas coercivity (Hc) increases with the increase of Ga

contents (x). The values of Hc for all of the investigated samples lie in the range of few

hundred Oersteds which is one of the necessary conditions for EM materials. The

microwave absorption property is enhanced in the frequency (with respect to -20dB)

from 0.5-13 GHz, and the bandwidth reaches 0.899 GHz. The attenuation peak value is -

32dB at the matching thickness of 3.4mm.

Rare earth substituted SrNdxZn2Fe16-xO27 W-type single phase hexagonal ferrites (x =

0.0---0.25) have been investigated. It is shown that lattice parameters increases with the

increase of Nd content due to larger ionic radius of Nd3+ than Fe3+ and grain size is also

increased due to crystal deformation and inner stress. Saturation magnetization increases

may be due to enhancement of magneto crystalline anisotropy with anisotropic Fe2+ ions

locating on 2a sites as usually found in rare earth ions substitution. This material can be

used for application in high density recording media. Dielectric behavior of material

deceases with the increase of applied field frequency according to Maxwell and Wagner

two layer model and the material is useful for the absorption of microwave radiations

and attenuation of electromagnetic interference due to high value of dissipation factor.

61
TABLE OF CONTENTS

Chapter – 1 Introduction
1.1 Ferrites 1
1.2 Hexagonal Ferrites 4
1.3 Hexagonal Closed Packed (HCP) Structure
1.4 Chemical Composition of Hexaferrites 6
1.5 W-Type Hexagonal Ferrites 7
1.6 Microwaves 10
1.7 Microwaves Absorbers 12
1.8 Principle of Operation 13
1.8.1 Impedance Matching Conduction
1.8.2 Quarter Wave Thickness Phenomenon
References 15
Chapter – 2 Literature Review 18
References 33
Chapter – 3 Experimental Techniques
3.1 Chemical Formulae of Ferrites 37
3.2 Methods of Preparation
3.2.1 Co-precipitation
3.2.2 Sol-Gel Auto Combustion 41
3.3 Characterization 46
3.3.1 Thermo Gravimetric and Differential Thermal Analysis 47
3.3.2 Fourier Transform Infrared (FTIR) Spectroscopy 48
3.3.3 X-ray Diffraction (XRD)
3.3.3.1 Physical Density 48
62
3.3.3.2 X-ray Densities 49
3.3.3.3 Porosity
3.3.4 Grain Size Measurements
3.3.5 D.C Resistivity Measurements 50
3.3.6 Dielectric Measurements 51
3.3.7 Magnetic Measurements 52

3.3.8 Microwave Absorption

References 53
Chapter – 4 Results and Discussion
4.1 BaHoxZn2Fe16-xO27Hexagonal Ferrite 54
4.1.1 Structural Properties
4.1.1.1 X-ray Diffraction
4.1.1.2 Grain Morphology 55
4.1.2 Magnetic Properties 57
4.1.3 Electrical Properties 59
4.1.4 Dielectric Properties 60

4.2 Ba1-xHoxCo2Fe16O27Hexagonal Ferrite 64

4.2.1 Thermal Analysis

4.2.2 IR Spectra 65
4.2.3 Structural Measurements 67
4.2.4 Physical Properties 69
4.2.5 Grain Morphology 70
4.2.6 Electrical Resistivity 72
4.2.7 Dielectric Measurements 73

4.3 SrZn2GaxFe16-xO27Hexagonal Ferrite 77

4.3.1 Structural Properties
4.3.1.1 Thermal Analysis
4.3.1.2 X-ray Diffraction 78
4.3.1.3 IR Spectral Study 80
4.3.1.4 Grain Morphology 82
4.3.1.5 EDX Analysis 85

63
4.3.2 Electrical Properties
4.3.3 Magnetic Properties 86
4.3.4 Permittivity Spectra 89
4.3.5 Permeability Spectra 90
4.3.6 Microwave Absorption 91

4.4 SrNdxZn2Fe16-xO27 Hexagonal Ferrites 94

4.4.1 Thermal Analysis
4.4.2 Structural Analysis 95
4.4.3 SEM Analysis 97
4.4.4 Magnetic Analysis 99
4.4.5 High frequency dependent Dielectric Properties 102
4.4.5.1 Dielectric Constant
4.4.5.2 Dielectric loss Tangent 103
4.4.5.3 Dielectric Dissipation Factor 105
References 107
Conclusion 111
Future Recommendation 113
List of Publications 114

64
 LIST OF TABLES

No. Title of Table page

1.1 Ferrimagnetic oxides in BaO–MeO–Fe2O3 ternary phase 7
1.2 Number of ions, coordination and spin orientation for the various 10
cations of W-type structure.
1.3 Definition and application areas of the frequency bands 11
3.1 Chemical Name, chemical Formula, Formula weights of chemical 38
Compounds
3.2 Stoichiometric calculations of BaHoxZn2Fe16-xO27Ferrites 39
3.3 Chemical formulae and formula weight of the materials used 42
3.4 Atomic weight of the elements 43
3.5.1 Ba1-xHoxCo2Fe16O27(x= 0.0, 0.02, 0.04, 0.06, 0.08, 0.1) hexaferrites. 43
3.5.2 SrZn2GaxFe16-xO27 (x= 0.0, 0.1, 0.2, 0.3, 0.4) hexaferrites. 43
3.5.3 SrNdxZn2Fe16-xO27 for (x= 0.0, 0.05, 0.1, 0.15, 0.2, 0.25) hexaferrites. 44
4.1(a) Lattice constants, c /a ratio, X-Ray density, Activation energy, 57
Resistivity for BaHoxZn2Fe16-xO27ferrites
4.1 (b) Coercivity, Saturation Magnetization and remanance for BaHoxFe16- 59
xO27ferrites
4.2 (a) Lattice constants „a‟, „c‟, c /a ratio, cell volume, X-ray density, Bulk 68
density, Porosity, Grain size and Activation Energy of Ba1-xHoxCo2Fe16-
xO27.
4.3 (a) Lattice constants (a and c), c/a ratio and cell volume of all 80
SrZn2GaxFe16-xO27 hexaferrites samples.
4.3 (b) The values of saturation magnetization (Ms), remanance (Mr), 88
squareness ratio (Mr /Ms), magnetic moment (nB) and coercivity (Hc) of
all SrZn2GaxFe16-xO27 hexaferrite samples.
4.4 (a) Lattice constants „a‟, „c‟, c /a ratio, cell volume of SrNdxZn2Fe16-xO27. 97
4.4 (b) The values of saturation magnetization (Ms) and coercivity (Hc) of all 101
SrNdxZn2Fe16- xO27 hexaferrite samples.

LIST OF FIGURES

No Title of Figures Page

1.1 ababab hexagonal closed packed structure 5
1.2 HCP and CCP structure 5
1.3 Relation of the phase equilibria of the BaO: Fe2O3 - Fe2O3 system 6
65
 with hexagonal ferrites M, W, Y, and Z.
1.4 Representing the arrangement of SSRSS* R* blocks in W-type 9
hexagonal ferrites
1.5 Electromagnetic waves spectrum. 11
1.6 Resonant absorber showing out of phase condition b/w reflected and 13
emergent wave.
3.1 Flow chart of co-precipitation method. 41
3.2 The scheme shows the step of sample preparation using sol gel 45
technique.
3.3 Coordinate system and specific angles for XRD measurements. 48
3.4 Circuit diagram of two probe method. 50
3.5 Two probe sample holder for resistivity measurements. 51
4.1(a) X-ray Diffraction patterns of BaHoxZn2Fe16-xO27 ferrites (x = 0.0, 0.2, 55
0.4, 0.6, 0.8, 1.0)
4.1 (b) SEM micrographs of BaHoxZn2Fe16-xO27 ferrites. 56
4.1 (c) M H loops of the BaHoxZn2Fe16-xO27 ferrites. 58
4.1 (d) Arrhenius plots of the BaHoxZn2Fe16-xO27 ferrites. 60
4.1 (e-i) Real part of dielectric constant (έ) of BaHoxZn2Fe16-xO27 ferrites. 62
4.1 (e-ii) Imaginary part of dielectric constant (ε‫ )״‬BaHoxZn2Fe16-xO27 ferrites. 62
4.1(e-iii) Dielectric loss factor (tan δ) as a function of frequency for 63
BaHoxZn2Fe16-xO27 Ferrites.
4.2 (a) DT/TGA curves of as prepared Ba0.9Ho0.1Co2Fe16-xO27hexaferrite 65
powder.
4.2 (b-i) FTIR spectra of unsintered powder of Ba1-xHoxCo2Fe16-xO27 (x=0.1) 66
hexaferrite samples.
4.2 (b-ii) FTIR spectra ofsintered powder of Ba1-xHoxCo2Fe16-xO27 (x=0.1) 66
hexaferrite samples.
4.2 (c) XRD patterns of all substituted Ba1-xHoxCo2Fe16-xO27 hexaferrites. 68
4.2 (d) SEM images of all substituted Ba1-xHoxCo2Fe16-xO27 hexaferrites. 71
4.2 (e) Arrhenius plots of Ba1-xHoxCo2Fe16-xO27hexaferrite. 73
4.2 (f-i) Real part of dielectric constant (έ) of Ba1-xHoxCo2Fe16- 75
xO27hexaferrite.
4.2 (f-ii) Imaginary part of dielectric constant (ε‫ )״‬Ba1-xHoxCo2Fe16- 75
xO27hexaferrite.
4.2 (f- Dielctric loss factor (tan δ) as a function of frequency for 76
iii) Ba1xHoxCo2Fe16O27 hexaferrites.
4.3 (a) DT/TGA curves for SrZn2Fe16O27hexaferrite powders. 78
4.3 (b) XRD patterns of SrZn2GaxFe16-xO27 (x=0, 0.1, 0.2, 0.3, 0.4) 80
hexaferrite powders.
4.3 (c-i) FTIR spectra of an unannealed hexaferrite powders. 82
4.3 (c-ii) FTIR spectra of annealed hexaferrite powders. 82
4.3 (d) SEM images of SrZn2GaxFe16-xO27 (x=0, 0.2, 0.3, 0.4) hexaferrite 84
powders.
4.3 (e) EDX spectrum of SrZn2Ga0.2Fe15.8O27hexaferrite powder. 85
4.3 (f) Room temp resistivity SrZn2GaxFe16-xO27hexaferrite powder. 86
4.3 (g) M-H loops of SrZn2GaxFe16-xO27 (x=0, 0.1, 0.2, 0.3, 0.4) hexaferrite 88
powders.
4.3 (h) Frequency dependence of έ (real) and ε‫( ״‬img) of SrZn2Ga0.2Fe15.8O27 90
hexaferrite powders.
4.3 (i) Frequency dependence of ‫(׳‬real) and ‫(״‬img) of SrZn2Ga0.2Fe15.8O27 91
hexaferrite powders.
4.3 (j) Reflection loss as a function of frequency of 93

66
 SrZn2Ga0.2Fe15.8O27hexaferrite powder.
4.4 (a) DT/TGA curves of as prepared SrZn2Nd0.1Fe15.9O27 hexaferrite 95
powder.
4.4 (b) XRD patterns of SrZn2Nd0.1Fe15.9O27 hexaferrites. 96
4.4 (c) SEM images of SrZn2Nd0.1Fe15.9O27 hexaferrites. 98
4.4 (d) MH loops of SrZn2Nd0.1Fe15.9O27 hexaferrites. 101
4.4 (e-i) Real part of dielectric constant (έ) of SrNdxZn2Fe16-xO27hexaferrite. 103
4.4 (e-ii) Dielectric loss tangent (tan δ) as a function of frequency for 104
SrNdxZn2Fe16-xO27 hexaferrites.
4.4 (e- 106
Dielectric dissipation factor (ɛʺ) of SrNdxZn2Fe16-xO27hexaferrite.
iii)

67
 CHAPTER-1
INTRODUCTION

68
 CHAPTER-2
LITERATURE
REVIEW

69
 CHAPTER-3
EXPERIMENTAL
TECHNIQUES

70
 CHAPTER-4
RESULTS AND
DISCUSSION

1.1 Ferrites

Ferrites are magnetic ceramics containing iron oxide as a major constituent in it. Ferrites

since some 70 years appeared to be an important new category of magnetic materials due

to higher resistance, low loss behavior and varied vast technological applications [1].

Now these materials constitute a well-established group. About 70-80% electronic

materials utilize the applications of ferrites. Home appliances, communication

equipment‟s and data processing devices are common examples of such electronic

materials [2-3]. These ferrites have also contributed materially to the advances in

electronics. In the area of new materials, ferrites with permeability up to 30,000 and

power ferrites for frequencies up to 10 MHz have been made available commercially [4].

Along with advancement and innovations, further applications, theoretical frame work

and technologies are under way in the study of ferrites.

71
Some materials exhibit noticeable magnetic characteristics e.g. nickel, cobalt and iron.

Magnetism is there whenever a charge particle is in motion. Magnetism is being

originated by the orbital and spin motion of electrons. Pauli Exclusion Principle states

that when the electrons spin results in random orientation then there would be no

magnetic effect on the average behavior.

Behavior of materials varies depending on the structure and electronic configuration. On

the basis of magnetic successptibility (χ) the magnetic material are classified in to

different types as follow;

1. Paramagnetic materials.

2. Diamagnetic materials.

3. Ferromagnetic materials.

4. Ferrimagnetic materials

5. Anti-Ferromagnetic materials

In paramagnetic materials as orbit is partially filled hence the electrons are unpaired

consequently leading some atoms and ions to have a net magnetic moment when there is

no applied field. The total magnetization is zero because individual magnetic moment

does not interact magnetically. In the presence of field all magnetic moment aligned in

the field direction, results a net small positive magnetic effect so positive susceptibility

occurs. Increase in temperature results in displacement of magnetic domain due to

thermal agitation.

In diamagnetic atoms due to completely filled orbits no net magnetic moment exists and

having no unpaired electrons. Further, when there is no external field, the magnetization

produced is negative leading towards negative susceptibility.

In ferromagnetic materials a bulk net magnetization is present if no external field is

applied. It is possible to be produced by the materials where magnetic moments are

72
aligned parallel. Two prominent features of ferromagnetic materials are (a) Curie

Temperature (b) Spontaneous Magnetization.

At a certain degree of temperature electronic exchange forces are overcome by thermal

energy and magnetic domain is misaligned. This temperature is called Curie temperature.

The net magnetization that exists inside a uniformly magnetized microscopic volume in

the absence of any field is called Spontaneous Magnetization. Magnitude of

magnetization at absolute zero depends upon the spin magnetic moment of electrons.

Ferrimagnetic materials are permanent magnetism or magnetic materials that occur in

solids where magnetic field is linked with individual atoms that spontaneously align

themselves, some parallel and some anti-parallel. These materials are less magnetic than

ferromagnetic.

In antiferromagnetic materials the spin of electron aligns in a regular pattern with

neighboring spin opposite in direction. Generally anti-ferromagnetic material behaves

paramagnetic materials at certain high temperature. This temperature is called Neel

temperature.

A magnetic domain describes area within a material which has aligned magnetization.

The thickness of magnetic domains is approximately 5 to 200 nanometers and depends

on the type of magnetic material.

The magnetization / demagnetization curve of a ferromagnetic material provides a great

deal of information during magnetic characterization. Processing route of powder

metallurgy makes the magnets and during processing there are no powder oxidation

problems due to stability of oxides. Powder-processing assures small grains necessary to

produce coercivity. In this processing, the powder is compacted in a magnetic field in

order to align the easy direction of magnetization of the particles and consequently

increases the remanence and the maximum energy level/gain [5]. A magnet is basically

an energy conservation material. It stores energy when magnetized. This energy remains

73
for the unlimited time and cannot drain away by repeated use, like that of a battery. It is

so because a magnet does not have any network on its surroundings [6].

Iron containing complex oxides is known as ferrites. Structural formula of ferrites is

(Fe2O3.OMe) where Meis a divalent metal ion like cobalt, nickel and zinc. These are

counted good magnetic materials whose resistivity varies 102 to 1011(ohm-cm) depending

on the structural formula. Ferrites are hoping semiconductors and their resistivity varies

inversely with temperature. Ferrites are insulator which are crystalline and magnetic in

nature and work wonder fully at max frequency because of minimum eddy current

losses.

Based on crystal structure, ferrites are segmented in to four classes.

 Spinel Ferrites

 Ortho ferrites

 Garnets Ferrites

 Hexagonal ferrites

The spinal ferrites have basic formula (M.O Fe2O3) where M is a divalent ion. Spinel

ferrites are also soft ferrites. When magnetized, materials do not retain their magnetism.

They have narrow hysteresis loops having highly saturated magnetization but a little

coercive force typically from0.5 to 4 Oe [7]. Typical applications are switched power

supplies and transformers [8].

Ortho ferrite structure is also called perovskite structure. The formula is MFeO3 where M

is rare earth. The structure is orthorhombic.

The general formula for garnet is Me3Fe5O12 Me is rare earth e.g. La, Y and Gd.

1.2 Hexagonal Ferrites

Hexagonal ferrites are combination of spinel ferrites and metal ions. The lattice has three

sites tetrahedral, octahedral and trigonal bipyramid. As hexagonal ferrites are hard so

74
they do not easily magnetize because of wide hysteresis loop with high coercivity greater

than10 kAm-1.

Some permanent magnets are used in radios due to having square hysteresis loop, large

coercive force and remanent magnetization [7-8]. Magnetic materials can be

distinguished by their maximum Permeability and maximum resistivity, therefore their

usage in industry, technology, communication equipment‟s, electronic devices, high

density magnetic media, recording media, material are for permanent magnets [9-13].

1.3 Hexagonal Closed Packed (HCP) Structure

In two possible ways the atoms of same size can be arranged and its demonstrate ion is

likely balls representing atoms as shown in Fig.1.1, the first layer is marked as „a‟ then

place a second layer on the

indentation of first layer that is the layer

„b‟.

Fig.1.1 “ababab” hexagonal closed packed structure

The third layer can be added in two ways either in cubic closed pack or hexagonal closed

pack (hcp) structure as show in Fig.1.2.

75
 Fig. 1.2 HCP and CCP structure

These closed packed layers represent the holes as interstitials sites in the lattice. Many

ionic crystal structure consisting of closed packed arrangement of anions with smaller

cations occupying these sites. There are two types of holes, tetrahedral and octahedral

together with the ccp and hcp packing‟s. It has been observed that an hcp structure

repeats after every other layer. In ferrites there is closed packing of oxygen and metal

oxides on interstitial sites.

1.4 Chemical Composition of Hexaferrites

The chemical composition of the hexagonal compounds is shown in Fig. 1.3by ternary

phase diagram of the BaO-MeO-Fe2O3system.

76
Fig. 1.3 Relation of the phase equilibria of the BaO:Fe2O3 - Fe2O3 system with
hexagonal ferrites M,W,Y and Z [14]

It is evident that hexaferrites include a large amount of different compounds and have

many types, including (M-type), (X-type), (W-type), (U-type), (Z-type), and (Y-type).

where Me shows a divalent ion, such as Fe2+, Co2+, Ni2+, Cu2+ and Zn2+, and a

combination of them. The Table 1.1 enlists these six possible types [15].

Table1.1: Ferrimagnetic oxides in BaO–MeO–Fe2O3 ternary phase [16-17]

No. of
Crtsallographic molecules c-axis
Symbol Composition
build up /unit cell (Å) Abbreviation

M BaFe12O19 RSR*S* (MM*) 2M 23.2 M

77
 X Ba2Me2Fe28O46 MM*S 3MeX 84.0 Me2X
W BaMe2Fe16O27 MSM*S* 2MeW 32.8 Me2W
U Ba4Me2Fe36O60 MM*Y* MeU 38.1 Me2U
Z Ba3Me2Fe24O41 MYMY 2MeZ 52.3 Me2Z
Y Ba2Me2Fe12O22 3TS 3MeY 43.5 Me2Y

1.5 W-Type Hexagonal Ferrites

Went et al. [18] observed one of the major compound is referred to as W-compounds,

which have the chemical formulae of BaO.2MeO.8Fe2O3 (BaW), SrO.2MeO.8Fe2O3

(SrW) and PbO.2MeO.8Fe2O3 (PbW).

The cross section of the W-structure with hexagonal packing is shown inFig.1.4 that is

similar to the M-structure. The difference between these two is R-blocks that are

interspaced between two S-blocks. The cations of Me2+ and Fe3+ have seven different sub

lattices of 12k, 4e, 4fIV, 4fVI, 6g, 4f and 2d are shown in Table 1.2. These ferrites have

two basic axes one is the major axis „c‟ and other is the minor axis „a‟ and the unit cell of

this ferrite is combination of four S-blocks and two R blocks along the hexagonal c-axis.

RSSR*S*S* where R is three-oxygen layer block having composition Fe6O11, S is a two-

oxygen layer block having composition Fe6O8 and the asterisk means that the subject

block has been turned 180 0C along the hexagonal axis [19].

These ferrites have a prominent position in the permanent magnet market for electrical,

electronic and automobile devices because of their magnetic performance, low cost and

are suitable due to their highly saturated magnetization. These hexaferrite materials are

used in industrial applications because of their high coercivity and saturated

magnetization as compared to other type of ferrites [20-26]. These ferrites are also useful

for both longitudinal and perpendicular recording media [27].

78
These ferrites are most popular and having a salient feature as a microwave absorber

because of soft magnetic character [28]. This behavior shows the formation at a high

sintering temperature greater than 1200 0C which implies a large grain size [29]. These

hexagonal ferrites are most popular in microwave absorption materials because of their

higher efficiency, lower cost and their very low dielectric loss [30]. So this is most

appreciable magnetic materials than those of other materials [31].

79
Fig. 1.4 Representing the arrangement of SSRSS*R* blocks in W-type
hexagonal Ferrites [32]

80
Table 1.2: Number of ions, coordination and spin orientation for the various
cations of W-type structure.

Type of Number of
Sublattice Coordination Blocks Spin
Structure Positions
12K Octahedral 12 R-S ↑
4e Tetrahedral 4 S ↓
4fIV Tetrahedral 4 S ↓
W-Type 4fVI Octahedral 4 R ↓
6g Octahedral 6 S-S ↑
4f Octahedral 4 S ↑
2d Hexahedral 2 R ↑

1.6 Microwaves

Microwave is a widely used term to denote AC signals “having frequencies between 300

MHz and 300 GHz with a corresponding wavelength between 1m and 1mm respectively.

Fig.1.5 (a) shows the location of the microwave frequency band in the electromagnetic

spectrum [33] and Fig.1.5 (b) shows the typical frequencies and approximately band

designation. The different information of frequency band and its application areas in the

ferrites microwave absorption are shown in Table 1.3.

81
 Fig.1.5 Electromagnetic waves spectrum

Table 1.3: Definition and application areas of the frequency bands [34]

Frequency Band Definition Application Areas

Navigation, Sonar, sound
3-30 KHz Very Low Frequency(VLF)
waves
Direction finding with radio
30-300 KHz Low Frequency(LF)
waves, Surveillance with radio
Medium Frequency(MF)
300-3000 KHz AM radio, Direction finding
Telephone, Fax, Short wave
3-30 MHz High Frequency(HF)
radio
FM Radio, TV, Air traffic
30-300 MHz Very High Frequency(VHF) control,
Mobile phones
TV, Satellite communication,
300-3000 MHz Ultrahigh Frequency(UHF) Wireless data, Microwave
oven
Airplane radars, Satellite
3-30 GHz Super high Frequency(SHF)
Communication
Extreme High
30-300 GHz Radar, Space exploration
Frequency(EHF)

82
1.7 Microwaves Absorbers

These are referred as materials with altered electrical and magnetic properties so that

they can absorb microwaves at certain frequencies. Two conditions are necessary for the

preparation of a low-reflecting absorber. (a) Maximum flux of incident wave could be

entering the absorber (impedance matching characteristic) (b) maximum attenuation and

absorption of electromagnetic wave within the absorber (attenuation characteristic) [35].

Various studies using single-layer absorbers of ferrite, carbonyl iron etc. revealed that

the single layer absorbers do not realize low reflection in wide range of electromagnetic

spectrum. The same phenomenon was observed in double layer microwave absorber of

soft ferrites and ferroelectric materials [36–38]. An increased use of Electromagnetic

wave in giga hertz range in wireless communication instruments, local area networks

(LAN), personal digital assistant and some other communication equipment created a lot

of problems which are due to the disoperation of high tech electronic devices and

leakage of valuable information because of leakage of electromagnetic wave. Therefore

lot attenuation is being focused on electromagnetic compatibility (EMC) and

electromagnetic interference (EMI)”to find a suitable microwave absorber [39-41]. The

electromagnetic reflection can be minimized by the use of microwave absorber. This

type of usage is evident in ships, air crafts, electronic equipment, tanks, and walls of the

anechoic chambers [42-43].

Microwave absorbing materials are based on the fact that some substances absorb energy

from electromagnetic fields passing through them. Such materials are characterized by

the indices of refraction, which are complex numbers, such as permittivity (ε=ε'− jε" )

and permeability (μ=μ'− jμ"). The imaginary components in the indices of refraction (ε"

and μ") account for the microwave energy loss in the materials. The loss is actually the

conversion of EM wave energy into heat.

83
1.8 Principle of Operation

When an electromagnetic wave is reflected by metal plate as shown in the Fig.1.6, the

wave is shifted into two components by phase difference of 180° at air-absorber-metal

interfaces and cancels the effect of each other resulting in minimum reflection [44].

The magnitude of reflection co-efficient is given as

RL (dB) = -20 log10 [(Z1-Z0)/ (Z1+Z0)] (1.1)

Z1 = Input impedance of the absorber.

Z0 = 377Ώ = Impedance of free space (vacuum, air).

Fig. 1.6 Resonant absorber showing out of phase condition b/w reflected and
emergent wave.

1.8.1 Impedance Matching Condition

If Z1 = Z0 is satisfied at matching frequency (fm), then minimum reflection losses occur.

1.8.2 Quarter Wave Thickness Phenomenon

In a conventional way, as the thickness of absorber is increased, absorption is increased.

But if ferrite contents in the sample are increased, thickness is decreased with the

increase of frequency range i.e.

84
 Thickness (t) = λ0 /4 (μrllЄr)1/2 (1.2)

Where λ0 = c/ f (wavelength of incident wave), thickness α 1/ f and thickness α

1/absorption. This is called the quarter wave thickness phenomenon [45].

85
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Ferrites were given a great attention by various research groups and scientist due to large

number of applications. Among different classes of ferrites hexagonal ferrites are

extensively studied. Hexagonal ferrites due to their existence in structural variation are of

much interest which makes them applied in different devices like electronic devices,

microwave devices, industry, and technology and communication equipment.

Smit et al. [1] studied the BaZn2-xMgxFe16O27 by ceramic method. Single phase with W-

type structure was observed at 1250 0C by X-ray diffraction analysis. The dielectric and

ac conductivity measurements were conducting by coupling impedance technique.

Frequency dependence of the dielectric constant at different temperature was also

analyzed. It was concluded that the sample with composition x = 2 (maximum Mg

content) shows no frequency dependence at room temperature besides it has a relatively

low value of  ' . In other words by increasing Mg content the dielectric constant

decreases.

88
Leccabue et al. [2] prepared the BaZn2Fe16O27 hexagonal ferrites by co-precipitation

technique sintered at 600-1500 0C for different times. The curie temperatures of the

BaZn-W phase vary from 370 to 410 0C depending on the heat treatment of the sample.

Three different compounds were formed after the heat treatment i.e. Zn-spinel (ZnFe2O4)

BaFe12O19 and BaZn2-W ferrites. It was also observed that the solid state reaction

completed above 1270 0C, and only Zn2-W phase was present.

Kim et al. [3] reported the behavior of resistivity barium titanate. RT curve were plotted

at different temperature. It was concluded that resistance increases of all samples at room

temperature and then sharply decreased as temperature increased. Electrical breakdown

of the positive temperature coefficient was observed.

W-type hexaferrites prepared by a double-sintering ceramic method have been reported

by Ata et al. [4]. The dielectric constant έ, dielectric loss tan δ and initial magnetic

permeability μo was studied. An increase in dielectric constant έ and tan δ with increasing

nickel ions substitution was justified using of hopping conduction mechanism and

Rezlescu model. It was noted that the increase in temperature increased the magnetic

permeability. This anomalous behavior with temperature is due to the chemical

composition.

W-type hexaferrites BaCo2-xNixFe16O27 prepared by solid state reaction at 1250 0C for 4

h by Ata et al. [5]. Due to increase in the replacement Co2+ ion by Ni2+dc electrical

conductivity is increased while in the case of Ni-ion substitution the activation energy is

decreased. A decrease in frequency dependent dispersion in ac conductivity is observed

with increase in temperature on the basis of Koop‟s model.

Sawadha et al. [6] studied W-type hexagonal ferrites with composition of CaCu2Fe16O27

prepared by standard ceramic technique. X-ray diffractometery shows that it has a single

phase W-type structure. A See-beck study shows that the sample is P-type

semiconductor. Wanga et al. [7] studied W-type BaZn2-xCoxFe16O27 nanocrystalline

89
hexaferrites powder prepared by stearic acid gel process. They also studied the X-ray

diffraction, transmission electron microscope (TEM) and by vibrating sample

magnetometer (VSM).

Ismael et al. [8] studied the hexaferrite BaCo2-xZnxFe16O27 prepared by ceramic method.

The dielectric constant (ε‫ )׳‬and dielectric loss (δ) and temperature decreases with the

increase of frequency. Saadawy [9] reported that dielectric constant and dc electrical

resistivity depends on temperature and composition. It was observed that room

temperature resistivity, dielectric constant, Curie temperature and activation energies for

electrical conduction increases as Cu-ion substitution increases. The dc electrical

conductivity increases as temperature increases.

Bilal et al. [10] synthesized the BaxCo3-xFe16O27 (x = 0.5, 1.0, 1.5, 2.0, 2.5) by co-

precipitation method at 1300 0C. They studied the Electrical resistivity and activation

energy. An increase in resistivity was observed with Ba concentration while a decreasing

trend in temperature ranges 13-200 0C. This indicates the semi conducting behavior of

the samples.

BaZn2-zCo2Fe16O27 prepared by citrate sol-gel sintered at 1200 0C for 5 h studied by

Haijun et al. [11]. Complex permittivity and complex permeability behavior as observed

in frequency range 0.1-6 GHz revealed that there is decrease in real part permeability. In

addition, imaginary part of permeability approaches a peak value with frequency

increase and start decreasing as zinc ion content increases. M-type ferrites are surveyed

by Grossinger et al. [12]. It was studied that the anisotropy and coercivity increases due

to La-Co substitution additionally substituted of Sm which also leads to a strong increase

of coercivity.

Verma et al. [13] studied the D.C. resistivity of Ni-Zn ferrites in the range of 107 to

1011 and samples were sintered at 1200 0C and 1300 0C. The conduction mechanism

was determined as hopping. They have also analyzed the fact that with the increases of

90
sintering temperature the resistivity decreases. Resistivity also observed to decrease with

the decreasing the Zn content. The increase in the resistivity corresponds to the grain size

of the sample.

Z.W et al. [14] prepared BaZn2-xCoxFe16O27 W-type hexagonal ferrites (x = 0.0 to 2.0) by

ceramic technique. X-ray diffraction showed that all samples are single phase, lattice

parameters „a‟ and „c‟ decreases from 0.5918 nm to 0.5904 nm and 3.303 nm to 3.288

nm respectively. So BaZn2-xCoxFe16O27 is converted from Zn2W to Co2W due to small

ionic radius of Co (0.065nm) than Zn (0.074nm). The c/a ratio 5.575 is an indication of

co-concentration independence. A decrease in coercivity i.e. 184 Oe to 15 Oe was

observed as Co-concentration increased from x = 0 to x = 2. Hence Ms increases at x =

0.7 and after that decreases.

Sudakar et al. [15] reported the single phase, structural, magnetic and microwave

absorption studies of the Ba Co2 Fe16 O27 (W-Co2) and BaCo2Fe12O22 (Y-Co2)

hexaferrites at very high frequencies. The average grain size was calculated 20 m.

Magnetic parameter was observed between -9 and +9 k Oe. Saturation magnetization Ms

=69.7 emu/g and coercivity Hc=190 Oe in (W-Co2) whereas Ms= 53 emu/g and Hc = 500

Oe in (Y-Co2) hexaferrite was observed. It was argued that formation of defective matrix

is due to decrease in Ms and increase in coercivity Hc.

Yang et al. [16] enhanced the w-type hexaferrite particles (Ba (Co0.5Zn0.5)2Fe16O27) by

combination of co-precipitation and mechanical milling. The peak value of real part of

complex permeability in frequency range 2-18 GHz determined the effect of

demagnetizing field. On the other hand, imaginary part of complex permeability showed

a weak frequency dependent phenomenon which was attributed to increase in effective

reluctance of composite. Scanning electron microscope shows hexagonal crystal grains

of Ba-Nd-Co. Yamamoto et al. [17] observed a small value of temperature coefficient for

M-type ferrite synthesized by the chemical Co-precipitation method. Magnetic and

91
structural properties of La-Zn substituted M-type Ba ferrite fabricated by sol-gel method

have been investigated by Lee et.al [18]. Hang et.al [19] discussed the M-Type

Ba(MnTi)x Fe12-2xO19 hexaferrites (x = 0,0.5,1.0,1.5,2.0) by taking ACS (Auto

Combustion Synthesis) and LCS (Low Temperature Combustion Synthesis) of citric acid

–metal nitrates sol-gel system. XRD analysis proves that all powders of Ba (MnTi)x Fe12-

2xO19 are hexaferrites. The lattice constants were a = 5.89-5.91Ǻ, c = 23.11-23.28Ǻ.

TEM observation indicates that the powder particles have an average diameter of 50nm.

Magnetic hysteresis loop measurements of the series Ba (MnTi)x Fe12-2xO19, exhibit that

the saturation magnetization (Ms), the remanent magnetization (Mr) and the coercivity

(Hc) of compounds depend strongly on the chemical composition of materials.

Sudakar et al. [20] used G-C (Gel to Crystallite) conversion method to study BaO-NiO-

Fe2O3, ternary phase composites of hexa and nickel ferrites. In the composites, coercivity

showed a decreasing trend for W-S line while an increasing trend for Y-S line. Zinc

ferrite powders (ZnFeO) particles synthesized by co-precipitation of a bi-ionic Fe / Zn

solution with 1M solution of n-butyl amine as precipitating agent at low temperature by

Vidales et al. [21]. The ferrite precursors thus produced were characterized by X-Ray

diffraction, Fourier Transform Infrared spectroscopy, thermal analysis, scanning and

transmission electron microscopy and nitrogen adsorption volumetric techniques.

M-type hexagonal ferrites Sr1-xSmxFe12O19 were studied by Lechevallier et al. [22]. They

observed that Sr and Sm secondary phases are related to (Sr, Sm) FeO3-δ perovskite

phase. It was explained that a nominal increase of Sm increases the coercivity while

magnetization and anisotropy field remains constant.

Attia et al. [23] reported the transport properties of W-type hexaferrites for the

composition BaZn2-xMgxFe16O27. A lower value of transition temperature Ts as compared

to curie points was observed in dc conductivity studies. Thermoelectric power

measurements showed that these ferrites are n-type semiconductors and hopping

92
conduction mechanism is dominant. While ac conductivity revealed that multiple

hopping is predominant conduction mechanics.

Polycrystalline samples of BaCo2-xNixFe16O27 studied by Durge et al. [24]. They

observed that the temperature dependent D.C. resistivity of barium cupromolybdate

ceramic. The room temperature resistivity of the sample was 4.42 x105 (ohm-cm)

sintered at 1100 0C. On the other hand the resistivity of the sample was 2.68 x105 (ohm-

cm) sintered at 1200 0C. The conductivity was observed directly proportioned to

sintering time. At higher temperatures, curve of resistivity shows the semi conducting

behavior of the ceramic.

Choi et al. [25] studied (La-Co) substituted Sr based M-type hexa-ferrites, (La-Co) xSr1-

xFe12-xO19 powders synthesized by sol-gel process. The ferrite powders were sintered at

950 0C. Single phase M-type hexaferrites were characterized by X-ray diffraction. It was

observed that magnetization is 63.9 emu/g and coercivity increased with the increase of

(La-Co) concentration.

Wu et al. [26] studied high frequency magnetic and attenuation properties of undoped

and V2O5 doped W-type barium ferrites. A comparison to undoped samples showed the

permeability ‫׳‬0.5 and ‫״‬max are increased about 50% and 40% for sample doped with 1.0

wt% of V2O5 respectively, due to the significant contribution of domain wall

permeability. These composites have superior attenuation properties of more than 10 dB,

with low reflectivity and broad band width covering S, X and Ku bands.

Yan et al. [27] studied the Ba (CoxZn1-x) Fe16O27W-type hexagonal ferrites at calcination

temperature of 800 0C using auto Combustion dried –gel method. They observed an

increase in grain size at higher temperature.

M-type Barium hexaferrites BaLaxFe12-xO19 / SiO2 synthesized by sol-gel method were

studied by Zhidong et.al [28]. XRD, FTIR and SEM analysis reveals that SiO2 has no

effect on the structure, but the presence of SiO2 greatly enhances the homogeneity and

93
particle size is decreased ~100nm. In these ferrites X-Ray diffraction analysis showed no

impurity but a relatively small and uniformly distributed grain size was observed in

synthesized BaFe12O19 powder is small and distribution is uniform by SEM.

Sharma et al. [29] in their study of structural and magnetic properties of barium hexa

ferrites observed that the Ba substitution did not affect the lattice parameters but

produced smaller crystallites. The lower magnetization and higher coercivity was

attributed to the reduction of average magnetic moment of the lattice and the

improvement occurred in the crystallite size.

Feng et al. [30] reported the use of BaZn1.5Co0.5Fe16O27 and carbonyl powders in

magnetic filter microwave absorber. They observed the single and double-layer

absorbers of the microwave absorbers. They showed that barium W-type ferrites single

and a relatively higher reflection could be observed over a wide range of frequency in

carbonyl iron and barium ferrites. The phenomenon may be attributed to fact that

absorption band in single layer absorber decreases with reflection loss.

Ba(Zn0.5Co0.5)2Fe16O27 prepared by sol-gel method have been investigated by

A.Oikonomoua.et al. [31]. A multi-layer electromagnetic absorber resulted variable

absorption performance combined in ZnCo W-type ferrites. BaM is studied by Malick et

al. [32]. They observed the isochronal and isothermally complex permitivity and

dielectric loss tangent over 1MHz-1GHz in the frequency. The high value of relative

permitivity of 32 and low loss tangent of 0.329 indicates suitable high frequency

characteristics for barium hexaferrite. The flat response over frequency of the measured

parameter shows the atomic / structural rearrangement in the BaM. It did not reach the

natural resonant frequency because the binding in the crystal and transfer of max energy

at this frequency is not lower than 3GHz. So hexagonal ferrite such as barium ferrites are

extensively a used as permanent magnets.

94
Hemeda et al. [33] studied the Zn2-xCoxBaFe16O27 prepared by ceramics technique. The

M-H loop for all samples sintered at 1300 0C revealed that the ferrites belongs soft

ferrites family. M-type strontium hexaferrites in two series of samples (Sr1-xGdx) O5.25

Fe2O3 andSr1-xGdxFe12-xCoxO19 studied [34] by Litsardakis, using ceramic method. The

Coercivity and magnetization in the Sr-Gd-Co series decreases with substitution degree.

Fe-Mössbauer measurements have been performed on aluminum substituted M-type

barium hexaferrites of composition BaFe12-xAlxO19 (0_<x_<9.6) above their Curie

temperature by Albanese et al. [35]. This study revealed the temperature dependence of

the quadropole splitting values, the angle between the Hhf direction and the EFG axis for

Fe nuclei in the octahedral coordinated sub lattices of BaFe12O19 ferrite. Sol-gel and

PMMA techniques were combined to develop rod-shaped nanoparticles of M-type

barium hexaferrites by Mu et al. [36]. A comparative study of microwave absorption

characteristics showed better value of rod-shaped BaFe12O19than granular in 5-

15GHzfrequency range. The physical and magnetic properties of Ho substituted Mn-Zn

ferrite ferro fluid by Upadhyay et al. [37] revealed the effectiveness of these particles in

biomedical applications. The substitution of rare earth not only improved spin magnetic

anisotropy but a strong frustration at low temperature i.e 10-700 Oe indicated the

emergrnce of Ising spins.

Mallick et al. [38] reported an increasing permeability when Co2+/ 3+concentrations in M-

type barium hexaferrites increased up to5%. However a subsequent decrease was

observed in permeability as the doping touched 30% while coercivity Hc sharply

increased. DTA, TGA showed decarboxylation and the XRD data proved the Co ions

substituting Fe sites.

Abbas et al. [39] reported M-type hexaferrite BaCo+2 0.09 Fe+20.05 Si+4 0.09 Fe+310.1O19 that

was prepared by solid- state reaction technique. Polyurethane (PU) matrix has been

studied in the X-band (8.2-12.4GHz) range. An improvement in complex permittivity

95
and permeability with respect to microwave absorption were observed with increasing

ferrite contents in the polymer matrix.

Shepherd et al. [40] prepared single-phase barium hexaferrite by co-precipitation

method. They measured permeability and magnetic loss tangent over 1MHz-1GHz under

sintering temperature 1300 0C. They also measured the Curie point (Tc) of 452 0C and

observed ferromagnetic resonance centered at 500 MHz.

Hessien et al. [41] studied Strontium M-Type hexaferrite having the formula SrFe12O19

in the form of powders synthesized using co-precipitation technique. They also studied

the calcinations route effects of Fe3+ / Sr2+mol ratio, annealing temperature and pH

formation and reported the X-Ray Diffraction (XRD), Scanning electron microscope

observations. Decrease in Fe3+ / Sr2+ ratio produced a single-phase SrFe12O19 powder.

The decrease in Fe3+ / Sr2+ mol ratio also result maximum saturation magnetization and

hexagonal-shape structure.

Sharma et al. [42] prepared nano crystalline W-type hexaferrites by low temperature

combustion synthesis (LCS) method. The samples thus synthesized were single phase

having W-type structure. SEM patterns showed surface morphology of the nonporous

ultra-fine particles. The TEM micrographs showed the particles size which is 10nm. Ms

indicates super paramagnetic effect of material under the magnetic field (10KG max)

with the annealing temp at 400-1000 0C for 4 hours. There was observed an increase in

grain size and saturation magnetization from 10-70 nm and 26.7-44.5 emu/gm

respectively.

Ahmed et al. [43] prepared W-type single phase hexagonal ferrites BaCoZn1-

xMgxFe16O27 (0≤x≤0.6) by ceramic method. Structural and magnetic studies with respect

to composition pointed out that statistical distribution of sites drags Zn ions to occupy

tetrahedral sites and Mg2+ to occupy octahedral sites. A small addition of Mg2+ ions on

tetrahedral sites in W-type structure enhanced magnetic properties.

96
Rare earth metals Dy structural and electromagnetic variation in Ba (MnZn)Co [RE] FeO

W-type ferrites using rare earth elements Dy, Nd and Pr were studied by Jing et al.[44].

The structure was determined single phase hexagonal. Substitution of RE elements

altered cell parameter but no change in cell type was observed. There was a decrease in

cell parameters except the sample with pr substitution where value of „c‟ showed

different behavior. Variation in values of „a‟ and „c‟ was a proof that Fe3+ ions have been

substituted by RE3+ ions. Frequency increases and obvious relaxation, especially for the

specimen with Dy substituted. Results showed that difference in ionic radius of Fe3+ and

RE3+ ions and interaction between RE3+ and its surrounding are responsible for the

phenomenon that a little amount of RE3+ can replace Fe3+ ions. Increase in resonance

frequency and decrease in complex permittivity were also observed.

Hongying et al. [45] prepared Ba1-xLaxCo2Fe16O27 single phase W-type hexaferrite by

solid state reaction method at 1250 0C. They studied the structural, magnetic and

microwave absorbing properties. Their result showed and increasing phase transition

temperature with respect to La3+ substitution. Replacement of Ba2+ by La3+ microwave

properties improved when measured in 0.5-18.0 GHz range. The coercive force (Hc) and

residual magnetization decrease and microwave properties increased.

Rare earth substituted SrFe1-xRxO19 (R = La, Gd and Er) ferrites studied by Rezlescu has

been reported [46]. The X-Ray diffraction analysis reveals M-type hexagonal structure.

A reduced grain growth due to internal stress generated by „R‟ ions was observed and

attributed to temperature dependency. Heat treatment after critical temperature also

produced increased coercivity.

Polycrystalline ferrites Sr0.5Pb0.52+Fe12-xPbx3+O19 were studied by Shahid et al. [47].

Successive addition of Pb increased the values of lattice parameters resulted an

enhancement of X-ray density and porosity while addition of Pb content resulting an

97
increase in dc resistivity and activation energies at room temperature according to

hopping model.

Zn2-xCuxBaFe16O27 Polycrystalline ferrites were synthesized by ceramic method by

Hemeda et al. [48]. An X-ray measurement confirms the presence of W-type hexagonal

ferrite phase at room temperature. Closed loop hysteresis was an indication of low

anisotropy and saturation magnetization field. Hopping of holes between Cu2+ and Cu3+

ions results a decrease in thermoelectric power with increase of Cu2+ content. Drift

mobility was found temperature dependent which increased the electrical conductivity.

The magnetic and electrical behavior of SrZrxCuxFe12-2xO19 (x= 0.0-0.8) hexaferrites are

studied by Iqbal et al. [49]. They studied the structural parameters FTIR, XRD, EDX,

SEM and TEM analysis and confirm the materials are single phase.AC magnetic

susceptibility and dc electrical resistivity measurement were in the temperature range

300-800 K and by the substitution of Zr-Cu Curie temperature decreases. The drift

mobility, dielectric constant and dielectric loss factor decreases while the dc electrical

resistivity and activation energy increases for the sample x  0.4. The dielectric

measurements are taken in the frequency range 80Hz-1MHz.

Dhahri et al. [50] studied the influence of potassium (K+) doping on the structure of

multiferroic with its relation with ferroelectric and magnetic properties. The results of the

structural refinement on single crystals show that the average rhombohedral with R3c

group evolves towards a pseudo-cubic symmetry due to a disorder related to the K+

doping. Magnetic measurements show that all compounds remain anti ferromagnetic at

room temperature (RT) with no change in the transition temperature (Neel temp (TN)).

W-type hexaferrites of BaZn2CrxFe16-xO27 (x1) prepared by wet chemical method or co-

precipitation method have been reported by Javed et al. [51]. Homogenous single phase

nano-particles of Cr substituted powder were obtained. A comparative study indicated

98
that there is no change in lattice constants „a‟ and „c‟ of doped and undoped samples.

However doping of Cr results an increase in electrical resistivity.

Ibal et al. [52] synthesized the strontium hexaferrites doped with Zr-Zn by chemical co-

precipitation method. They observed the temperature dependent resistivity in the range

of 388-400 K. They found that Curie temperature, dc resistivity, Activation energy

decreases whereas dielectric constant and dielectric loss and drift mobility increase by

improving Zr-Zn content.

Strontium hexaferrite SrZnxCdxFe12-2xO19 studied by Ashiq et al. [53]. They studied the

magnetic and dielectric properties. Saturation magnetization increases while coercivity

decreases which make suitable this material for use in recording media. Relative

permittivity measurements were recorded in 500 Hz-1 MHz frequency range.

Iqbal et al. [54] synthesized the Ce-Ni ions substitution nano crystalline strontium

barium hexaferrite by chemical Co-precipitation method. After heat treatment at 1323 K

for 6 hrs a single magnetoplumbite phase of Sr-Ba was observed. Dc electrical resistivity

increases from 1.8x1010 to 1.25x1010 ohm-cm and drift mobility, dielectric constant,

dielectric loss tangent decreases with the increase of Ce-Ni content. These materials are

suitable for fabricating the multi-layer chip inductor (MLCI).

XU et al. [55] studied W-type ferrites having single phase and grain size synthesized by

sol-gel technique. They studied the effect of the substitution Nd3+ rare earth ions for Ba2+

ions on the microstructure, complex permeability, permittivity and microwave absorption

of the samples. Increasing Nd3+ substitution result the following effects; an increase in

real and imaginary parts of complex permittivity while real part of complex permeability

decreased and imaginary part increased. Also doping of Nd3+ ions improved microwave

absorption characteristics.

BaFe12-xGaxO19 prepared by ball milling at 1100 0C was sintered by Soul et al. [56]. They

investigated XRD, TEM and VSM. XRD patterns show the single hexagonal phase with

99
crystallite size range 37nm-45nm. TEM images (x=0.0, 1.0) shows the particle diameter

29nm and 27nm respectively. The saturation magnetization decreases and Hc increase

due to the effect of Ga and magnetic exchange coupling. There was an increase in

coercivity as Ga replaced Fe which was due to change in magnetic coupling. Double

confirmation of exchange coupling was done by broadening of SFD decreases in

remanence ratio and Curie temperature with increasing Ga.

Rare earth substituted M-type hexaferrite (Ba1-xREx)O.525(Fe2O3) synthesized by

chemical Coprecipitation by Stergiou et al. [57]. They found the complex permittivity εr*

and permeability r* in the 2-18 GHz frequency range, and observed the correlation of

electromagnetic behavior with dielectric polarization and magnetic interaction

mechanism.

Vindon et al. [58] studied the nanocrystalline Cr3+ substituted barium hexaferrites by

auto-combustion technique. Saturation magnetization (Ms), Remanence Magnetization

(Mr), Coercivity (Hc) and magnetic number (nB) decrease with the increase of Chromiun

content (x) due to greater magnetic moment of Fe3+ (5µB) ions than Cr3+ (3µB).

Iqbal et al. [59] observed the single phase BaCo2Fe16-2x (ZrMn)xO27 W-type hexaferrite

prepared by co-precipitation technique at 1153 K. It is observed that increasing amount

of Zn-Mn increased grain growth and lattice parameter values. Resistivity enhanced at

value of 2.82x103 cm. Addition of Zr-Mn content also increased dissipation factor

having value 6.49x103 to 9.97x103 at frequency 10 KHz. Eminent values of saturation

magnetization (67emu /g) and remanent magnetization (34.7 emu /g) and Coercivity

(1861 Oe) were observed and these materials are suitable for data processing devices.

Muhammad et al. [60] studied the strontium hexaferrites having Al-Cr binary mixture by

chemical co precipitation method. A thoroughly study of magnetic and electrical

properties with respect to synthesis conditions and site occupation by substituted cations

was performed. The increasing Al-Cr sub lattices result a decrease in saturation

100
magnetization, remanence, coercivity and magnetic moment. The outcomes as certained

the material sublattice for recording media. BaZn2CrxFe16-xO27 developed by chemical

co-precipitation method was found utile to bring down eddy current loss in high

frequency magnetic materials and for radar wave absorbing material.

Rai et al. [61] studied theBaCd2-xSrxFe16O27 W-type hexagonal ferrite devised by

ceramic method, sintered at temperature 1400 0C for 6 h. They examined morphological

dielectric and magnetic characteristics. The saturation magnetization step-up with

addition of Sr2+ while coercivity value fluctuated because of liking of Cd2+ for

tetrahedral sites and the number of spin-down magnetic ions. Parts, the real and

imaginary of complex permittivity (έ, ε‫ )״‬and tangent loss assessed between 0.1 to107 Hz

ranges of frequency. It is observed that due to interfacial polarization dielectric constant

(real and imaginary part) and dielectric loss decreases with the increase of Sr2+

concentration.

Khan et al. [62] studied the interchange Ce and Mn by Sr and Fe respectively prepared

by co-precipitation method. They studied the structural, magnetic, electrical properties.

The magnetic parameters accounted from hysteresis loop were noticed increasing with

increasing Ce-Mn immersion. The resistivity is showing the trend of metal-to-

semiconductor transition Temperature curve. These results showed that material is

important for switching applications.

Iqbal et al. [63] worked on the W-type hexaferrite with new composition BaCoZnFe16-

2yAlCeyO27 prepared by chemical co-precipitation technique. They studied the structural

and magnetic properties. They also studied the complex permittivity and permeability

using network analyzer in the range 0.5 GHz to 10 GHz. These materials are suitable for

fading the electromagnetic intervention and as radar absorbing devices.

Stergiou et al. [64] studied the Ni and La substituted SrCo2Fe16O27 W-type hexaferrites

and their electromagnetic properties in microwave frequency set out 2-18 GHz. The

101
complex permittivity spectra shows no variation in the specified testing frequency band

while dielectric polarization increase with Ni and La content, that appears to enhance

dielectric dipoles concentration.

Deng et al. [65] studied W-type hexaferrites; Ba1Co0.9Zn1.1Fe16O27 and

Ba0.8La0.2Zn1.1Fe16O27 were developed by sol-gel technique. They studied

electromagnetic and microwave behavior of the ferrites in frequency set-out 2-18 GHz. It

was observed that there was an improvement in microwave absorption functioning as

Ba2+ was replaced by La3+. In addition a wider band width of value 8 GHz below -10 dB

was ascertained. Prime value of -39 for reflection loss at -39 dB in 2mm thick layer was

discovered.

Ahmad et al. [66] studied the single phase W-type hexaferrite. The samples are sintered

in the temp range 1000-1200 0C for 5h. They studied the TG, DTA, XRD, and VSM.

These samples are also important for the application of high density recording media.

Grain size calculated by Sherrer‟s equation was in 36-47 nm range.

Guo et al. [67] synthesized W-type rare earth substituted hexaferrite

Ba0.9RE0.1Co2Fe16O27 fabricated using solid state reaction technique at 1250 0C for 5 h.

They investigated the single phase Plate-let like shape of the samples. The lattice

parameter „a‟ and „c‟ decreases with the decrease of rare earth ionic radius whereas

saturation magnetization (Ms) and coercivity (Hc) of rare earth doped devices increased.

Complex permittivity and permeability were observed from 0.5-1.8 GHz frequency

range. Moreover, it was analyzed that RE substitution improved to super high frequency

for microwave absorption whereas La substitution showed optimum dielectric loss at 16

GHz.

Wu et al. [68] studied the W-type ferrite with composition BaCoNiPrxFe16-xO27

synthesized by sol-gel technique. All the samples seem plate-let shape W-type showing a

decrease in grain size with successive addition of Pr3+. The addition of Pr3+ increased Ms

102
While real part of complex permittivity (ε‫ )׳‬decrease and imaginary part (ε‫ )״‬increases.

Microwave absorbancy reaches outdo between 4-14 GHz frequencies spectra.

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106
3.1 Chemical Formulae of Ferrites

A series of mixed ferrites of various compositions were fabricated using well established

technique i.e. Co-precipitation and Sol gel auto-combustion methods. The following

compositions were fabricated and characterized.

1. BaHoxZn2Fe16-xO27 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0)

2. Ba1-xHoxCo2Fe16O27 (x= 0.0, 0.02, 0.04, 0.06, 0.08, 0.1)

3. SrZn2GaxFe16-xO27 (x= 0.0, 0.1, 0.2, 0.3, 0.4)

4. SrNdxZn2Fe16-xO27 (x= 0.0, 0.05, 0.1, 0.15, 0.2, 0.25)

3.2 Methods of Preparation

3.2.1 Co- Precipitation

In this study a series of W-type hexagonal ferrites with chemical formula BaHox Zn2Fe16-

xO27 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) were synthesized by Co-precipitation technique. This
107
technique is used for the synthesis of magnetic micro particles and nanoparticles. It is

one of the wet-chemical method synthesize ceramic powder of narrow particle size [1-2].

The phenomenon responsible for co-precipitation is adsorption, formation of solid

solution and mechanical inclusion. The precipitates are in the form of hydroxides,

oxalates etc. All of them can be thermally decomposed. The precipitation can be

accomplished either chemically or electrically.

The parameters used in this method like mixing rate, pH value (i.e. 11-12), temperature,

concentration have to be properly adjusted. To obtain nanostructure material required

drying and subsequent annealing.

This method was used because of the following advantages.

 Greater homogeneity.

 High reactivity.

 High purity

 Fine particle size

 Elimination of calcination

The starting materials to prepare these ferrites were metal chlorides, oxides and nitrates.

The metal chlorides, oxides and nitrates (99.99%) purity were used in chemical co-

precipitation method. Their Chemical name, chemical formulae, formula weights are

given in the Table 3.1.

Table 3.1: Chemical Name, chemical formula, formula weights of chemical

compounds

Name Chemical Formula Molecular Weight

Barium nitrate Ba (No3)2 261.35 g/mol
Holmium Oxide Ho2O3 377.89 g/mol
Iron Oxide Fe2O3 159, 69 g/mol

108
NaOH and Na2Co3 were used as precipitating agent. In chemical co-precipitation method

distilled water was used throughout the process.

The Stoichiometric amount of metal chlorides, oxides and nitrates were weighted using

Sartorius electronic balance having an accuracy of 10-4gm.

The weight (wt) percentage of each compound was calculated by using the formula;

Wt % of compound =

Mole fraction (in grams) of parent oxide materials for 2gm sample of BaHoxZn2Fe16-xO27

ferrites are listed in Table (3.2).

Table 3.2: Stoichiometric calculations of BaHoxFe16-xO27 hexaferrites

Ba(No3)2 Ho2O3 FeCl3.6H2O Na2CO3 NaoH

Conc.(x)
(g) (g) (g) (g) (g)
0.0 2.178 0 12.01 5.30 2
0.2 2.178 0.104 11.86 5.30 2
0.4 2.178 0.210 11.71 5.30 2
0.6 2.178 0.314 11.56 5.30 2
0.8 2.178 0.418 11.40 5.30 2
0.1 2.178 0.525 11.26 5.30 2

BaHoxZn2Fe16-xO27(x = 0.0, 0.2, 0.4, 0.8, 1.0) were prepared by co-precipitation

technique. Analytical grade ferric chloride (FeCl3.6H2O), barium nitrate Ba(NO3)2, Zinc

oxide (ZnO) and Holmium oxide (Ho2O3) were used as starting materials for the

preparation of BaHoxFe16-xO27 powder. After stoichiometric calculations the required

109
amount of parent materials was dissolved in de-ionized water. Since Ho2O3 is insoluble

in water, first it was dissolved in nitric acid at 80 0C in order to make nitrate and then

poured into the as-prepared solution. Proportionate amount of NaOH and Na2CO3 was

used as reagents to precipitate the metals as hydroxides. Calculated amount of NaOH and

Na2CO3were dissolved in 100 ml de-ionized water and added slowly drop-wise into

metal solution with constant stirring until precipitation is complete. The precipitates were

allowed to settle down and the as prepared liquid was tested with NaOH and Na2CO3

solution for any more precipitation. Filtration of precipitates was carried out with the

help of filtration flask operating on a water suction pump. In order to free the precipitates

from Cl- ions, these were washed using distilled water which were checked with the help

of AgNO3 solution. The precipitated product contained hydroxides of Ho3+, Ba2+, and

Fe3+. It was dried in an electric oven at a temperature of 110 0C for 24 h.

The grinding of dried powder for 2 hrs using mortar and pestle produced a homogenous

mixture. The pestle and mortar were rinsed with acetone before and after process. The

dried powder was calcined at 1050 0C for 2 hours, before final sintering and moulding of

powder into pellets was done using Paul-Otto Weber hydraulic press at pressure of ~35

kN / mm2. In order to get the required phase the pellets were then finally sintered at

1320 0C for 8 hours followed by air quenching. The step by step process for the

production of W-type hexaferrites using co-precipitation method is described in a flow

chart as shown in Fig.3.1.

110
 FeCl3.6H2O Ba(No3)2 Ho2O3 Citric acid

Deionized water Deionized water Nitric acid+80 0C Deionized water

+D.Water

NaOH Na2CO3

NaOH+ Drops Solution, RT 0C

Na2CO3

Suspension,
stirring, 1.5 h

Suspension aged,
12h

Filtration and wash until no Cl-1 ions

removed

Precipitates

Dried in oven, 110

0
C

Grinding

Calcination

Sintering

Characterization

Fig. 3.1 Flow chart of Co-precipitation method

3.2.2 Sol-Gel Auto Combustion

Another technique of the sample preparation is the sol-gel auto combustion. In material

science and ceramic engineering areas of research, wet chemical technique is widely

used because of lower sintering temperature and lesser time is involved when compared

to other methods. In short it is single and low cost method with advantage of high yield.

111
These hexagonal ferrites with composition Ba1-xHoxCo2Fe16O27 (x= 0.0, 0.02, 0.04, 0.06,

0.08, 0.1), SrZn2GaxFe16-xO27 (x= 0.0, 0.1, 0.2, 0.3, 0.4), SrNdxZn2Fe16-xO27 (x= 0.0,

0.05, 0.1, 0.15, 0.2, 0.25) were prepared by Sol-gel auto combustion method. The

starting materials were nitrates of metals with 99.99% purity used in this method.

The name of the chemicals, formulae and formula weights are given in the Table 3.3.

Table 3.3: Chemical formulae and formula weight of the materials used

Name Chemical Formula Formula Weight

Barium nitrate Ba(NO3)2 261.34 gm/mol

Strontium nitrate Sr(NO3)2 211.63 gm/mol

Iron nitrate Fe(NO3)3.9H2O 276.00 gm/mol

Cobalt nitrate Co(NO3)2.6H2O 291.04 gm/mol

Zinc nitrate Zn (NO3)2 297.48 gm/mol

gallium nitrate Ga(NO3)2.6H2O 255.74 gm/mol

Holmium Oxide Ho2O3 377.86 gm/mol

Neodymium oxide Nd2O3 336.48 gm/mol

Citric acid C3H4OH(COOH)3 192.12 gm/mol

Ammonia NH4OH 40.00 gm/mol

The required amount of chemicals was calculated by stoichiometric ratios and is given in

Table 3.4. These materials were then weighed using Sartorius electronic balance having

accuracy of 10-4gm.Stoichiometric calculations of all series are given in Table 3.5 (1-3).

112
 Table 3.4: Atomic weight of the elements

Elements Atomic weight gm/mol

Fe 55.85
Ba 137.33
Sr 87.62
Co 58.93
Zn 65.38
O 15.99
Ho 164.93
Ga 69.72
Nd 144.24

Table 3.5.1: Ba1-xHoxCo2Fe16O27 (x= 0.0, 0.02, 0.04, 0.06, 0.08, 0.1) hexaferrites.

Ba(NO3)2 Ho2O3 Co(NO3)2.H2o Fe(NO3)3 Citric acid

Conc.(x)
(g) (g) (g) (g) (g)
0.0 0.327 0 0.728 8.08 7.69
0.02 0.32 0.0095 0.728 8.08 7.69
0.04 0.314 0.019 0.728 8.08 7.69
0.06 0.307 0.028 0.728 8.08 7.69
0.08 0.30 0.038 0.728 8.08 7.69
0.1 0.29 0.047 0.728 8.08 7.69

Table 3.5.2: SrZn2GaxFe16-xO27 (x= 0.0, 0.1, 0.2, 0.3, 0.4) hexaferrites.

Sr(NO3)2 Zn(NO3)2 Ga(NO3)2 Fe(NO3)3.9H2O Citric acid

Conc.(x)
(g) (g) (g) (g) (g)
0.0 50 50 0 100 6.839828
0.1 50 50 1.25 99.375 6.839828
0.2 50 50 2.5 98.75 6.839828
0.3 50 50 3.75 98.125 6.839828
0.4 50 50 5 97.5 6.839828

113
Table 3.5.3: SrNdxZn2Fe16-xO27 (x= 0.0, 0.05, 0.1, 0.15, 0.2, 0.25) hexaferrites.

Sr(NO3)2 Zn(NO3)2 Fe(NO3)3.9H2O Citric acid

Conc.(x) Nd2o3 (g)
(g) (g) (g) (g)
0.0 6.25 10 0 40 6.839828
0.05 6.25 10 1.25 39.88 6.839828
0.1 6.25 10 2.5 39.75 6.839828
0.15 6.25 10 3.75 39.625 6.839828
0.2 6.25 10 5 39.5 6.839828
0.25 6.25 10 6.25 39.375 6.839828

These synthesized ferrites with compositions Ba1-xHoxCo2Fe16O27(x= 0.0, 0.02, 0.04,

0.06, 0.08, 0.1), SrZn2GaxFe16-xO27 (x= 0.0, 0.1, 0.2, 0.3, 0.4), SrNdxZn2Fe16-xO27 for (x=

0.0, 0.05, 0.1, 0.15, 0.2, 0.25) have been prepared by sol-gel auto-combustion method.

Nitrates having 99.99% purity were used as starting materials in this method. Using

stoichiometric calculation, salt solution was prepared in 100 ml de-ionized water.

Stirring continues for half hour without heating each salt solution. Then all the solutions

are mixed together. Ammonia solution was used to maintain its pH value at 7-8, stirred

continuously at a temperature of 80 oC to transform the sol into gel. The gel is ignited at

a temperature of 250 0C to convert into fluffy and loose powder. To obtain W-type

hexagonal ferrites the powder was finally sintered at 950 oC for 8 h. In order to get

cations equilibrium position, samples were cooled inside furnace. The powder was then

molded into pellets under pressure of 40 kN/ mm2 for 1-2 minutes. The complete

procedure for the synthesis of these hexaferrites is shown in Fig.3.2.

114
 Fe (NO3)3 Ba (NO3)2 Co (NO3)2 Citric acid
+De-ionized +De-ionized +De-ionized +De-ionized
water water water water

Ammonia Aqueous solution

solution
PH= 7-8
Stirring+800C
for 5-6hrs

Transformation
of sol into gel

Combustion at
2500C

Grinding

Sintering at 9500C for

5 hrs

Characterization

Fig. 3.2 The scheme shows the step of sample preparation using sol gel
technique

115
3.3 Characterization

W-type hexagonal ferrites were characterized by using the following experimental

techniques:

 Thermo gravimetric and differential thermal analysis (TGA / DTA)

 Fourier Transform Infrared Spectroscopy (FTIR)

 X-ray diffraction (XRD)

 Grain size Measurements

 D.C Resistivity measurement

 Dielectric measurement

 Magnetic measurements

 Microwave absorption

3.3.1 Thermo Gravimetric and Differential Thermal Analysis (TGA / DTA)

Thermo gravimetric analysis or thermal gravimetric analysis (TGA) is a type that

determines changes in weight as a function of temperature. Such analysis is based upon a

high degree of precision, weight temperature gradient. The interpretation of results

required a pre-transformation weight loss curve. The pre-transformation curve identifies

the dominant point of weightlessness and reduces the limitation of interpretation. To

determine degradation temperatures, moisture content, portion of organic and inorganic

components and decompose points of explosives and solved residuals from various

solids. It is also helpful in estimation of corrosion kinetics.

TGA-DTA/DSC determines heat flow and weight changes in a material as a function of

temperature or time in a controlled environment. These measurements provide

information to determine the final sintering temperature. The endothermic and

116
exothermic peaks can be differentiated using the information with no associated weight

loss (e.g., melting and crystallization) or those involve a weight loss (e.g., degradation).

3.3.2 Fourier Transform Infrared (FTIR) Spectroscopy

Infrared spectroscopy covers the region of the electromagnetic spectra having longer

wavelength and lower frequency range. Most widely used IR technique involves

absorption spectroscopy to identify the ingredients of some compounds. The three

regions used to determine vibrational and translational modes are the near, mid and far

infrared of electromagnetic spectrum. The higher energy near infrared region ranging

from 14000-4000 cm-1 (0.8-2.5m) may excite harmonic vibrations. The mid infrared

region ranging 4000-400cm-1 (2.5-25m) may be used to identify basic vibration and

linked rotational, vibrational structure. The low energy far infrared region ranging 400-

10cm-1 (25-1000 m) may be used for rotational spectroscopy.

FTIR spectroscopy technique involves the irradiations of material with complete IR

spectrum. Various bonds present in the molecules excite after absorbing energy of IR-

spectrum at particular frequencies. The peaks present in wave numbers Vs absorption

plots determined the bond present [5, 6].

3.3.3 X-ray Diffraction (XRD)

A Schimadzu X-Ray diffracto-meter equipped with Cu-Kα radiation with λ=1.5406Å and

wavelengths of about 10-10Å have been used to study the crystal structure. The spacing

between the diffraction crystal planes (d) and the angle of incident X-ray (θ) obey

Bragg‟s Law:

2d sinθ = nλ (3.1)

Where n is the order of reflection,  is the wave length of the X-ray source. The sample

was placed on a low X-ray absorption glass to get diffraction pattern.

117
Sample holder is rotated within a range of angles 2θ (10° to 75°). The diffracted X-rays

of the sample are then collected at the detector and then displayed on XY-plotter and

peaks can be matched by the JCPDS data [7]. The schematic representation of angle

measurement by XRD is shown in Fig.3.3. An X-ray beam impinges on a sample and the

intensity of scattered beam is measured.

Fig. 3.3 Coordinate system and specific angles for XRD measurements

3.3.3.1 Physical Density

The bulk density Db (g/cm3) or physical density of the sintered samples was measured by

Archimedean principle with the help of toluene as a liquid. The pellet is dipped in liquid

(toluene) to show the force of buoyancy and this force is equal to the weight of the liquid

displaced by the volume of the sample. Sample is to be weighed in air and liquid also by

the hydrostatic balance. So the density of solid can be determined if the density of liquid

is known and can be calculated by the following equation. [8];

D = [Wair / Wliquid - Wair]× density of toluene (3.2)

Where

118
Wair= weight of sample in air, Wliquid= weight of sample in liquid and density of toluene

is 0.857g/cm3 and Wliquid - Wair = weight loss in liquid.

3.3.3.2 X-ray Densities

Following relation determines the X-ray densities [9],

Dx = 2M /NAV (3.3)

Where

M = molecular weight

NA= Avogadro‟s no

„V‟ = volume of the unit cell for the sample which was calculated from the X-ray

diffraction pattern.

3.3.3.3 Porosity

Porosity (P) percentage is determined using [8];

P (%) = [1- Db / Dx] ×100 (3.4)

Where Dx and Db are the X-ray and bulk densities respectively.

3.3.4 Grain Size Measurements

For grain size and morphology study, SEM micrographs are obtained on the surface of

the samples with the help of Hitachi Scanning Electron microscope SU-1500, and the

applying accelerating voltage 0.3-30 KV working in the oil rotary pump at room

temperature. It is extensively used in surface imaging, microstructure examination and

particle size evaluation. Using the line intercept method the average grain size was

observed by SEM patterns.

119
3.3.5 D.C Resistivity Measurement

Two point probe technique was used to calculate dc resistivity. A copper electrodes

having effective area 0.14 cm2 made contacts on both sides of samples. Silver paste

helped to obtain good ohmic contacts. Keithly source / measure unit model 2400 was

used to acquire 1-V data.

The connections were in series as shown in Fig.3.4. A typical sample holder is used in

this study as shown in Fig. 3.5. The resistivity is calculated by two-probe method using

the following formula;

ρ = RA/t (3.5)

Where

R = resistance of the sample

A = effective area of the electrode

t = thickness of the sample.

The effective area of the circular electrodes was calculated by using the relation [10];

A= πr2 (3.6)

Where r is radius of the electrode.

Fig. 3.4 Circuit diagram of two probe method [11]

120
 Fig. 3.5 Two probe sample holder for resistivity measurements [11]

Both sides of the sample were polished before measurements to remove oxide layer their

sides. The pressure contacts were used to fix the pellets. Temperature dependent

electrical resistivity measurements were taken in the temperature range 33-200 0C. The

temperature was maintained in a furnace controlled by varying potential with an

accuracy of 2◦C. Keeping voltage fixed at 10 V across sample, temperature was varied

in steps of 10 0C and corresponding current was measured using electrometer. The data

was processed to get activation energy by using Arrhenius relation.

3.3.6 Dielectric Measurements

An LCR meter model (LCR-8101, frequency range 20 Hz- 1MHz) was used to study the

dielectric response of the hexagonal ferrites. Complex dielectric constant ( is defined

by equation.

(3.7)

is the complex dielectric constant, is the real part of dielectric constant, and is

the imaginary part of the dielectric constant; where

(3.8)

C = capacitance in Farad,
121
d = thickness of pellet in meters;

A= area of the flat surface of the pellet,

˳= permittivity of free space [12];

The dielectric loss or loss tangents is determined by the relation,

(3.9)

3.3.7 Magnetic Measurements

Vibrating Sample Magnetometer (VSM) is widely used technique to study magnetic

properties. Measurements were taken at 300 K at zero applied magnetic fields and at 50

Hz frequency with small amplitude (~1mm).The MH loops were traced at maximum

applied field i.e, 8000 Oe to determine saturation magnetization, remanence, and

coercivity. The MH loops results parameter values in milli volts which are converted to

electromagnetic unit (emu) using nickel as standard. The conversion of units is done by

dividing the data by mass or volume for each sample [13].

3.3.8 Microwave Absorption

In microwave absorption Vector Network Analyzer is widely-used equipment for the

high frequency measurements. In this study, the complex permeability μ and permittivity

ε were determined using a VNA (Vector Network Analyzer hp 8510C) 0.5-13 GHz. A

composed sample with epoxy was mixed for the purpose of measurement with

concentration of 75:25 by weight. The purpose of this epoxy was to use as a binder

matrix. A ring shaped specimen with inner and outer diameter of 3mm and 7mm

respectively with different thickness was used and composite sample pressed into it [14-

18].

122
References

[1] Dhage S R, Ravi V and Date S K Bull.J. Magn.Mater.Sci. 26 (2003) 215.

[2] Gaikwad S P, Dhesphande S B, Khollam Y, Samuel V and Ravi Mater. Lett.58

(2004) 34.

[3] Z. Yue, L. Li, J. Zhou, H. Zhang, Z. Gui, Mat. Sci. Engg. B 64 (1999) 68.

[4] M. D. Nersesyan, A. G. Peresada, A. G. Merzhanov, Int. J. SHS 7 (1998) 60.

[5] William Kemp, Organic spectroscopy 3rd ed.; Mac Millan press Ltd. (1991).

[6] Raul Valenzuela, “Magnetic Ceramics”, Cambridge University Press (1994) 62.

[7] B. D. Cullity, Elements of X-ray Diffraction 2nd ed.: Addison-Wesley

Publishing Company, Inc. (1978).

[8] Noboru Ichinose, Introduction to Fine Ceramics, Ohmsha Ltd., Japan, (1987).

[9] William F. Smith, “Principles of Materials science and Engineering”,2nd ed,

McGraw- Hill, Singapore Inc (1990) 90.

[10] Muhammad JavedIqbal, MahRukhSiddiquah, J Magn. Magn.Mater.320 (2008)

845.

[11] M.M. Barkat, M.A.Hanaish, S.A Olofa and A. Tawfik, J.Thermal Analysis 37
(1991)241.

[12] E. C. Snelling, Soft Ferrites; Properties and applications, Butterworth, London,

(1990).

[13] Foner, S. “The vibrating sample magnetometer”: Experiences of a volunteer

Invited, J. Applied Physics 79(1996) 4740.

[14] Naito, Y. in Proc. 1st Int. Conf. on Ferrites. (1970).

[15] Nakamura, T., J. Magn. Magn.Mater. 168 (1997) 285.

[16] MamataMaisnam, SumitraPhanjoubam, H.N.K. Sarma, L. Radhapiyari Devi,

O.P. Thakur, Chandra PrakashPhysica B 352 (2004) 86.

[17] Dr. moIng. Carl Heck, “Magnetic Materials and their Applications”,
Butterworths Co. (Publishers) Ltd, London (1974) 30.

[18] A.C. Razzitte, S.E. Jacobo, W.G. Fano, J. Applied Physics 87 (2000) 6232.

123
4.1 BaHoxZn2Fe16-xO27 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) Hexagonal
Ferrite Series I

4.1.1 Structural Properties

4.1.1.1 X-Ray Diffraction

X-Ray diffraction patterns show single phase W-type structure of all compositions as

shown in the Fig. 4.1 (a). The parameters „a‟ and „c‟ were calculated by abinito

method using following equation;

Sin2θ = λ 2/3a2 (h2+ hk+ k2) + (λ 2 /4c2) l2 (1)

The (c/a) ratio varies from 5.5- 5.8, that falls in the allowed range of W-type hexagonal

ferrites. The change in the values of „a‟ and „c‟ suggests that the Fe 3+ ions have

been substituted by RE3+ ions and this change is occurred due to difference between

ionic radii of RE3+ and Fe3+ ions and interaction between rare earth and surrounding

ions [1]. The ionic radius of Ho (0.901Å) is greater which prefers octahedral sites

followed by the migration of some Fe3+ (0.67Å) ions from octahedral sites to tetrahedral

sites [2, 3]. Therefore with the increasing Ho content both lattice parameters „a‟

and „c‟ increases [4, 5]. The variation of lattice parameters and the (c/a) ratio versus

Ho concentration is given in Table I. X-ray density and Bulk density is also listed in

Table 4.1 (a).

124
The X-ray density was calculated by using the formula:

Dx = 2M / NAV (2)

„M‟ is the molar mass „N A‟ is Avogadro‟s number and „V‟ is the volume of unit

cell which is calculated using the relation, V = a2c sin1200. It was observed that the X-

ray density (Dx) increases from 5.0 to 5.5 g /cm3. The increase in X -ray density may be

due to the greater atomic mass of Ho+3 (164.93a.m.u) than that of Fe3+ (55.85a.m.u) [6].

Fig. 4.1:(a) X-ray Diffraction patterns of BaHoxZn2Fe16-xO27 ferrites

(x=0.0,0.2,0.4,0.6,0.8,1 .0)

4.1.1.2 Grain Morphology

Fig.4.1 (b) SEM images of all samples of different composition that confirms the nano

size particle of BaHoxZn2Fe16-xO27 hexagonal ferrites. The grain size measured from

SEM micrographs varies from 205 to 188 nm respectively for the compositions x = 0.0,

0.2, 0.4, 0.6, 0.8, 1.0. It is evident that the crystallites are homogenous, uniform in size

and irregular in shape.

125
X = 0.0 X = 0.2

X= 0.8 X=1.0

Fig. 4.1(b) SEM Micrographs of BaHoxZn2Fe16-xO27 ferrites

126
Table 4.1 (a): Lattice constants, c /a ratio, X-Ray density, Activation energy,
Resistivity for BaHoxZn2Fe16-xO27 ferrites

Parameters X = 0.0 X = 0.2 X = 0.4 X = 0.6 X = 0.8 X = 1.0

Lattice constant, a(Å) 5.86 5.87 5.88 5.87 5.88 5.91

Lattice constant,c(Å) 32.6 32.87 33.34 33.30 33.5 33.45

c /a 5.55 5.59 5.67 5.67 5.69 5.66

X-Ray density
5.01 5.03 5.07 5.11 5.13 5.16
Dx (g cm-3)
Activation energy
0.178 0.413 0.619 1.23 0.55 0.318
(eV)
Resistivity ,
7.36x102 3.46x10 4 2.62x10 7 6.05x108 1.11x109 3.7x109
(Ω-c m )

4.1.2 Magnetic Properties

The magnetic properties of all given samples have been investigated from M H-Loops as

shown in Fig.4.1(c). The saturation magnetization (Ms), remanence (Mr) and coercivity

(Hc) are listed in Table 4.1 (b). Ms and Mr depend on the R3+ substitution for Fe3+ ions.

Coercivity is a collective property of the system of interacting grains. In the present work

our results show that the magnetization increases with the increase of Ho concentration

because of larger magnetic moment of Ho (10µB) than Fe (5µB). The Hc increases that

may be due to the enhancement of magneto crystalline anisotropy [7] with anisotropic

Fe2+ ions located on 2A sites as usually found in rare earth substitution [8,9] and this

happens due to elevated sintering temperature [10]. Coercivity increases with the

increase of Ho concentration. It is observed that Hc is inversely proportional to the

packing of magnetic materials or the grain size that is Hc α 1 / r. Our results agree with

the reported results on W-type hexagonal ferrites [11].

127
Fig. 4.1 (c) M H loops of the BaHoxZn2Fe16-xO27 ferrites

128
Table 4.1 (b): Coercivity, Saturation Magnetization and remanence for
BaHoxZn2Fe16-xO27 ferrites

X Hc(Oe) Ms(emu/g) Mr (emu /g)

0.0 1041.7 3.648 1.334

0.4 1358.4 21.078 8.347

0.8 1709.6 31.831 14.492

4.1.3 Electrical Properties

Room temperature resistivity of BaHoxZn2Fe16-xO27 ferrites was measured in the

temperature range 40-200 0C is listed in Table 4.1 (a). The room temperature resistivity

increases significantly from 7.36×102 to 3.7×109 ohm-cm with the increase of Ho

concentration. The room temperature resistivities of W-type hexaferrites reported by

various authors are found to be in the range of 104-107:-cm [5, 2]. Our results of

resistivity fall in the reported range. The increase in the resisitivity may be attributed to

the obstruction in the Verwey's mechanism due to larger density of grain boundaries

produced by fine grains. Moreover the resistivity of Ho (81.4×10-8 ohm-m) is larger

than Fe (9.71×10-8 ohm-m) and Ba (33.2×1 0-8) at 300K which is responsible for the

enhancement of resistivity. Temperature dependent dc electrical resistivity is shown in

the Fig. 4.1 (d). It can be seen that as the temperature increases the resistivity decreases

verifying the equation:

ρ = ρo exp (-Ea / kBT) (3)

Where kB is the Boltzmann constant and T is absolute temperature. It also showed that

by increasing temperature, the conductivity of ferrite increases, indicating that these

ferrites exhibit semiconducting behavior. The activation energy (Ea) of hopping for the

different samples is calculated Arrhenius plots.

129
The increase in activation energy may be attributed to the creation of more cations and

developing of oxygen vacancies which might have been produced due to rise in

temperature. It is concluded that concentration of oxygen vacancies is an important

factor in sintering process as well as in dc electrical resistivity [6].

Fig. 4.1 (d) Arrhenius plots of the BaHoxZn2Fe16-xO27 ferrites.

4.1.4 Dielectric Properties

Fig. 4.1(e- i, ii) shows the real (έ) and imaginary (ε ‫ )״‬part of complex permittivity

BaHoxFe16-xO27 ferrites. It is observed that real and imaginary part of complex

permittivity decreases with the increase of frequency. The dielectric properties of

polycrystalline ferrites are mainly due to interfacial polarization and intrinsic electric

dipole polarization, it conformity with Koop‟s phenomenological theory. The

substitution of Ho3+ for Fe2+ contribute to the increment of interfacial polarization with

the increase of iron ions because iron ions are easily polarized and intrinsic electric

130
dipole polarization due to electronic transfer between Fe2+ and Fe3+ on the octahedral

sites, with the increase of iron ions, the enhance of electron hopping increase. This could

to lead higher permittivity. The decrease of both the real and imaginary parts of

permitivitty because of occupation of Ho ions at the octahedral where hopping is a

reason of conduction. The reduction in dielectric constant originates as a result of

replacement of iron ions from octahedral sites by doping cations. This replacement

decreases iron ions and hopping electrons resulting the decrease in dielectric constant. As

the microwave devices require highly resistive materials, therefore Ho doped synthesized

materials can be useful [12, 13].

Fig. 4.1 (e-iii) shows the variation of dielectric loss factor vs frequency. It can also be

observed that the value of tan (δ) decreases with the increase in frequency. This decrease

in tan loss with increasing frequency can be justified on the basis of Koop‟s theory. The

sample x=0.8 exhibit the loss peak and this peak value occurs when the hopping

frequency of electron between Fe2+ and Fe3+ is equal to the frequency of the applied

field [14].

131
 Fig. 4.1 (e-i) Real part of dielectric constant (έ) of BaHoxZn2Fe1 6-xO27

Fig. 4.1 (e-ii) Imaginary part of dielectric constant (ε ‫ )״‬of BaHoxZn2Fe1 6-xO27

132
Fig. 4.1 (e-iii) Dielectric loss factor (tan δ) as a function of frequency for
BaHoxZn2Fe1 6-xO27

133
4.2 Ba1-xHoxCo2Fe16 O27 (x= 0.0, 0.02, 0.04, 0.06, 0.08, 0.1) Hexagonal
Ferrite Series II

4.2.1 Thermal Analysis

The DT/TGA curve of as-prepared powder Ba1-xHoxCo2Fe16 O27 (x= 0.1)) is shown in the

Fig. 4.2(a). The curve exhibits two distinct weight loss steps corresponding to

exothermic and endothermic peak in the DTA curve. The graph shows the weight losses

at different peaks. The first weight loss (1%) in the temperature range of about 100 0C

corresponds to the removal of water from the as-prepared sample which is accompanied

by an endothermic peak at around 100 0C in the DTA curve. The strong exothermic peak

at about 300 0C is sharp and intense and shows conversion of metal hydroxides into

oxides with a subsequent weight loss of 5%. The second endothermic peak appears at

500 0C which is attributed to the formation of mono ferrites (BaFe2O4) [15] and showing

a weight loss of about 3%. Finally an exothermic is also appearing at 720 0C and this

peak is attributed to the decarboxylation of the mixture of carbon and iron oxide [16]. It

is obvious that there is no weight loss after 800 0C which indicates the completion of

formation of hexaferrite, thus 950 0C temperature is sufficient to obtain the single phase

hexaferrites prepared by the sol gel method which is known to cause lowering the

sintering temperature. The sintering temperature in the present study is much lower as

compared to other reports for similar structure [2].

134
Fig. 4.2 (a) DT/TGA curves of as prepared Ba0.9Ho0.1Co2Fe16-x O27 hexaferrite
powder.

4.2.2 IR Spectra

Fig. 4.2 (b-i, ii) the FTIR spectra of Ba1-xHoxCo2Fe16O27for the un-sintered and sintered

(950 0C) samples. The specta of un-sintered sample have the peaks of absorption bands

at 3450 cm-1 which is due to stretching vibration of O-H due to water present in the

sample during preparation, anti-symmetrical vibration of carbonates around to 1576cm-1,

N-O stretching vibration of nitrates at about 1378 cm-1 and metal-oxygen stretching

vibrations at 574 cm-1 which is considered to be due to presence of α-Fe2O3 in the

as-prepared sample [17]. Sintered sample shows that there are no characteristics bands of

O-H, carbonates and nitrates in the sample. The spectrum bands of these ions disappear

when the powder is sintered at 950 0C and only the well resolved absorption bands at

about 582 and 430 cm-1 are observed which originates from the presence of tetrahedral

and octahedral complexes. The FTIR results are in good agreement with those observed

in XRD analysis.

135
Fig. 4.2 (b-i, ii) FTIR spectra of un-sintered (i) and sintered (ii) powder of
Ba1-xHoxCo2Fe16-x O27 (x=0.1) hexaferrite samples.

136
4.2.3 Structural Measurements

The phase purity was identified by X-ray diffractometer and patterns of all hexaferrite

samples Ba1-xHoxCo2Fe16O27 (x= 0.0, 0.02, 0.04, 0.06, 0.08, 0.1) are shown in Fig. 4.2

(c). It is observed that all samples exhibits single phase hexagonal structure. The

diffraction peaks are found to compare to those of the standard patterns (JCPDS 78-

0135). No characteristic peak due to impurities is detected in the XRD patterns of all the

samples hence showing that the samples are single phased and crystallized in space group

p63/mmc [17,18, 19,]. The lattice parameters „a‟ and „c‟ were calculated by the

following equation [20];

1 /d2hkl = 4( h2+ hk+ k2) / 3a2 + l2/c2 (4)

Where d is the interplanner spacing and hkl are miller indices. The calculated lattice

parameters, corresponding c/a ratio are summarized in Table 4.2 (c). It is clear that the

calculated values of lattice parameters „a‟ and „c‟ for an unsubstantiated sample are

5.85Å and 33.48Å which are agreement with those reported for the similar structure [2].

The unit cell volume was also calculated from the lattice constant „a‟ and „c‟ by using the

following relation and its values are summarized in Table 4.2 (a).

V = a2 c sin1200 (5)

137
 (225)

(301)

(311)

(311)
(211)
(111)

(201)
(112)

(315)
0.1

0.08

intensity (counts/sec) 0.06

0.04

0.02

x=0.0

20 30 40 50 60 70 80
2

Fig. 4.2 (c) XRD patterns of all substituted Ba1-xHoxCo2Fe16-x O27 hexaferrites.

Table 4.2 (a): Lattice constants „a‟, „c‟, c /a ratio, cell volume, X-ray density, Bulk
density, Porosity, Grain size and Activation Energy of
Ba1-xHoxCo2Fe16-x O27

Concentration
x = 0.0 x= 0.02 x = 0.04 x = 0.06 x = 0.08 x = 0.1
(x)
Lattice constant, a
5.85 5.81 5.83 5.79 5.82 5.84
(Å)±0.001
Lattice constant, c
33.48 33.41 33.39 33.34 33.29 33.23
(Å)±0.001
c/a ratio 5.72 5.75 5.73 5.76 5.55 5.52

Cell volume V(A 3 ) 992.2 976.7 982.8 967.9 976.2 981 .5

d x (g/cm 3 ) 5.22 5.14 5.17 5.1 5.14 5.17

Bulk
2.53 2.69 2.75 2.65 2.75 2.60
density(g/cm 3 )±0.01
Porosity (%) 52 48 47 48 46 49

Grain size (nm) 44.08 41.33 39.89 35.91 36.00 34.14

Activation Energy
0.43 0.94 0.32 0.76 0.94 1 .0
E a (eV)

138
4.2.4 Physical Properties

Bulk density plays an important role in analyzing the magnetic ceramics for specific

applications. In the present study, the density of samples is measured by the following

equation;

dB = m/πr2h (6)

Where

m = mass

d = height (thickness)

r = radius of the pellet.

X-ray density (dx) for all samples was extracted from X-ray data by the formula;

dx = 2M/N AV (7)

Where

M = molecular mass

NA = Avogadro‟s number

V= volume of the unit cell

The value of bulk density (dB) is smaller than that of X-ray density (dx) which is due to

the presence of unavoidable pores during the sintering process. It is observed that the

value of lattice constant „a‟ is fluctuating and „c‟ decreases with the increase of Ho3+

content due to the smaller value of ionic radius of Ho3+ (0.901Å) as compared to that of

Ba2+ (1 .35Å), since Ba2+ is found in R-blocks, the replacement of Ba2+ by Ho3+ results in

decreases of distance between layers as well as the decrease in the lattice parameter c (Å).

So the increase in Ho3+ contents results a decrease in lattice parameters (c). The value of

bulk density as compared to theoretical density is lower because of pores produced in

sintering process [20]. The values of bulk density are lower than those of corresponding

X-ray density owing to the pores formed and developed during the sintering process

[21]. The porosity of the sample was determined by the relation;

139
 P (%) = (1-dB/dx) ×100 (8)

The porosity of the sample with the increase of concentration „x‟. The porosity decreases

is an indication that doped element did not retard densification of hexaferrite matrix [22].

The calculated parameters and values are listed in the Table 4.2 (a).

4.2.5 Grain Morphology

Fig. 4.2 (a) shows SEM of all investigated samples. The white spots show that the

material is not homogenous but as the substitution is increased the material becomes

homogenous and mono dispersed. The values of grain size calculated by line intercept

method from these micrographs are in the range of 34-44 nm and are summarized in

Table 4.2 (a). A good signal to noise ratio is achievable if grain sizes is less than 50nm

[20]. It is evident that the grain size gets smaller and is homogenously spread with

increasing substituent. This is due to the reason that rare earth substitution inhibits the

grain growth [23].

140
Fig. 4.2 (d) SEM images of all substituted Ba1-xHoxCo2Fe16-xO27 hexaferrites.

141
4.2.6 Electrical Resistivity

Fig. 4.2 (e) shows the plot of electrical resistivity as a function of temperature which

decreases with increasing the temperature according to the following relation thereby

showing the semiconducting behavior of the investigated ferrites.

ρ =ρ 0 exp (-Ea/kBT) (9)

Where

ρ = resistivity

kB = Boltzmann constant

Ea = activation energy of hopping electron

The room temperature dc electrical resistivity can be explained on the basis of Rezlescu

model; the conductivity in ferrites is due to hopping of electrons between Fe3+ and Fe2+

ions at octahedral sites [16]. The substitution of Ho3+ ions to the nearest neighbors of

Ba2+ ions in the Ba-layer are 12k,4f2 and 2b (octahedral sites) where 2b site is at

minimum distance to the Ba2+ ion site (d = 0.340 Ǻ) compared to the 4f2 site (d= 0.3660

Ǻ) [17]. The presence of Ho3+ ion near the octahedral site would not only change the

separation between the Fe2+ and Fe3+ ion but may also reduce the Fe2+-O-Fe3+ bond

angle. Thus it impedes an electron transfer process between Fe2+, Fe3+ ions and increases

the resistivity [17]. The temperature dependence of resistivity can be described on the

basis of Verwey‟s hopping mechanism. According to this, the electron conduction in

ferrite is due to hopping of electrons between ions of the same element in different lattice

sites [6]. In the semiconducting region the activation energy (Ea) is calculated from the

slope of linear plots which is plotted between log ρ and reciprocal of the temperature.

The increase in activation energy due to increase in cations and developing of oxygen

vacancies might be due to rise in temperature. The variation of activation energy

corresponds to the variation of resistivity; the sample of high resistivity also has high

142
energy of activation and vice versa. The resistivity and activation energy data seems to

support each other [22].

Fig. 4.2 (e) Arrhenius plots of Ba1-xHoxCo2Fe16-xO27 hexaferrite.

4.2.7 Dielectric Measurements

The dielectric constant (real and imaginary part) and dielectric loss are shown in Fig. 4.2

(f-i, ii, iii) respectively. It is observed that all the samples exhibit frequency dependent

phenomenon and the value of έ decreases with the increase of frequency. This is the

normal trend for hexaferrite (1 M Hz) and can be explained on the basis of space charge

polarization and Maxwell-Wagener Koop‟s model. The space charge polarization arises

due to inhomogeneous dielectric structure of the material. Polarization is determined in

response of electron exchange among Fe2+ and Fe3+ ions where local displacement

occurs on application of electric field. A substantial decrease in polarization with

increase in frequency approaches to a constant value due to fact that, after a certain
143
frequency of applied field, the electron exchange among Fe2+ and Fe3+ ions does not

follow the changing field and by Koop‟s model the dielectric constant at low frequency

comes from the grain boundary because high dielectric constant due to high resistivity at

grains boundary. At low frequency the larger value of dielectric constant is due to the

predominance of species like Fe2+ ions, interfacial dislocation, pile-ups, oxygen

vacancies and grain boundary defects. The dielectric constant at high frequency comes

from the grains which have a small dielectric constant values due to low resistivity. The

decrease in dielectric constant with frequency due to the fact that any species

contributing to polarizibility is bound to show the lagging behind the applied field at

higher frequency [24]. The dielectric loss is the ratio of loss or resistive current to the

charging current in the sample. The dielectric loss for all samples is shown in Fig. 4.2 (f-

iii). All of the samples show decrease in tanδ with increasing frequency. More energy is

required for electron exchange between Fe2+ and Fe3+ ions. The energy loss is high when

more energy is required for electron exchange among Fe2+ and Fe3+ ions and resistive

grain boundaries were more effective at higher frequency and energy loss is low when

less energy is required for electron exchange among Fe2+ and Fe3+ ions [25, 26].

144
Fig. 4.2 (f-i) Real part of dielectric constant (έ) of Ba1-xH oxCo2Fe16O27 hexaferrite.

Fig. 4.2 (f-ii) Imaginary part of dielectric constant (ε ‫ )״‬Ba1-xH oxCo2Fe16O27

hexaferrite.

145
Fig. 4.2 (f-iii) Dielctric loss factor (tan δ) as a function of frequency for
Ba1-xH oxCo2Fe16O27 hexaferri tes.

146
4.3 SrZn2GaxFe16-xO27 (x= 0.0, 0.1, 0.2, 0.3, 0.4) Hexagonal Ferrite
Series III

4.3.1 Structural Properties

4.3.1.1 Thermal Analysis

The DTA/TGA curve for an unannealed sample with composition SrZn2GaxFe16.xO27 is

shown in Fig.4.3 (a). The thermal analysis is carried out to evaluate the mechanism for

the formation of phase and to observe the effect of heating on structural changes of the

synthesized sample. The loss at 110 0C is due to loss of water and that at 316 0C is due to

decomposition of metallic hydro oxide into oxide. The loss at 761 0C and 827 0C is

attributed to the formation of strontium mono ferrite and strontium hexaferrites

respectively. TG analysis indicates that the hexagonal phase formation begins at 761 0C

and gets completed at 950 0C [2]. Above 950 0C no further indistinguishable weight loss

was detected indicating that all organic constituents were eliminated. This can be

associated with self propagation nature of the combustion process of the dried gel once

ignited. The decomposition of the dried gel occurs suddenly in a single step, as observed

in other system [16].

147
 Fig. 4.3 (a) DT/TGA curves for SrZn2GaxFe16.xO27 hexaferrite powders.

4.3.1.2 X-ray Diffraction

Fig.4.3 (b) shows the X-ray diffraction patterns of SrZn2GaxFe16.xO27 (where x= 0.0,

0.1, 0.2, 0.3,0.4) single phase W-type hexagonal ferrite samples. Lattice constants (a and

c) and cell volume (Vcell) is calculated from XRD using formulae;

1/d2 = 4/3 (h2+hk+k2)/a2 +l2/c2 (1)

Vcell = a2csin1200 (2)

Where d is the inter planner spacing and hkl are miller indices.

The values of lattice constants and corresponding c/a ratios are given in the Table 1. It is

evident that both lattice constants decrease with the increase of Ga contents (x).The

decreasing lattice constants with the increasing Ga3+ is because of replacement of higher

ionic radii of Fe+3 (0.67 Ǻ) with Ga3+ (0.64 Ǻ) and the unit cell volume decreases with

the increase of Ga3+ contents. This behavior is evident that a negligible rise in molar

148
mass of doped cations results a decrease in cell volume. The doping of Ga3+ ions

contracted the unit cell volume of Sr-hexaferrite..

149
 Fig. 4.3 (b) XRD patterns of SrZn2GaxFe16.xO27 (x=0, 0.1, 0.2, 0.3, 0.4) hexaferrite
powders.

Table 4.3 (a): Lattice constants (a and c), c/a ratio and cell volume of
SrZn2GaxFe16.xO27 hexaferrites samples

X a(Å) c(Å) c/a(Å) V(Å)3

0 5.819 32.892 5.652 965.174
0.1 5.816 32.881 5.654 963.857
0.2 5.811 32.86 5.655 961.586
0.3 5.814 32.832 5.647 961.759
0.4 5.812 32.892 5.652 965.174

4.3.1.3 IR Spectral Study

The FTIR spectra of unannealed and annealed samples are shown in Fig. 4.3 (c-i, ii, iii).

IR analysis helps out to understand the structural changes and formation of crystal phase

in combustion process. The infrared spectrum of sample (SrZn2Fe16O27) was recorded

by FTIR spectrometer showing the absorption bands. The unannealed sample shows the
150
absorption bands at 3449, 1624, 1387, and 546 cm-1. The absorption bands at 3449,

1624 peaks are due to the stretching vibrations of O-H mode of water. The band at 1387

cm-1 shows N-O stretching vibrations of No3 ions. The band at 546 cm-1 is due to iron-

oxygen bonds which are characteristics of magnetite (γ-Fe2 O3 ) [27]. The annealed

samples at 950 0C shows the absorption bands at 593 cm-1 and 432 cm-1 identified as the

metal oxygen stretching vibrations of hexaferrites.

151
Fig. 4.3 (c-i, ii) FTIR spectra of an un-annealed (i) and annealed (ii)
hexaferrite powders.

4.3.1.4 Grain Morphology

Fig. 4.3(d) exhibits the SEM images of, samples of varying composition. The grains are

homogenously distributed and become smaller as the substitution increase up to 0.4. The

grain size is calculated by intercept method. The estimation of grain size is in the range

of 139-76 nm which is considered to be in the nanosized range as reported earlier in the

literature [28, 29]. The results show that the grain size of Sr-based W-type hexaferrites

152
was observed to decrease after the substitution of Ga3+ ions [20]. In addition, a smaller,

more perfect and homogenous grain is observed Ga3+ doped ferrite. The co-relation

between cell parameters calculated from XRD and SEM data revealed that there is

decrease in cell volume as Ga3+ content is increased [35]. Therefore decrease in grain

size may be linked with lattice constant when Ga3+ is substituted at Fe3+ sites due to the

smaller ionic radius of Ga3+ that is substituting Fe3+, thus causing slight distortion in Ga -

doped lattice yielding smaller sized grains [30,31].

153
Fig. 4.3 (d) SEM images of SrZn2GaxFe16.xO27 (x=0, 0.2, 0.3, 0.4) hexaferrite
powders.

154
4.3.1.5 EDX Analysis

Fig. 4.3 (e) shows the EDX spectrum of SrZn2Ga0.2Fe15.8O27 ferrites that confirms the

presence of Fe, Ga, Zn, Sr ions in proper ratio. [20]. Elemental percentage of each

element may be observed in EDX analysis. Peak height in the graph represents the

proportion of each element in sintered sample. A change can be observed in the size and

height of the peak of Ga-substituted sample. In the present study the Ga is substituted for

iron [32].

Fig. 4.3 (e) EDX spectrum of SrZn2Ga0.2Fe15.8O27 hexaferrite powder

4.3.2 Electrical Properties

Room temperature electrical resistivity was measured using two probe technique. Fig.

4.3 (f) shows resistivity as a function of Ga content (x). It can be seen that the resistivity

increases with the increase of Ga content (x). This may be due to the fact that Ga3+ (9.61

10-7) is more resistive than Fe3+ (2.79 10-7) [33]. Resistivity of W-type hexagonal ferrites

found in the range 104-109 ohm-cm [2] and the same observed in present work. This

range is best to reduce eddy current at high frequencies.

155
 Fig. 4.3 (f) Room temp resistivity SrZn2GaxFe16-xO27 hexaferrite powder.

4.3.3 Magnetic Properties

The M-H loops for all SrZn2GaxFe16-xO27 W-type hexagonal ferrite samples are shown in

Fig. 4.3 (g). The parameters like saturation magnetization (Ms), remanent magnetization

(Mr) and coercivity (Hc) were calculate d from the loops and listed in Table 4.3(b). The

shape and width of the loops depend upon chemical composition, cation distribution,

porosity, grain size, etc. The monotonous increase in width of loops shows an increase in

Hc with the substitution amount of Ga3+. The coercivity is based upon intrinsic and

extrinsic properties of the materials. The Intrinsic properties involve structural and

chemical composition, Ms, Tc, etc. while extrinsic properties involve microstructure,

grain size and shape and defects etc. A small coercive field is required for soft magnetic

materials. The increase of Hc is due to the decrease in grain size which is inversely

related [11]. The coercivity value is in the range of few hundred Oersted which is

suitable for longitudinal magnetic recording media [22]. Moreover the low value of

coercivity is also one of the necessary conditions for EM materials [34]. The results also

show that with the increase of Ga3+ substitution, Hc increases due to attenuation of

156
exchange coupling which leads to increase Hc and decrease of Mr. The observed decrease

in saturation magnetization may be ascribed to the hard reversible displacement or

domain wall movement in the applied magnetic field direction. For this displacement to

occur, the energy of the domain wall pinning must be greater than that of the applied

external field. Thus, harder the displacement, the smaller would be the saturation

magnetization. Furthermore, as the compensated magnetization of two interstitial sites

can be described as M =(Mb–Ma), where Mb and Ma are magnetizations due to octahedral

B-sites and tetrahedral A-sites respectively, hence M decreases with the substitution of

Ga3+ ions at B-site because the substituting Ga3+ ions preferably occupy the B-site [35].

Note that the magnetic moment of Fe3+ ions is larger than that of nonmagnetic Ga3+ ions.

When the number of Fe3+ ions at B-site decreased, the magnetization of B-sublattice

decreased, consequently a decrease in the saturation magnetization has been observed for

the Ga-substituted ferrite samples. The decrease in Ms and Mr at higher substitution may

be attributed to breaking of co-linearity and spin canting [36]. Besides above mentioned

parameters, the magnetic moment nB (µB) for all the samples was also calculated by

using the relation [37]:

nB (μB)= M×Ms / 5585 (3)

Where Ms is the saturation magnetization of the sample.

The value of magnetic moment goes on decreasing with the increase of Ga substitution

due to replacement of Ga3+ (2.02 µB) having smaller value of magnetic moment as

compared to that of Fe3+ (5µB ). The values of squareness ratio (Mr /Ms ) were also

calculated which lie in the range of 0.359-0.598 for all samples. It may be concluded that

magnetic properties are affected by substitution of Ga in strontium hexaferrites.

157
Fig. 4.3: (g) M-H loops of SrZn2GaxFe16-xO27 (x=0, 0.1, 0.2, 0.3, 0.4) hexaferrite
powders.

Table 4.3: (b): The values of saturation magnetization (Ms), remanence (Mr),
squareness ratio (Mr /Ms), magnetic moment (nB) and
coercivity (Hc) of all SrZn2GaxFe16-xO27 hexaferrite samples.

X Ms (emu/g) Mr (emu/g) Mr / M s nB (µB ) Hc (Oe)

0 51.04 18.34 0.359 14.699 183.27
0.1 47.64 20.09 0.422 13.137 330.45
0.2 44.20 20.52 0.464 12.199 439.8
0.3 40.90 21.27 0.520 11.299 613.4
0.4 35.77 21.4 0.598 9.89 966.72

158
4.3.4 Permittivity Spectra

Fig. 4.3 (h) shows the variation with frequency of the real (έ) and imaginary (ε ‫)״‬

part of the permittivity of the sample in the range 0.5-13 GHz. The real (έ) part of the

permittivity decreases with the increase of frequency. It is a typical dielectric behavior

of the ferrite, simulated by heterogeneous medium of conducting grains separated by thin

layer of poorly conducting grain boundaries [38]. The imaginary part of the permittivity

remains almost constant with the increase of frequency and the small appearance of

resonance peak in imaginary part of permittivity can be explained in terms of the

matching of the hopping frequency with the externally applied field. The dielectric

behavior of ferrites is attributed to the hopping of electrons between Fe+3 to Fe2+ ions, the

probability of jumping from Fe3+ to Fe2+ ion and vice versa being the same. Depending

upon this probability, the ions exchange position between two states at a frequency

called the natural frequency of jump for the two positions. If the frequency of applied

field is the same as the natural frequency, the maximum electrical energy is transferred to

the oscillating ions and power loss shoots up resulting in a resonance [39]. Interfacial and

dipole polarization are responsible for dielectric behavior of polycrystalline ferrites. The

fact that Fe2+ is easily polarized, play an important role to enhance hopping between Fe2+

and Fe3+ ions and thus increasing the dipole polarization. Meanwhile present of Fe2+ ions

elevate the interfacial polarization. Thus there is a resultant increase in polarization [13].

159
Fig. 4.3 (h) Frequency dependence of έ (real) and ε ‫( ״‬imginary) of
SrZn2Ga0.2Fe15.8O27 hexaferrite powders.

4.3.5 Permeability Spectra

Fig. 4.3(i) describes the frequency dependence of the real (µ´) and imaginary (µ˝) parts of

the permeability of the sample in the range 0.5-13 GHz. The real part of the permeability

shows a decreasing trend with increasing frequency which describes the relaxation

phenomenon of domain magnetization rotation or domain wall dipole moment occurring

in the GHz region [38]. The imaginary part of the permeability spectra shows the

resonance peak at 1.8 GHz and this peak can be shifted to any frequency region by

appropriate pair of divalent and trivalent ions substitution in place of Fe3+ ions [40].

Ferromagnetic theory states that permeability spectra may be distributed in four parts,

low, intermediate, high and ultrahigh frequency. In high and ultra high frequency

spectrum (f> 106Hz), µ´ descends greatly [41].

160
 Fig. 4.3 (i) Frequency dependence of µ‫( ׳‬real) and µ‫( ״‬imaginary) of

4.3.6 Microwave Absorption

Fig 4.3 (j) shows reflection loss (RL) curve of one layer absorber with thickness of 3.4

mm of the Ga substituted ferrites. It was found that the peak value of RL for the sample is -

32 dB and frequency (with respect to -20dB) starts from 8.2 GHz and the bandwidth is

around 0.899 GHz [42].

Transmission line theory describes the reflection coefficient (dB) as a function of the

impedance expressed as follows;

Z in  Z 0
RL (dB )  20 log 10[ ]
Z in  Z 0
(4)

Where Z0=377 Ω, the characteristic impedance of free space and is given by

0
Z0  (5)
0

Zinis the input impedance at the air-absorber interface and is represented by

161
 r 2ft
Zin  Z 0 tanh[(  j ) r r ] (6)
r c

Where μr=‫׳‬-j‫״‬and εr=ε‫׳‬-jε‫״‬are the complex permeability and complex permittivity

respectively, for the absorber medium, f is the frequency, c is the velocity of light and t is

the thickness of samples. The conditions of impedance matching i.e. Zin = Z0 is fulfilled

at certain thickness called matching thickness (tm) and matching frequency (fm). The max

value of matching thickness (tm) determines the reflection loss and calculated using the

relation;

a c (7)
tm  
4 4 f r r
Where

λa = wavelength inside the absorber

f = incident frequency of free space

It is evident from equation 7 that the wave reflected at absorber–metal interface

satisfying quarter-wave thickness criteria [43]. The thickness is inversely proportional to

frequency, since the absorption is increased as the thickness reduced. This is based on

quarter wave principle. When an electromagnetic wave is incident on an absorber sample

baked by metal plate, it is partially reflected from air to absorber interface and partially

reflected from absorber to metal interface. These two reflected waves are out of phase by

180 0C and cancel each other at air-absorber interface for absorbers satisfying the

quarter-wave thickness criteria [40].

162
Fig. 4.3 (j) Reflection loss as a function of frequency for Sr Zn2Ga0.2Fe15.8O27
hexaferrite powder.

163
4.4 SrN dxZn2Fe16- xO27 (x= 0.0, 0.05, 0.1, 0.15, 2.0, 2.5) Hexagonal
Ferrites Series IV

4.4.1 Thermal Analysis

The DT/TGA curve of as-prepared powder with composition SrZn2NdXFe16-xO27 (x= 0.1)

is shown in the Fig. 4.4 (a). The curve exhibits two distinct weight loss steps

corresponding to exothermic and endothermic peak in the DTA curve. The graph shows

the weight losses at different peaks. The first weight loss (1%) in the temperature range

of about 100 0C corresponds to the removal of water from the as-prepared sample which is

accompanied by an endothermic peak at around 100 0C in the DTA curve. The strong

exothermic peak at about 300 0C is sharp and intense and shows conversion of metal

hydroxides into oxides with a subsequent weight loss of 5%. The second endothermic

peak appears at 500 0C which is attributed to the formation of mono ferrites (SrFe2O4)

[15] and showing a weight loss of about 3%. Finally an exothermic is also appearing at

720 0C and this peak is attributed to the decarboxylation of the mixture of carbon and

iron oxide [16]. It is obvious that there is no weight loss after 800 0C which indicates the

completion of formation of hexaferrite, thus 850 0C temperature is sufficient to obtain

the single phase hexaferrites prepared by the sol gel method which is known to cause

lowering the sintering temperature. The sintering temperature in the present study is

much lower as compared to other reports for similar structure [2].

164
 Fig. 4.4 (a) DT/TGA curves of as prepared SrNd0.1Zn2Fe15.9O27 hexaferrite powder

4.4.2 Structural Analysis

Fig.4.4 (b) shows the crystal structure of W-type hexagonal ferrites which matches the

JCPS 78-0135. The lattice parameters and volume are shown in table and are also

calculated by standard formulae [25]. It is shown from the table that lattice constant (a &

c), c/a ratio and cell volume (Vcell) increases with the increase of Nd3+ content. The

increase of these parameters are because of larger ionic radius of Nd3+ (1.12Å) than that

of Fe (0.67Å) and the interaction between rare earth and neighboring ions. So the

shifting of Fe3+ ions at octahedral sites to tetrahedral sites that increases the lattice

parameters [28]. The increase of lattice parameters is also due to strong binding energy

of rare earth ions at octahedral sites [44] and the c/a ratio varies from 5.67 Ǻ to 5.714 Ǻ

that lies in the range of W -type hexagonal ferrites [45].

165
 1021,2018
2111,306
1010
1011
1012
201

2110
207
109

220
x=0.25

x=0.2
Intensity (a.u)

x=0.15

x=0.1

x=0.05
106

x=0.0

20 30 40 50 60 70 80
2 (degree)

Fig. 4.4 (b) X RD patterns of SrNdxZn2Fe16- xO27hexagonal ferrites.

166
Table 4.4 (a): Lattice constants „a‟, „c‟, c /a ratio, cell volume of
SrN dxZn2Fe16- xO27.

X a (Å) c (Å) c/a (Å) V (Å) 3

0.00 5.865 33.261 5.671 990.8074

0.05 5.871 33.482 5.703 999.4324

0.10 5.869 33.363 5.685 995.2019

0.15 5.873 33.491 5.703 1000.382

0.20 5.872 33.512 5.707 1000.669

0.25 5.878 33.589 5.714 1005.019

4.4.3 SEM Analysis

Fig.4.4 (c) shows the SEM patterns that measured the grain size. It is observed

that the grain size is increased with the increase of concentration. The crystallite size

is larger in undoped sample and is agglomerated. These results are agree with

lattice parameters that increase with the increase of Nd 3+ content, which leads to

the crystal deformation and inner stress [46].

167
Fig. 4.4 (c) SEM images of SrN dxZn2Fe16- xO27 hexagonal ferrites.

168
4.4.4 Magnetic Analysis

The M–H loops for all the Nd-substituted samples have been shown in Fig. 4.4 (d). It can

be seen from the results that coercivity (H c) was found to be a few hundred Oersteds

for all the compositions which reveal that the investigated ferrites have soft character.

The variation of coercive field (Hc) with increasing Nd-concentration has been given in

Table 4.4 (b). The results show that the values of Hc for Nd-substituted samples are

higher than that for unsubstituted sample. This behavior may be due to the

enhancement of the magneto-crystalline anisotropy with anisotropic Fe 2+ ions locating

on 2a sites as usually found in rare earth ions substitution [47]. Also this is attributed to

the fact that rare earth substitution inhibits the grain growth [48] in hexagonal ferrites.

Moreover the rare earth substitution promotes the ferritization reaction and also

improves the mechanical materials hardness [49]. The experiments carried out by Dung

et al. [50] showed that this substitution improves the hard magnetic properties of

hexaferrite.

The values of saturation magnetization (M s) for all the samples were also obtained

from the M -H loops and are listed in Table 4.4 (b). It was found that Ms value for

unsubstituted sample was smaller as compared to the values for Nd-substituted samples.

Furthermore, it has been observed that the substitution of Nd3+ ions for Fe3+ ions causes

the higher values of magnetization in these ferrites. This is because of the fact that Nd

has a higher value of magnetic moment (7μ B) as compared to that for Fe (5μ B). The

relationship between the permeability and saturation magnetization can be represented

by the following equation [51];

(4M s ) 2
i  1 
(4M s ) H a  ( f / 2.8) 2  j (4M s )( f / 2.8) (1)

169
where f is the frequency, Ms is the saturation magnetization and Ha is the magnetic

anisotropy field. From the above equation, it is obvious that permeability increases with

the increase of Ms and the decrease of Ha. Due to the high Ms, low Hc and larger sized

grains; these materials can be used to improve the permeability and absorption. It is also

known that the enhanced absorption bandwidth and the minimum reflection losses can be

achieved by higher permeability of ferrites. Therefore, excellent electromagnetic

properties can be achievable by microwave absorbing materials filled with the

investigated ferrites to consider as potential candidates for microwave absorbing

purposes.

170
 Fig. 4.4 (d) M H loops of SrNdxZn2Fe16- xO27 hexagonal ferrites.

Table 4.4(b): The values of saturation magnetization (Ms) and coercivity (Hc) of all
SrNdxZn2Fe16- xO27 hexaferrite samples.:

Sample (x) M s (emu/g) H c (Oe)

0.00 54.95 336

0.05 63.20 434

0.10 64.95 575

0.15 66.70 891

0.20 57.70 481

0.25 62.70 668

171
4.4.5 High Frequency Dependent Dielectric Properties

4.4.5.1 Dielectric Constant (ɛ´)

The variation of dielectric constant (ɛ‫ )׳‬versus applied field high frequency in the range 1

MHz -3 GHz. The value of dielectric constant (ɛ‫ )׳‬is higher at the lower frequencies

compared with the higher frequencies. The large values of dielectric constant (ɛ‫ )׳‬at

lower frequency may be may be due to Fe2+ ions, oxygen vacancies, grain boundary

defects, interfacial dislocation pile ups and voids [52, 53]. The dielectric constant

reduced sharply in low frequency range compared with the high frequencies region and

became almost constant at further higher frequencies range. The decrease in the

dielectric constant with the increase of applied field frequency is a normal ferromagnetic

behavior for ferrites. The charge carriers in a dielectric lined up in a finite time parallel to

an alternating applied electric field. When the frequency of the applied ac field increased,

then at certain point space charge carriers could not follow the applied field and the

charge carriers lagged behind the applied field [54]. Hence, the dielectric constant of a

material decreased. According to the Maxwell and Wagner two-layer model [52, 55] the

space charge polarization is because of the inhomogeneous dielectric structure of the

material. The structure was formed by well-conducting grains separated by thin less-

conducting intermediate grain boundaries [56]

172
Fig. 4.4 (e-i) Real part of dielectric constant (έ) of SrNd x Zn 2 Fe 1 6 -
x O 2 7 hexaferrite.

4.4.5.2 Dielectric Loss Tangent (tan δ)

The variation in dielectric loss tangent (tan δ) vs. applied field frequency in the range

1MHz -3 GHz. The value of dielectric tangent loss (tan δ) is smaller at lower frequencies

range compared with the higher frequencies range. The dielectric tangent loss (tan δ)

increased with the increasing of applied field frequency. The phenomenon of dielectric

dispersion in ferrites is based upon Maxwell-Wagner model [52, 53] and Koop‟s

phenomenological theory [57]. Dielectric loss in ferrites can be attributed to two

phenomena‟s such as hopping of electrons and charged defect dipoles [58]. When the

polarization lagged behind the applied ac field, then the dielectric loss occurred that may

be due to the impurities and imperfections in the crystal lattice structure [59]. The

resonance peaks in the patterns of dielectric tangent loss (tan δ) are shown in Fig. 4.4 (e-

ii). The peaks appeared when the jumping frequency of electrons between Fe2+ and Fe3+

is equal to the frequency of applied ac field [60]. The appearance of resonance peaks can

be elaborated by an analogy: if an ion has two equilibrium states Y and Z with same

potential energies separated by a potential barrier. The jumping probability of an ion is

173
same from Y to Z and from Z to Y. The frequency at which an ion changed its position

between the equilibrium states Y and Z is called the natural frequency of jump between

these two states. When the frequency of external applied ac field became equal to the

natural frequency of ions, then maximum electrical energy transferred to the oscillating

ions and the power loss highly increased and as a result the phenomenon of resonance

occurred. As a result, the resonance peaks appeared [61].

Fig. 74: (e-ii) Dielectric loss tangent (tan δ) as a function of frequency for
SrNdxZn2Fe16-xO27 hexaferrites.

174
4.4.5.3 Dielectric Dissipation Factor (ɛʺ)

Fig.4.4 (e-iii) shows the variation of dielectric dissipation factor (ɛʺ) vs. applied field

frequency. The dissipation factor directly depends upon the dielectric tangent loss (tanδ).

The dissipation factor shows the magnitude of energy dissipated in a dielectric material

for the applied oscillating electric field and the dielectric loss increased with the

increasing of applied field frequency as shown in Fig. 4.4 (e-ii). The internal friction

resisted the movement of each dipole, which produced heating in the material and power

loss occurred. The power loss in dielectric materials occurred due to work done to

overcome the frictional damping forces acting upon the dipoles during their rotation.

Hence, the materials with high resistivity (low conductivity) exhibited low dielectric

losses and vice versa [62]. The electromagnetic materials with excellent absorbing ability

should have high dielectric loss (ε") at microwave frequency. The dielectric loss (ε") is

characterized for the microwave energy loss in the materials. Actually, the loss is the

conversion of electromagnetic wave energy into heat. The microwave absorbing

materials are coated on the metallic structures for reducing the scattering. The material

should absorb maximum amount of electromagnetic waves at microwave frequency.

Therefore, the electromagnetic materials with excellent absorbing ability should have

high dielectric loss at microwave frequency. The materials may be useful for the

absorption of microwave radiations and attenuations of electromagnetic interference due

to high values of dissipation factor [63].

175
 X=0.0 X=0.0
0.8
X=0.15
X=0.2
0.6 X=0.25

Dielectric Loss Factor ('')

X=0.15
0.4

X=0.2
0.2

0.0 X=0.0

-0.2

0.0 500.0M 1.0G 1.5G 2.0G 2.5G 3.0G

Ferequency (GHz)

Fig. 84 (e-iii) Dielectric dissipation factor (ε") of SrNdxZn2Fe16-xO27 hexaferrite.

176
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180
CONCLUSION

In this work four series namely,BaHoxZn2Fe16-xO27 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0),Ba1-

xHoxCo2Fe16O27(x= 0.0, 0.02, 0.04, 0.06, 0.08, 0.1), SrGaxZn2Fe16-xO27 (x=0.0, 0.1, 0.2, 0.3, 0.4),

SrNdxZn2Fe16-xO27 (x=0.0, 0.05, 0.1, 0.15, 0.2, 0.25) hexagonal ferrites were prepared and found

single phase hexagonal structure.

The co precipitation method is found suitable for homogenous single phase nano particle of Ho

doped hexa ferrites. The lattice constant „a‟ and „c‟ increases with the increase of Ho

concentration due to large ionic radius of Ho. Coercivity follows Hc α 1 / r behavior. dc

electrical resistivity increases due to large density of grain boundaries that hinder the Verwey

mechanism. The present samples are useful at high frequency applications due to enhanced

resisitivity and coercivity. The last two sample (x = 0.8 and 1.0) have highest resistivity which

are the best samples in the present studies.

Single phase nanomaterials of the composition Ba1-xHoxCo2Fe16O27 were successfully

synthesized by sol-gel auto-combustion method. The substitution of Ho3+ for Ba2+ shows an

improvement in the formation of W-type phase sintered at 950 0C. The study of IR spectra of

sintered powder shows two absorption bands at 430cm-1 and 582cm-1 which are well-known

bands for hexaferrites. The grain size decreases with Ho-concentration from 44 to 34 nm that is

less than 50 nm and this range is suitable to obtain high signal-to-noise ratio in high density

recording media. The result shows that electrical resistivity decreases with the increase of

temperature according to the Verwey‟s hopping mechanism. The room temperature resistivity

values for substituted samples are higher as compared to unsubstantiated one due to conversion

of Fe3+ ions to Fe2+. The substitution of Ho3+ atom decreases the dielectric constant (real and

181
imaginary part of complex permittivity) and loss tangent, confirms that these nano ferrites are

suitable for high frequency application such as microwave absorber or microwave devices.

The effects of substitution of Ga3+ ions in W-type ferrites prepared by sol-gel method have been

investigated. The XRD data confirms that all samples have single W-type phase and particle size

is measured by SEM analysis that confirms the nano size. The increase the value of coercivity Hc

till 900 Oe suggests that the synthesized samples are better to use for longitudinal recording

media. The real (έ) part of the permittivity decreases with the increase of frequency. It is a

typical dielectric behavior of the ferrite, simulated by heterogeneous medium of conducting

grains separated by thin layer of poorly conducting grain boundaries .The imaginary part () of

the permittivity remains almost constant with the increase of frequency and the small appearance

of resonance peak in imaginary part of permittivity can be explained in terms of the matching of

the hopping frequency with the externally applied field. The microwave absorption property is

enhanced in the frequency (with respect to -20dB) begins from 0.5-13 GHz, and the bandwidth

reaches 0.899 GHz. The peak value is -32dB at the matching thickness of 3.4mm.

The effects of rare earth substitution Nd3+ ions in W-type ferrites prepared by sol-gel method

have been investigated. The XRD data confirms that all samples have single W-type phase. The

M-H loop confirms the ferrites have soft character and increase of saturation magnetization and

coercivity suggests that material can be used for application in high density recording media.

Dielectric measurements are taken in the range of 1MHz-3GHz and the behavior of the material

is showing the normal ferromagnetic ferrites. This makes the ferrites useful for absorption of

microwave radiation and attenuation of electromagnetic interference due to high value of

dissipation factor.

182
FUTURE RECOMMENDATIONS

In this study some aspects have been needed for further investigation.

 The MH loops may also be carried out from helium temperature to 6000C in order to find

out the curie temperature of the material.

 The microwave absorption studies of the remaining samples can be carried out at high

frequency (up to 0.5 to 20 GHz) using vector network analyzer.

 Temperature dependent Dielectric properties can also be measured.

 Thermoelectric power measurement can be studied to know mobility of the charge

carriers.

 TEM measurements can also be used for particle size measurements.

183
List of Publications

1. Faiza Aen,Mukhtar Ahmad,M.U.Rana, J.Current Applied Physics,13 (2013) 41-46.

2. FaizaAen, ShahidaB.Niazi, M.U.Islam, Mukhtar Ahmad, M.U.Rana. J.Ceramics

International 37 (2011) 1725-1729.

184