MICROSTRUCTURAL AND MAGNETIC PROPERTIES OF YTTRIUM …

MICROSTRUCTURAL AND MAGNETIC PROPERTIES OF YTTRIUM

IRON GARNET DERIVED FROM STEEL WASTE PRODUCT

NURAINE MARIANA BINTI MOHD SHAHRANI

ITMA 2016 25

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By


Thesis submitted to the School of Graduate Studies,

Universiti Putra Malaysia, in Fulfillment of the

Requirement for the Degree of Master of Science

December 2016

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Commercial use of material may only be made with the express, prior, written

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Abstract of thesis presented to the Senate of Universiti Putra Malaysia in

fulfillment of the requirement for the Degree of Master of Science



By


December 2016

Chairman: Raba’ah Syahidah Azis, PhD

Institute: Institute of Advanced Technology

In this research work, the morphology and magnetic properties-evolutions in Yttrium Iron Garnet (YIG) were studied in details, focusing on parallel evolving

relationship with their dependences on sintering temperature. The iron oxide that

has been used to synthesize YIG was obtained from the steel waste product, mill

scale. There is less study and no reports published regarding the evolution of

microstructure and magnetic properties YIG from low sintering temperature to

high sintering temperature by mill scale waste product. The raw mill scale went

through the milling and purification process by magnetic and non-magnetic

separation and curie temperature separation technique to produce high purity iron

oxide powder as main raw material in preparing YIG and fabricate YIG by high

energy ball milling process. The obtain iron oxide was characterized by X-ray

Diffractometer (XRD), X-ray fluorescence (XRF), X-ray photoelectron

spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy for mineralogical composition and chemical analysis. The results of

XRD indicated that the synthesized iron oxide identified as a α-Fe2O3 (hematite).

Moreover, XRF, XPS, FTIR and Raman data was found to correspond with pure

hematite.

Among the characterization procedures, the highlight properties were phase

identification by XRD, microstructure by FESEM, magnetic permeability by

impedance material analyzer and saturation magnetization by VSM. The XRD

pattern of YIG showed an improvement of crystallinity with increasing sintering

temperature. Full YIG phase was seen for samples sintered at 1100oC and upwards. The temperature obtain of YIG fabricate is comparable with high energy milling

method by commercial iron oxide raw material. FESEM micrographs showed

larger grains as the sintering temperature increased, and the amounts of porosity

were decreased, as the some grains grew at the expense of others. The initial

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permeability, showed the highest value of 51.70o at 1400oC, and decrement

values of initial permeability at 700oC to 800oC because of the presence of weak

ferromagnetic phases. The results of VSM showed an increasing tendency of

saturation magnetization, with increased grain sizes, and the decrement value

for samples sintering at 700oC to 800oC. These results can be associated with the

formation of weak ferromagnetic behavior of α-Fe2O3 and YFeO3 phases. A

particular pattern of the magnetic properties with sintering temperature is a

manifestation of the phase purity level and microstructural factors. Thus, three

groups of ferromagnetic behavior of YIG can be classified based on those factors.

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Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai

memenuhi keperluan untuk Ijazah Master Sains

MIKROSTRUKTUR DAN SIFAT-SIFAT MAGNET DALAM YTTRIUM

IRON GARNET YANG DIPEROLEHI DARIPADA BAHAN BUANGAN

BESI

Oleh


Disember 2016

Pengerusi: Raba’ah Syahidah Azis, PhD

Institut: Teknologi Maju

Dalam kerja-kerja penyelidikan ini, morfologi dan sifat-sifat magnet-evolusi dalam

Yttrium Iron Garnet (YIG) telah dikaji secara terperinci, memberi tumpuan kepada

hubungan perkembangan selari mereka dengan suhu pensinteran. Oksida besi yang

telah digunakan untuk mensintesis YIG diperoleh daripada bahan buangan keluli,

di kilang. Terdapat kurang kajian dan tiada laporan bercetak mengenai evolusi

mikrostruktur dan sifat-sifat magnet YIG dari suhu pensinteran rendah kepada suhu pembakaran tinggi oleh bahan buangan besi dari kilang. Sisik besi mentah telah

melalui proses pengilangan dan pemurnian oleh pemisahan magnet dan bukan

magnet dan teknik pemisahan suhu curie untuk menghasilkan serbuk oksida besi

berketulenan tinggi sebagai bahan mentah utama dalam penyediaan YIG dan

pembuatan YIG oleh proses pengilangan bola tenaga tinggi. Penghasilan oksida

besi telah dicirikan oleh pembelauan sinar-X (XRD), pendarfluor sinar-X (XRF),

spektroskopi fotoelektron sinar-X (XPS), spektroskopi inframerah transform

Fourier (FTIR) dan spektroskopi Raman untuk komposisi mineralogi dan analisis

kimia. Keputusan XRD menunjukkan bahawa oksida besi yang disintesis dikenal

pasti sebagai α-Fe2O3 (bijih besi). Selain itu, data XRF, XPS, FTIR dan Raman

telah didapati sepadan dengan bijih besi tulen.

Di antara prosedur pencirian, sifat-sifat yang diketengahkan adalah pengenalan

fasa oleh XRD, mikrostruktur oleh FESEM, kebolehtelapan magnet oleh

penganalisa bahan galangan dan pemagnetan tepu oleh VSM. Pola XRD daripada

YIG menunjukkan peningkatan penghabluran dengan peningkatan suhu

pensinteran. Fasa YIG penuh dapat dilihat pada sampel sinter pada 1100oC dan ke

atas. Suhu ini adalah setanding dengan kaedah pengilangan bola tenaga tinggi

daripada bahan mentah oksida besi yang komersial. Mikrograf FESEM

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menunjukkan bijirin lebih besar kerana suhu pembakaran meningkat, dan jumlah

keliangan telah menurun disebabkan oleh beberapa bijirin berkembang sesama

sendiri. Kebolehtelapan awal, menunjukkan nilai tertinggi 51.70o pada suhu

1400oC, dan kebolehtelapan awal susut pada 700

oC dan 800

oC kerana kehadiran

fasa lemah feromagnet. Keputusan VSM menunjukkan pemagnetan tepu, yang

semakin meningkat dengan saiz bijirin meningkat, dan nilai susut pada sampel

pensinteran 700oC dan 800oC. Kesusutan pada suhu ini boleh dikaitkan dengan

pembentukan tingkah laku fasa lemah feromagnet α-Fe2O3 dan YFeO3. Corak

tertentu sifat-sifat magnet dengan pensinteran suhu adalah manifestasi daripada

kesucian tahap fasa dan faktor-faktor mikrostruktur. Maka, tiga kumpulan tingkah laku feromagnet daripada YIG boleh dikelaskan berdasarkan faktor-faktor tersebut.

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ACKNOWLEDGEMENT

First praise is to Allah, the Almighty, on whom ultimately we depend for

sustenance and guidance. With His blessings, help and will, we are able to make

this work a success.

My sincere appreciation and gratitude goes to my supervisor, Dr. Raba’ah

Syahidah Azis for her continuous guidance, advice and support. With her timely

and efficient contribution helped me shape this into its final form and I express my sincerest appreciation for her assistance in any way that I may have asked. I would

also like to extend my appreciation to my supervisory committee member, Assoc.

Prof. Dr. Zulkifly Abbas and Dr. Ismayadi Ismail for their helps throughout this

project.

I gratefully acknowledge the staff of Material Synthesis and Characterization

Laboratory (MSCL), Institute of Advanced Technology, and Faculty of Science for

allowing me to utilize their lab facilities. I would also like to thank Universiti Putra

Malaysia for the financial support by Geran Putra-IPS and Graduate Research

Fellowship Scheme.

A lot of thanks to my colleagues in the Magnetic and Nanostructure Evolution

Group (MNEG), sis Idza Riati Ibrahim, sis Rodziah Nazlan, sis Fadzidah Mohd

Idris, sis Nor Hapishah Abdullah, and sis Wan Norailiana Wan Abdul Rahman for

their concerns, moral support and encouragement. I also appreciate them for the

discussion, ideas and time spent throughout this research. To my fellow friends

during my postgraduate study, Azelah Khairudin and Adilah Zakaria, I would like

to say thanks for everything. Finally, I am forever indebted to my family; parents,

my younger brothers and sisters for their sacrifice, patience, love, understanding,

support and their prayers during these years that I have spent in pursuit of my

master’s degree.

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This thesis was submitted to the Senate of Universiti Putra Malaysia and has been

accepted as fulfillment of the requirement for the degree of Master of Science. The

members of the Supervisory Committee were as follows:

Rabaah Syahidah binti Azis, PhD

Senior Lecturer

Faculty of Science

Universiti Putra Malaysia

(Chairman)

Zulkifly bin Abbas, PhD

Associate Professor

Faculty of Science


(Member)

Ismayadi bin Ismail, PhD

Fellow Researcher

Institute of Advanced Technology


(Member)

ROBIAH BINTI YUNUS, PhD

Professor and Dean

School of Graduate Studies


Date:

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Declaration by graduate student

I hereby confirm that:

this thesis is my original work;

quotations, illustrations and citations have been duly referenced;

this thesis has not been submitted previously or concurrently for any other

degree at any other institutions;

intellectual property from the thesis and copyright of thesis are fully-

owned by Universiti Putra Malaysia, as according to the Universiti Putra

Malaysia (Research) Rules 2012;

written permission must be obtained from supervisor and the office of Deputy Vice-Chancellor (Research and Innovation) before thesis is

published (in the form of written, printed or in electronic form) including

books, journals, modules, proceedings, popular writings, seminar papers,

manuscripts, posters, reports, lecture notes, learning modules or any other

materials as stated in the Universiti Putra Malaysia (Research) Rules

2012;

there is no plagiarism or data falsification/fabrication in the thesis, and

scholarly integrity is upheld as according to the Universiti Putra Malaysia

(Graduate Studies) Rules 2003 (Revision 2012-2013) and the Universiti

Putra Malaysia (Research) Rules 2012. The thesis has undergone

plagiarism detection software.

Signature: _______________________ Date: __________________

Name and Matric No.: _________________________________________

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Declaration by Members of Supervisory Committee

This is to confirm that:

the research conducted and the writing of this thesis was under our supervision;

supervision responsibilities as stated in the Universiti Putra

Malaysia (Graduate Studies) Rules 2003 (Revision 2012-

2013) are adhered to:

Signature: _________________ Name of

Chairman of Supervisory

Committee: ________________

Signature: _________________

Name of

Member of Supervisory

Committee: ________________

Signature: _________________

Name of

Member of Supervisory

Committee: ________________

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TABLE OF CONTENTS

Page

ABSTRACT Ii i

ABSTRAK iii

ACKNOWLEDGEMENTS v

APPROVAL vi

DECLARATION viii

LIST OF TABLES xiii

LIST OF FIGURES xiv

LIST OF SYMBOLS AND ABBREVIATIONS xvii

CHAPTER

1 INTRODUCTION 1

1.1 Background of study 1

1.2 Magnetic ceramics 2

1.3 Introduction of Garnets 2

1.4 Mill scale as a potential of raw materials 2

1.5 Aim of study 4

1.6 Objectives 4

2 LITERATURE REVIEW 5 2.1 Introduction 5

2.2 Processing technique of Iron oxide using mill scale waste

product

5

2.3 Processing of YIG 6

2.3.1 Mixed oxides method 6

2.3.2 Coprecipitation 7

2.3.3 Sol-gel synthesis 8

2.3.4 Mechanical milling 9

2.4 Magnetic and electrical properties of garnet 10

2.4.1 Oxygen stoichiometry 11

2.5 Microwave properties of garnet 12

2.6 Microstructural dependence on magnetic properties of garnet

14

2.6.1 Effect of grain size on permeability 14

2.6.2 Effect of porosity on permeability 15

2.6.3 Effect of grain size and porosity on M-H

parameters

15

2.6.4 Imperfections 16

2.7 Microstructural dependence on microwave properties 16

3 THEORY 17

3.1 Introduction 17

3.2 Origin of magnetism 17 3.2.1 Ferrimagnetism 17

3.3 Superexchange interaction of YIG 19

3.4 Magnetic properties of ferromagnetic materials 21

3.4.1 Magnetic domains and Bloch walls 21

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3.4.1.1 Magnetostatic energy 23

3.4.1.2 Magnetocrystalline energy 23

3.4.1.3 Magnetostrictive energy 23

3.4.1.4 Domain wall energy 24

3.4.2 Saturation magnetization 24

3.4.3 Curie temperature 25

3.4.4 Magnetic anisotropy 26

3.4.5 M-H hysteresis curve 27

3.4.6 Magnetic losses 29

3.4.7 Resistivity 30

3.4.8 Permeability 31 3.5 Magnetic properties of garnets 33

3.6 Significance of high temperature 33

3.7 High energy ball milling method 34

3.7.1 Mechanism of high energy ball milling 35

3.8 Influence of temperature on microstructure and magnetic

properties

35

4 METHODOLOGY 37

4.1 Introduction 37

4.2 Preparation of hematite, Fe2O3 37

4.2.1 Selecting raw materials 39 4.2.2 Weighing and blending 39

4.2.3 Separation techniques 39

4.2.3.1 Magnetic and non-magnetic (MNM) 40

4.2.3.2 Curie temperature separation (CTS) 40

4.2.4 Fe2O3 production 41

4.3 Preparation of YIG 41

4.3.1 Powder preparation 42

4.3.2 Compact formation 43

4.3.3 Sintering 43

4.4 Sample measurement and characterization 44

4.4.1 Particle size analysis 45

4.4.2 Phase analysis 45 4.4.3 Microstructure analysis 45

4.4.4 Density measurement 46

4.4.5 Measurement of magnetization 46

4.4.6 Measurement of complex permeability 47

4.4.7 Measurement of curie temperature 47

4.4.8 Measurement of electrical resistivity 48

4.4.9 Structural analysis by FTIR spectroscopy 49

4.4.10 Structural analysis by Raman spectroscopy 49

4.4.11 Elemental composition by XRF spectroscopy 50

4.4.12 Elemental composition by XPS 50

4.4.13 Linewidth 50 4.5 Flowchart of characterization of YIG by mill scale 51

5 RESULTS AND DISCUSSION 53

5.1 Introduction 53

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5.2 Hematite characterization 53

5.2.1 Phase analysis 53

5.2.2 Elemental composition by XRF 55

5.2.3 Structural analysis by FTIR 56

5.2.4 Structural analysis by Raman 57

5.2.5 Elemental composition by XPS 59

5.3 YIG Characterization 62

5.3.1 Phase analysis 62

5.3.2 Structural analysis by FTIR 68

5.3.3 Structural analysis by Raman 69

5.3.4 Microstructural related analysis 70 5.3.4.1 Particle size 70

5.3.4.2 Morphology, grain size and porosity 71

5.3.5 Magnetic properties 78

5.3.5.1 Saturation magnetization and coercivity 78

5.3.5.2 Complex permeability 84

5.3.5.3 Curie temperature 84

5.3.6 Electrical resistivity 89

5.3.7 Linewidth 91

5.4 Summary 92

6 CONCLUSION AND SUGGESTIONS 95 6.1 Conclusion 95

6.2 Summary 96

6.3 Recommendations for further studies 98

REFERENCES 99

APPENDICES 104

BIODATA OF STUDENT 108

LIST OF PUBLICATIONS 109

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LIST OF TABLES

Table Page

3.1 Classes of magnetic ceramics. 19

3.2 The angle of yttrium-oxygen-iron and iron-oxygen-iron

linkages in YIG.

20

4.1 General properties of hematite, magnetite and wustite. 41

5.1 Parameters composition, chemical formula, crystal system,

space group, density x-ray (Dx), lattice parameters for (a)

mill scales, (b) after CTS and (c) after oxidation process.

55

5.2 Elemental composition of raw mill scale. 56

5.3 Elemental composition of hematite. 56

5.4 Raman wavenumbers and assignments of hematite compared

with values reported in the literature.

58

5.5 Binding energies in eV of major core lines in iron oxide,

hematite.

62

5.6 XRD details of the intense peaks before sintering (after 9

hours milling) and at sintering temperature 500oC to 1400oC.

65

5.7 Volume fraction of phases at sintering temperature 500oC to

1400oC.

66

5.8 Average grain sizes at sintering temperature 500oC to

1400oC.

72

5.9 Density, relative density and porosity at sintering

temperature 500oC to 1400oC.

78

5.10 Saturation magnetization at sintering temperature 500oC to

1400oC.

81

5.11 Initial permeability at sintering temperature 500oC to

1400oC.

88

5.12 Curie temperature at sintering temperature 500oC to 1400oC. 89 5.13 Resistivity at sintering temperature 500oC to 1400oC. 90

5.14 Linewidth at sintering temperature 500oC to 1400oC

measured at the frequency of 4-8 GHz.

91

5.15 Relationship of sintering temperature with volume fraction

of phases, bulk density db, porosity P, grain sizes D,

saturation magnetization Ms, coercivity Hc, initial

permeability µi, Curie temperature Tc, resistivity and

linewidth ΔH.

94

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LIST OF FIGURES

Figure Page

2.1 Phase diagram of the system Fe2O3-Y2O3 in air. 12

2.2 Linewidth, and dielectric loss tangent, tan measured

at 10 GHz as a function of initial iron defect for a material having the formula Y3Fe5(1-ε)O12.

13

2.3 Linewidth, ΔH versus temperature for two YIG’s which

have the following densities: (1) d1 = 5.151 g/cm3, (2) d2 =

5.128 g/cm3.

14

3.1 Schematic comparing dipole allignments in ferromagnetic,

antiferromagnetic and ferrimagnetic materials in A and B

sites.

18

3.2 The coordination of Y3+ ion in 24(c), Fe3+ ion in 16(a) and

Fe3+

ion in 24(d) with oxygen ion in YIG.

20

3.3 Schematic representation of the domains in a ferromagnetic; arrows represent atomic magnetic dipoles.

Within each domain, all dipoles are aligned, whereas the

direction of alignment varies from one domain to another.

22

3.4 Gradual change in direction of moments inside a domain

wall.

22

3.5 M-H curve. 25

3.6 The - behavior for a ferromagnetic material that was

initially unmagnetized. Domain configurations during

several

stages of magnetization are represented.

28

3.7 The - for a ferromagnetic material that is subjected to forward and reverse saturation.

29

3.8 Permeability spectrum of a YIG showing the frequency

course of the real and imaginary permeabilities.

32

3.9 Coercivity as a function of particle size. 36

4.1 Flowchart of Fe2O3 preparation from mill scale. 38

4.2 Separation set-up of MNM and CTS. 40

4.3 Flowchart of YIG preparation. 42

4.4 Illustration of a (a) pellet and (b) toroidal shape sample. 43

4.5 Density measurement set-up. 46

4.6 Air mill that used for making spherical shape sample. 47 4.7 Curie temperature measurement set-up. 48

4.8 Electrical resistivity measurement set-up. 49

4.9 Linewidth measurement set-up. 51

4.10 Flowchart of YIG bulk ferrite characterization. 52

5.1 XRD pattern of (a) mill scale, (b) mill scale after curie

separation technique (CTS) and (c) after oxidation process.

54

5.2 FTIR spectrum of hematite from mill scale. 57

5.3 Raman spectrum of hematite. 58

5.4 XPS response of full survey of iron oxide, hematite. 60

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5.5 Fe 2p3/2 and Fe 2p1/2 position of iron oxide, hematite. 60

5.6 Fe 3p and Fe 3s position of iron oxide, hematite. 61

5.7 The O 1s position of iron oxide, hematite. 62

5.8 XRD pattern of Fe2O3 + Y2O3 mixture milled at 9 hours and

sintered at different temperature (from 500oC to 1400oC)

for 9 hours.

64

5.9 Approximate comparison of percentage amorphous grain

boundary volumes in YIG with nanometer and micrometer

grain size.

67

5.10 FTIR spectra at sintering temperature 500oC to 1400oC. 69

5.11 Raman spectra at sintering temperature 500oC to 1400oC. 70 5.12(a) TEM image of the powder milled for 9 hours. 71

5.12(b) Particle size distribution of the powder milled for 9 hours. 71

5.13 FESEM micrograph at 500oC, 600oC, 700oC, 800oC, 900oC,

1000oC, 1100oC, 1200oC, 1300oC and 1400oC.

74

5.14 Grain size distribution at 500oC, 600oC, 700oC, 800oC,

900oC, 1000

oC, 1100

oC, 1200

oC, 1300

oC and 1400

oC.

76

5.15 Magnetization curve at sintering temperature 500oC to

1400oC.

79

5.15(a) Magnetization curve at sintering temperature 500oC to

800oC.

80

5.15(b) Magnetization curve at sintering temperature 900oC to

1400oC.

80

5.16(a) Saturation magnetization relationship with grain size as

increasing sintering temperature.

82

5.16(b) Coercivity relationship with grain sizes as increasing

sintering temperature.

83

5.17 Coercivity and morphology at sintering temperature 500oC

to 1400oC.

83

5.18 Real permeability at sintering temperature 500oC to

1400oC.

85

5.18(a) Real permeability at sintering temperature 500oC to 800oC. 85

5.18(b) Real permeability at sintering temperature 900oC to

1400oC.

86

5.19 Permeability loss factor at sintering temperature 500oC to

1400oC.

86

5.19(a) Permeability loss factor at sintering temperature 500oC to

800oC.

87

5.19(b) Permeability loss factor at sintering temperature 900oC to

1400oC.

87

5.20 Curie temperature at sintering temperature 500oC to

1400oC.

89

5.21 Resistivity at sintering temperature 500oC to 1400oC

Measured at room temperature.

90

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5.22 Linewidth at sintering temperature 500oC to 1400oC

measured at the frequency of 4-8 GHz.

92

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LIST OF SYMBOLS AND ABBREVIATIONS

Ni Nickel

Mn Manganese

Zn Zinc

Ba Barium

Sr Strontium Fe2O3 Iron (III) oxide; hematite

Y2O3 Yttrium oxide

Y3Fe5O12; YIG Yttrium iron garnet

Y Yttrium

FeO Iron (II) oxide

Fe3O4 Iron (II,III) oxide

Fe Iron

CTS Curie temperature separation

MNM Magnetic and non-magnetic separation

XRF X-ray fluorescence

XRD X-ray diffraction

Cu Copper Cr Chromium

YFeO3; YIP Orthoferrite

FMR Ferromagnetic resonance

ΔH Linewidth

Fe3+ Iron (III) ion; ferric ion

Fe2+ Iron (II) ion; ferrous ion

Hc Coercivity

Mr Remanence

M Magnetization

Tc Curie temperature

Ms Saturation magnetization H Applied field

Ρ Resistivity

HEBM High energy ball milling

FTIR Fourier transform Infrared spectroscopy

XPS X-ray photoelectron spectroscopy

µ’ permeability

µi Initial permeability

µ’’ Permeability loss factor

µB Bohr magneton

m Magnetic moment

Ca Calcium V Vanadium

Sn Tin

K Anisotropy

DC Direct current

AC Alternating current

VSM Vibrating sample magnetometer

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FESEM Field emission scanning electron

microscope

a-sublattice Octahedral sublattice

d-sublattice Tetrahedral sublattice

c-sublattice Dodecahedral sublattice

D Grain size

R Resistance

P Porosity

db Bulk density

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CHAPTER 1

INTRODUCTION

1.1 Background of study

Oxide ceramics which exhibit ferrimagnetic behavior play an important role in the

electronic industry. They are commonly known as ferrites. Ferrites are the mixed metal oxides containing iron oxide as their main component. There are three

important classes of commercial ferrites, and each of one having a specific crystal

structure. The first one is soft ferrites with cubic spinel structure, such as NiZn-

and MnZn ferrites. The second one is the soft ferrites with garnet structure, such as

the microwave ferrites, for example yttrium iron garnet, and the third one is hard

ferrites with the hexagonal structure such as Ba and Sr hexaferrites. The industrial

importance of ferrites becomes obvious when one examines the diversity of their

applications. Through the years, the demand of ferrites has steadily increased

together with the specific applications of ferrites, and have changed remarkably

and kept pace with the development in electronic technologies.

Ceramic technology has historically developed from an empirical method of

fabrication to one which is based more and more on the application of scientific

knowledge. It has become quite evident that the parameters determining the

suitability of materials for particular applications are chemical composition,

crystallographic structure and the so-called microstructure, which comprises such

important aspects as size of constituent crystallites (grains), their size distributions,

their boundaries (grain boundaries), their orientation (texture), and the voids

(pores) between them (Sun, 2007). To control and manipulate these parameters,

there must be a range of methods available for preparing ceramic powders. There

are three basic methods, which are mechanical, chemical, and vapor phase

methods.

Mechanical methods use coarse-grained materials which is often necessary to

eliminate aggregates and to reduce particle size. They are subjected to a series of

processes called as comminution. The steps involved crushing, grinding, and

milling. Mechanical methods of powder production are widely used in the industry

due to ability for high mass production of the product. Chemical methods such as

sol-gel processing offer several advantages over mechanical methods. This method

allows exceptional control over particle morphology and purity at lower

temperatures. Chemical processes are widely used in the production of advanced

ceramic materials such as fibers, coatings, etc. (Cheng et al., 2007). The other method is vapor-phase processes. Vapor-phase processes offer many advantages,

such as the ability to produce particles of non-oxides and nanoparticles, as they can

give high purity powders, discrete and non-aggregated particles, and nanoparticles

with narrow size distributions (Guo et al., 2005).

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In this chapter, the general information on ferrite magnetic garnets is introduced.

An introduction on raw steel waste (well-known as mill scale) and its potential in

producing iron oxide powder will be highlighted. In the thesis, we will discuss the

previous work on the synthesis compound within the Fe2O3-Y2O3 system by

mechanical alloying method and the statistical analysis data by this method.

Theories that are related with the results are also discussed. The materials used and

the procedure of the research will be compile followed with the results and

discussion. Based on the results, we will summarize and conclude the research

findings, in addition to some suggested recommendations for future work.

1.2 Magnetic ceramics

In recent years, ferrimagnetic garnet have attracted much attention as microwave

device materials, circulators, isolators, phase shifters, etc. due to its excellent

electromagnetic properties, including low dielectric loss, narrow ferromagnetic

resonance linewidth in microwave region and tailorable saturation magnetization

(Yu et al., 2011). Thus, research has been committed to the investigations of YIG

and doped-YIG by controlling the preparation conditions to tailor their

microstructure in addition to the design of chemical composition.

1.3 Introduction of Garnets

Generally, the chemical formula for garnet system is written as 3M2O3.5Fe2O3 or

M3Fe5O12. M represents yttrium (Y) or one of the rare earth ions. The rare earth

ions are large, so that they occupy the largest cation sites in the garnet structure,

which are dodecahedral sites. Note that in the magnetic garnet, the metal ions are

all trivalent. There are 24 dodecahedral, 16 octahedral, and 24 tetrahedral sites in a

unit cell containing 8 formula units. The prototype for ferrimagnetic iron garnet is

yttrium iron garnet (YIG). Garnets provide superior performance in microwave

devices because they have narrow resonance line width, one of the most important parameters from application point of view besides wide range of magnetization and

very low dielectric loss (Soleimani et al., 2012).

1.4 Mill scale as a potential of raw materials

The processes of manufacturing steel product from industry produce two times

more waste materials than the final product obtained. These results in the

formation of large amounts of waste materials in the form of slags, scale and dusts

(Martin et al., 2012). Currently, most of the waste is utilized in the same steelworks and passed to external customers or it is reused as a feeds for other technological

processes. In the case of Malaysia’s steel Industry, Malaysia’s consumption on

steel is expected to trend up along with on-going construction and mass transit

projects. The demand of steel is expected to rise up by 12.6% year-of-year (Export-

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Import Bank of Malaysia, 2015). In 2013, 11.69% million tons of steels are

produced and increased to 12.5% million tons in 2014 (“World Steel Association,”

2014). This trend is expected to increase up in year 2020. The steel industry in

Malaysia can be categorically subdivided into two main segments, namely long

products and flat products. Long products include billets, bars, wire rods, sections,

nails, wire mesh, nuts, bolts, etc. which are predominantly used in the construction

industry. Flat products are the products consumed mostly by the manufacturing,

construction and oil & gas sectors like hot-rolled plates and sheets, cold-rolled

coils, tubes, pipes, boiler and pressure vessels, etc. Irrespective of the products,

during processing of steel to yield long or flat product, mill scale is generated and

considered as a waste (Bagatini et al., 2011).

Mill scale is flaky that can be found on metals that have been rolled. Mill scale

forms an exterior surface of sheets and plates as they are being manufactured

through rolling steel billets and hot iron into rolling mills. Mill scale which

represents 2% of steel produced contains iron in elemental form and three types of

iron oxides: wustite (FeO), hematite (α-Fe2O3) and magnetite (Fe3O4) (Legodi and

de Waal, 2007). The chemical composition of mill scale depends on the type of

steel produced and the process used. The iron content in the mill scale is normally

around 72% Fe with small amounts of non-ferrous metals. Mill scale is

contaminated with remains of lubricants and other oils and greases from the equipment associated with rolling operations (Martin et al., 2012). The oil content

usually ranges between 0.1 % and 2.0%, and can reach up to 10.0%. In steelworks

plants, almost 85% of the mill scale generated is recycled within the steelmaking

industry and small amounts are used for ferroalloys, in cement plants and in the

petrochemicals industry. The balance part of the mill scale with particle size less

than 0.5 mm (finer mill scale or mill scale sludge), which is more heavily

contaminated with oils, ends up in landfills. Mill scale sludge cannot be recycled

via sintering since its fine particles contains a high oil level which is 5.0-20.0% and

is normally treated as a landfill waste. Mill scale with oil content more than 3.0%

is recycled after extracting the oil in a pre-treatment stage. Mill scale with oil

content less than 1.0% with the particle size between 0.5-5.0 mm can be returned

without any pre-treatment (Legodi and de Waal, 2007). Thus, the allowable limit for oil content in the mill scale is less than 1% for all usage.

Although most of the mill scales are consumed after recycling, and only small

amounts are used in ferroalloys, cement and petrochemicals industry, there is a

potential for production of steel increase up to 1.0 million tons with the increase in

construction activities, current economic needs in emerging markets and growing

concern over the use of steel in heavy industries. All the above gives an initiative

to find suitable means for effective utilization of mill scale and a low cost by-

product in the steelmaking industry. In the present research, we have employed the

mill scale waste product from the Malaysian steel factories. The steel are collected from Perwaja Steel Terengganu. The immense amount of steel waste give a

challenge for us to extract the iron oxide contained in the mill scale by a

purification technique and producing iron oxide for magnetic materials.

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1.5 Aim of study

In several past decades, studies on YIG by pure materials are reported in ferrite

literature. Instead, fabrication of YIG ferrite by using recycled steel waste product

(mill scale) is still investigated. There are no reports from literature on this work.

Steel waste products are collected from steel industry in Malaysia. It has high

content of iron (Fe) and gives us a challenge to purify and recycled the powder to

produce YIG ferrites. This project will highlight the low cost ferrite fabrication

from the waste material.

Ferrite magnetic materials are known very rely to their microstructure. Nowadays,

the fundamental on scientific enquiry of the microstructure-property evolution has

been neglected. Therefore, in this work, the evolutions of the microstructure-

magnetic properties relationship at various sintering temperature on the

morphology and material properties will be investigated.

1.6 Objectives

The interest of this research is to track down the parallel evolution of

microstructural and magnetic properties from lower sintering temperature (500oC)

to higher temperature (1400oC) of YIG. Hence, the study embarks on the following

objectives:

I. To purify recycled mill scale waste product by magnetic and non-

magnetic separation (MNM) and Curie temperature separation technique

(CTS) collected from steel industries in Malaysia to produce high purity

Fe2O3 as main raw materials in fabrication YIG ferrite by using

mechanical alloying technique.

II. To elucidate the parallel evolution of the magnetic properties with microstructural changes and their relationship in nano-micro yttrium iron

garnet ferrites at various sintering temperatures.

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