Studies of Structural and The Giant Magneto-Caloric Effect of Some Manganites Perovskite

STUDIES OF STRUCTURAL AND THE GIANT
MAGNETO-CALORIC EFFECT OF SOME MANGANITES

PEROVSKITE
MUHAMMED SHAFIQUL ISLAM

STUDENT: Ph. D. PROGRAM
ROLL NO.: P04031405P
SESSION: APRILL/2003
DEPARTMENT OF PHYSICS
BANGLADESH UNIVERSITY OF ENGINEERING & TECHNOLOGY (BUET)
JANUARY, 2011
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This the sis title d “STUDIES OF S TRUCTURAL AND THE G IANT M AGNETO-
CALORIC E FFECT OF S OME M ANGANITES P EROVSKITE” s ubmitted by
MUHAMMED SHAFIQUL ISLAM Roll No-P 04031405 P Registration No. 004583,
Session: A pril/2003 has be en accepted as s atisfactory in partial f ulfillment of th e
requirement for the degree of Doctor of Philosophy (Ph.D.) in Physics on 23 January,
2011.
BOARD OF EXAMINERS
1.
DR. MD. FEROZ ALAM KHAN Chairman
(Supervisor)
Professor, Department of Physics, BUET, Dhaka-1000
2.
DR. A.K.M. ABDUL HAKIM Member
(Co-Supervisor)
MMSD, BAEC, Dhaka-1000
3.
HEAD (Ex-Officio) Member
Department of Physics, BUET, Dhaka-1000
4.
DR. MD. ABU HASHAN BHUIYAN Member
5.
DR. JIBAN PODDER Member
6.
GOLAM MOHAMMED BHUIYAN Member
Professor, Department of Physics, Dhaka University, Dhaka-1000
7.
PROF. AMITABHA GHOSHRAY Member (External)
Head, Experimental Condensed Matter physics
Saha Institute of Nuclear Physics
1/AF, Bidhannagar, Kolkata-700 064, INDIA.
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DECLARATION
Muhammed Shafiqul Islam, has declared that this thesis, submitted in partial fulfillment
of t he r equirements f or t he D octor of P hilosophy, i n t he Faculty o f E ngineering,
Department of P hysics, B angladesh U niversity of E ngineering & T echnology,
Bangladesh, i s s olely and uni quely m y ow n w ork unl ess ot herwise r eferenced o r
acknowledged. T his doc ument ha s not be en s ubmitted f or a qua lification a t a ny ot her
academic institution.
Signature of the Candidate

Name of the Candidate
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To my late father and my late son
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Page No
List of Tables x
List of Figures xii
Physical Constants xxii
List of Symbols xxii
Glossary of Abbreviations xxiii
Acknowledgement xxiv
Abstract xxvi
Chapter One Motivation and Structure of this thesis

1.1 Introduction 1
References 5
Chapter Two General Introduction

2.1 Introduction 6
2.2 Crystal and Electronic Structure 15
2.2.1 Crystal Structure 16
2.2.2 Crystal Field 20
2.2.2.1 A Site 21
2.2.2.2 B Site 21
2.2.3 Electronic Structure 22
2.2.4 Ionic Model 24
2.2.5 Band Model 27
References 29
Chapter Three Literature Review

3.1 Introduction 35
3.2 Fundamental Aspects 36
3.2.1 Relation between Magnetic E ntropy a nd Adiabatic 36
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Temperature Change
3.2.2 Relation between Magnetic Entropy and Resistivity 37
3.2.3 Magneto-caloric behavior and Magnetic Transition 38
3.2.4 Magnetic Cooling Efficiency 39
3.3 Magneto-caloric Measurements 39
3.4 Manganite Materials 40
3.4.1. Structure 40
3.4.2. Magneto-Caloric Effect 41
3.4.2.1. (La 1-x M x ) MnO 3 where M = Na,K and Ag 41
3.4.2.2. (La 1-x M x ) MnO 3 where M = Ca, Sr, Ba, Cd and Pb 42
3.4.2.2.1 (La 1-x Ca x )MnO 3 42

3.4.2.2.2 (La 1-x Sr x ) MnO 3 43
3.4.2.2.3. (La 1-x Ba x )MnO 3 44
3.4.2.2.4. (La 1-x Cd x )MnO 3 44
3.4.2.2.5. (La 1-x Pb x )MnO 3 44
3.4.2.3. (La–Ca–M)MnO 3 where M = Sr, Ba, and Pb 45
3.4.2.4. (La–M–Ca) MnO 3 where M = Nd, Cd, Bi, Tb, Dy, 47
Gd and Ce
3.4.2.5. (La–M)(Mn–Mo) O 3 where M = Ca,Li,Sr and M= Ti, 47
Cr,Cu,Co,Ni
3.4.2.6. (La–Nd–Ca)(Mn–M` )O 3 where M` = Cr and Fe 49
3.4.2.7. (Nd 1-x M x ) MnO 3 where M = Ca and Sr 49
3.4.2.8. (Pr 1-x M x ) MnO3 where M = Ca, Sr and Pb 50
3.4.2.9. (La 1-x M x ) 3 Mn 2 O 7 where M = Ca and K 51
3.5 Concluding remarks of review 52
References 53
Chapter Four Theoretical Aspects of the Magneto-Caloric Effect

4.1 Introduction 59
4.2 Thermodynamic Theory of the Magneto-Caloric Effect 62
4.3 Perovskites Framework and General Remarks 65
4.4 Double Exchange and Super Exchange 71
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4.5 Magnetic Refrigeration 74
References 77
Chapter Five Preparation of Manganites Perovskite and Experimental

Techniques
5.1 Introduction 81
5.2 Target Compositions and Sample Designation 81
5.3 Sample Preparation Technique 82
5.4 Elemental Analysis 85
5.5 Experimental Techniques and Measurements 85
5.5.1 Introduction 85
5.5.2 Fabrication of the Sample 86
5.6 Differential S canning C alorimetry (DSC), Thermogravimetric A nalysis 89
(TGA) Measurements
5.7 Microstructure Observation and Composition Determination (SEM/EDS) 92
5.8 X-Ray Diffraction Analysis 93
5.9 Magnetic Measurement 93
5.9.1 The Zero Field C ooled ( ZFC) a nd F ield C ooled thermo– 93
Magnetization measurements
5.9.2 Measurement Process 95
5.10 SQUID Magnetometer 95
5.11 Isothermal Magnetization Measurements 98
References 99
Chapter Six Study of La 0.7 (Ca 1-x Pb x ) 0.3 MnO 3 perovskite
6.1 Introduction 101

6.2 Scanning Electron Microscope (SEM) Analysis 102
6.2.1 Grain Size and Morphology 103
6.3 Energy Dispersion Spectrum (EDS) Analysis 103
6.3.1 Elemental Analysis 103
6.4 Differential S canning Calorimetry ( DSC), Thermo- Gravimetric 105
Analysis (TGA) Measurements
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6.5.1 Structural Characterization 108
6.5.2 Rietveld Anlysis 110
6.5.3 Structural model 110
6.6 Magnetic Properties 124
6.6.1 The Th ermo-Magnetic Zero F ield C ooled and F ield C ooled 124
Measurements
6.6.2 Transition Temperature from Arrot plot Using M-H Curves 127
6.7 Relationship between Structure and Magnetism 128

6.8 The Hysteresis Loop Measurements of LCPMO series 131
6.9 Magneto-Caloric Properties of the La 0.7 (Ca 1-x Pb x ) 0.3 MnO 3 series 133
6.9.1 Introduction 133
6.9.2 The Magneto-Caloric Effect 134
6.10 Indirect Measurements of the Magneto-Caloric Effect 135
6.11 Magnetic I sotherm of L CPMO series and M agnetic E ntropy 137
Measurements
6.12 Summary 144
References 148
Chapter Seven Study of La 0.7 (Ca 1-x Sr x ) 0.3 MnO 3 perovskite

7.4 Differential S canning Calorimetry (DSC), Thermogravimetric A nalysis 157
(TGA) Measurements
7.5.1 Structure Characterization 161
7.6 Magnetic Properties 168
7.6.1 The T hermo-Magnetic Z ero Field-Cooled a nd F ield–Cooled 168
Measurements
7.6.2 The Hysteresis Loops of LCSMO series 171
7.7 Magnetic Isotherm o f LCSMO s eries and M agnetic E ntropy 172
Measurements
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7.8 Summary 180
References 182
Chapter Eight Study of La 0.7 (Ca 1-x Ba x ) 0.3 MnO 3 perovskite

8.4 Differential S canning Calorimetry (DSC), Thermogravimetric A nalysis 190
(TGA) Measurements
8.5.1 Structure Characterization 196
8.6 Magnetic Measurements 202
8.6. 1 The Hysteresis Loop of LCBMO series 202
8.6.2 The thermo-Magnetic FC and ZFC Curves of LCBMO Series 204
8.6.3 Arrot Plot from M-H Curves 207
8.7 AC Susceptibility of LCBMO series 209
8.8 Magnetic Isotherm of LCBMO series and Magnetic Entropy Measurements 214
8.9 Summary 218
References 222
Chapter Nine Conclusions

9.1 Conclusions 227
References 230
Appendix A: The basics of the Rietveld Refinement Technique 231

References 234
Publications 235
Conference Proceedings 236
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List of Tables
Chapter Two
Page No
Table-2.1 Ionic r adii i n ( Ca, Sr, Ba, P b)-doped l anthanum m anganite 16
perovskites (in nm).The A-site cation radii are given for twelve-fold
and nine-fold oxygen coordination (separated b y comma), while the
B-site cation radii are g iven f or six-fold ox ygen c oordination.
Source: Shannon (1976).
Chapter Five
Table-5.1 The chemicals employed for preparation of the samples 88
Chapter Six
Table-6.1 Lattice Parameters (From Single Phase) 111
Table-6.2 An ove rview of e quivalent c rystallographic p ositions ( given i n 116
Wyckoff notation) of t he s pace groups P bnm with corresponding
coordinates and the atomic occupation factors used for refinement of
the La 0.7 (Ca 1-x Pb x ) 0.3 MnO 3 series
Table-6.3 An overview of the most important parameters of the Rietveld model 117
and an indication whether they were fixed or allowed to vary during
refinement
Table-6.4 Lattice Parameters (From double Phases) 118
Table-6.5 Unit cell Volume 119
Table-6.6 Bond angle and Bond length 123
Table-6.7 Tolerance factor and transition temperature 123
Table-6.8 Transition Temperature by different process 124
Table-6.9 Saturation M agnetization, B ohr M agneton ( µ B ) C oercivity, a nd 133
Remanence
Table-6.10 Transition temperatures, M agnetic Entropy a nd R elative Cooling 144
Power at different magnetic field
Table-6.11 Comparative studies on Magneto-Caloric Effect for Lead (Pb) series 146
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Chapter Seven
Table-7.2 Unit cell Volume, Bond angle and Bond length 163
Table-7.3 Tolerance factor, Curie temperature 167
Table-7.4 Saturation Magnetization, Coercivity, and Remanence 172
Table-7.5 Magnetic Entropy and RCP of the LCSMO series 173
Table-7.6 Comparative s tudies on Magneto-Caloric E ffect for S trontium (Sr) 181
series
Chapter Eight
Table-8.2 Unit cell Volume, Transition temperature, Tolerance factor 201
Table-8.3 Bond angle and Bond length 201
Table -8.4 Saturation M agnetization, B ohr M agneton ( µ B ), Coercivity, a nd 204
Remanence
Table-8.5 Transition Temperature by different processes 209
Table-8.6 Transition temperature, Magnetic Entropy a nd R CP of LCBMO 218
Series
Table-8.7 Comparative s tudies on M agneto-Caloric E ffect for B arium (Ba) 220
series
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List of Figures
Chapter Two
Page No
Fig: 2.1 (a) R esistivity, ( b) M agneto r esistance i n 0.3 T and (c) M agnetization 7
of a (La 0.8 Sr 0.2 ) Mn O 3 ceramic. [Reprinted from Physica, Volume 20,
J. Volger, p. 49, 1954 [10]
Fig: 2.2 The i deal cubic pe rovskite s tructure, [H.D. M eggaw, A cta Cryst. 8
5(1952) 739], ABO 3. A is a large cation, similar in size to O2-; B is a
small cation such as Mn3+ or Mn4+, octahedrally-coordinated by oxygen.
Fig: 2.3 Some pos sible m agnetic m odes [20] for t he B- site cations i n t he 9
perovskite structure
Fig: 2.4 Low-temperature ma gnetic mode s ( letters) and ferromagnetic mom ent 10
for t he (La 1-x Ca x ) M nO 3 series c ompared w ith the electrical
conductivity at 80 K (- - -): (- ‘ -), the spin-only moment for a mixture
of Mn3+ and Mn4+ (fu, formula unit). (After [20, 25])
Fig: 2.5 (a) Charge ordering of Mn3+ and Mn4+ in a mixed crystal with x = ½. 12
2 3+
(b) Orbital ordering of the d z orbitals of Mn when x = 0.
(c) Combined charge and orbital ordering when x = ½
Fig: 2.6 (a) The O -type or thorhombic G dFeO 3 structure w hich is a di storted 17
version of i deal perovskites s tructure of figure 2.2 with a buckling
of t he ox ygen octahedra t o accommodate a s maller t han ideal A
cation.
(b) The O` - type orthorhombic LaMnO3 structure, which incorporates
a Jahn – Teller distortion [17] of the oxygen octahedral.
Fig: 2.7 Relation between the cells used to describe manganese perovskites 18
Fig: 2.8 Magnetic pha ses i n (La 1-x Ca x )MnO 3 . The s haded line r epresents t he 19
insulator-metal tr ansition. The r egions indi cated are a s f ollows: A I,
antiferromagnetic -insulator; CI, canted antiferromagnetic insulator; FI,
ferromagnetic ins ulator; F M, ferromagnetic me tal; P I pa ramagnetic
insulator [20, 50].
Fig: 2.9 Crystallographic and m agnetic ph ases i n (La 1-x Sr x )MnO 3 [51]. The 20
symbols have the same meanings as in figure 2.8 except that the regions
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labelled O`, O and R s eparated b y b roken curves r efer t o the cr ystal
structures.
Fig: 2.10 Crystal-field energy l evels i n (a) P rGaO 3 and ( b) NdG aO 3 determined 21
by inelastic neutron scattering [52, 53].
Fig: 2.11 Optical transitions for Mn3+ in (a) a free ion, (b) an octahedral site and 22
(c) a uniaxially distorted octahedral site [56].
Fig: 2.12 Occupancy of one – electron energy levels for Mn4+, Mn3+, and Mn2+ in 25
octahedral coordination. The effect of a tetragonal distortion is to lower
the energy of Mn3+ by δ JT , but it leaves the others unchanged [66].
Fig: 2.13 Illustration of the orbital overlap in a plane of the perovskite structure. 26
The d xy orbital (9a t 2g orbital) has little overlap with 2p orbitals of the
2 2
oxygen ne ighbours, whereas t he d x and d y orbitals ( e g orbitals)
overlap s trongly w ith t he ox ygen p x or p y orbitals t o f orm a • * ba nd.
Displacements of the oxygen atoms in the plane are indicated by arrows
Fig: 2.14 Schematic energy band structure of (La 1-x Ca x )MnO 3 26
Chapter Four
Fig: 4.1 Entropy versus T emperature di agram for t wo va lues of a pplied 63
magnetic field
Fig: 4.2 Cubic Perovskites framework 66
Fig: 4.3 Schematic framework of perovskite crystals 67
Fig: 4.4 (a) The octahedral in O - type orthorhombic GdFeO 3 structure which is 67
a di storted version of t he i deal pe rovskite s tructure i n f ig; 4.2 with a
buckling of t he ox ygen octahedral t o accommodate a smaller ion than
ideal A - site c ation. (b) T he oc tahedral in O -type orthorhombic
LaMnO 3 structure, which incorporates a Jahn - Teller distortion of the
octahedral oxygen.
Fig: 4.5 Energy le vels s plitting f or M n3+ ion in octahedral cr ystal-field Jahn- 68
Teller effect. (1): the move of energy caused by dipole interaction, (2):
energy le vels s plitting in octahedral c rystal-field, where ∆ are cr ystal-
field interactions, (3): J ahn-Teller levels s plitting, 2∆ JT , w hich is J T
stabilization energy
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Fig: 4.6 Jahn -Teller distortion of type - I , type - II (JT polaron) and of insulator 69
or magnetic Polaron
Fig: 4.7 Schematic electron configuration in d band of trivalent and quadrivalent 70
Mn and Co, (a) - Ma ion case, (b) - Co ion case
Fig: 4.8 The schematic diagram of the SE (a) and DE (b), (c) interactions. The 72
two states Mn 3+-Mn4+ and Mn4+-Mn3+ are degenerate if the manganese
spins are parallel
Fig: 4.9 Schematic c omparison of ( a) a non -distorted p erovvskite w ith (b) a 73
distorted perovskite s tructure due t o M n-O-Mn angle and
3+ 2- 4+
Mn -O -Mn interaction
Fig: 4.10 Carnot cycle: two isothermal (AB and CD) and two adiabatic (DA and 75
BC) processes
Fig: 4.11 Ericsson cycle: two isothermal (AB and CD) and two isofield (BC and 75
DA) processes
Fig: 4.12 Brayton c ycle: t wo i sofield ( BC a nd D A) a nd t wo a diabatic ( AB and 76
CD) processes
Fig: 4.13 Scheme to illustrate the magnetic refrigeration 76
Chapter Five
Fig: 5.1 Schematic di agram of s olid – state r eaction technique us ed f or 84
preparing investigated samples
Fig: 5. 2 Pre-sintering process for the samples 84
Fig: 5.3 Sintering process for the samples 85
Fig: 5.4 The experimental stages and procedures 86
Fig: 5.5 Schematic explanations of the methodologies and equipment employed 87
in the fabrication of the sample and for the measurements
Fig: 5.6 DSC, TGA, equipment 89
Fig: 5.7 Scanning Electron Microscope 89
Fig: 5.8 DSC, TGA, dTG of La 2 O 3 90
Fig: 5.9 DSC, TGA, dTG of CaCO 3 90
Fig: 5.10 DSC, TGA, dTG of MnCO 3 90
Fig: 5.11 DSC, TGA, dTG of BaCO 3 91
Fig: 5.12 DSC, TGA, dTG of SrCO 3 91
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Fig: 5.13 DSC, TGA, dTG of PbCO 3 91
Fig: 5.14 Information obtained by electron beam irradiation 92
Fig: 5.15 Advanced D 8 XRD at Chemical Department and D 5 XRD at CMS and 93
Uppsala
Fig: 5.16 VSM equipment at CMS 94
Fig: 5.17 Schematic mechanism of VSM Equipment 94
Fig: 5.18 External View of MPMS XL-5 SQUID Magnetometer 96
Fig: 5.19 Illustration of R SO me asurements w ith small a mplitude, (a) t he i deal 97
SQUID response for a dipole a nd ( b) t he m ovement of t he s ample
within the SQUID pick-up coils.
Chapter Six
Fig: 6.1 Surface electron micrographs of s elected La 0.7 (Ca 1-x Pb x ) 0.3 Mn O 3 102-103
Samples. T he s cale ba rs c orrespond t o 5 μm ( the i mages a re s caled
equally).
Fig: 6.2 EDS of LCMO and LCPMO series. Characteristic peaks are labeled by 104
corresponding elements
Fig: 6.3 DSC pattern of La 0.7 (Ca 1-x Pb x ) 0.3 MnO 3 series 106
Fig: 6.4 TGA pattern of La 0.7 (Ca 1-x Pb x ) 0.3 MnO 3 series 106
Fig: 6.5 dTG pattern of La 0.7 (Ca 1-x Pb x ) 0.3 MnO 3 series 107
Fig: 6.6 X-ray di ffraction pa tterns of La 0.7 (Ca 1-x Pb x ) 0.3 MnO 3 samples w ith 108
index number h, k, l
Fig: 6.7 Enlarged view of the 2θ = 32.0 0-33.50 for X-ray diffraction patterns of 109
La 0.7 (Ca 1-x Pb x ) 0.3 MnO 3 samples
Fig: 6.8 Lattice parameters as a function of Pb Content 111
Fig: 6.9 Reitveld refinement analysis of La 0.7 (Ca 1-x Pb x ) 0.3 MnO 3 samples 112-113
(12500) from X-ray diffraction patterns with considering single phase
Fig: 6.10 Reitveld refinement analysis of La 0.7 (Ca 1-x Pb x ) 0.3 MnO 3 samples 114-115
(12500) from
X-ray diffraction patterns with considering double phase
Fig: 6.11 Lattice parameters as a function of Pb Content from double phase 118
Fig: 6.12 Unit c ell V olume a s a f unction P b C ontent w ith s ingle a nd D ouble 119
Phase
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Fig: 6.13 Ionic Radius of A-site as a function Pb Content 119
Fig: 6.14 Bond angle as a function of Pb content 120
Fig: 6.15 Bond angle as a function of Ionic radius of A-site 120
Fig: 6.16 Bond Length (Mn-O P ) as a function of Pb content 120
Fig: 6.17 Bond Length (Mn-O a ) as a function of Pb content 121
Fig: 6.18 Tolerance factor as a function of Pb content 122
Fig. 6.19 Transition temperatures as a function of Pb content 122
Fig: 6.20 Transition temperatures as a function of Tolerance factor 122
Fig: 6.21 Transition temperature as a function Tolerance factor and Pb content 123
Fig: 6.22 The thermo-magnetic zero – field – cooled (ZFC) and field cooled (FC) 125
curves as a function of temperature of the LCPMO series
Fig: 6.23 dM/dT vs T graph of the LCPMO series 125
Fig: 6.24 Transition temperatures as a function volume 126
Fig: 6.25 Arrot Plot: Square Magnetization as a function of H/M for x=0.15 127
Fig: 6.28 Transition temperature as a function of mean ionic radius <r A > 130
Fig: 6.29 Transition temperature as a function of bond angle 130
Fig: 6.30 Transition temperatures as a function of bond length 130
Fig: 6.31 Hysteresis loop of La 0.7 Ca 0.3 MnO 3 sample 131
Fig: 6.32 Hysteresis loop of La 0.7 Ca 0.285 Pb 0.015 MnO 3 sample 131
Fig: 6.33 Hysteresis loop of La 0.7 (Ca 1-x Pb x ) 0.3 MnO 3 Series at 1000 Oe 132
Fig: 6.34 Hysteresis loop of La 0.7 (Ca 1-x Pb x ) 0.3 MnO 3 Series at 7000 Oe 132
Fig: 6.35 Hysteresis loop of La 0.7 (Ca 1-x Pb x ) 0.3 MnO 3 Series at 3.2 T 132
Fig: 6.36 Simplified illustration of the effect of an applied magnetic field H to a 134
ferromagnetic spin system
Fig: 6.37 Magnetic Isotherm of LCPMO series (x=0.15) at 5 T. 138
Fig: 6.38 Magnetic e ntropy as a f unction of te mperature at di fferent ma gnetic 138
fields
Fig: 6.39 Magnetic Isotherm of LCPMO series (x=0.20) at 5 T 139
Fig: 6.40 Magnetic e ntropy as a f unction of te mperature at di fferent ma gnetic 139
fields
Fig: 6.41 Magnetic Isotherm of LCPMO series (x=0.25) at 5 T 140
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Fig: 6.42 Magnetic ent ropy as a f unction of t emperature at di fferent ma gnetic 140
fields
Fig: 6.43 Comparison of magnetic entropy as a function of Pb content at different 141
applied magnetic fields.
Fig: 6.44 Comparison of magnetic entropy as a function transition temperature at 141
different applied magnetic fields
Fig: 6.45 Magnetic entropy as a function of Pb content and temperature at 5T 142
Fig: 6.46 Magnetic entropy as a function of Pb content and temperature at 2 T 142
Fig: 6.47 Comparison of R elative c ooling pow er as a f unction of P b c ontent a t 143
different applied fields
Fig: 6.48 Comparison of R elative c ooling pow er a s a f unction of T ransition 143
temperature at different applied fields
Fig: 6.49 Comparative studies on Magnetic entropy as a function of Pb content 145
Fig: 6.50 Comparative s tudies on M agnetic entropy a s a f unction o f C urie 145
temperature
Fig: 6.51 Comparative s tudies on Magnetic entropy a s a f unction of P b content 147
and Curie temperature
Chapter Seven
Fig: 7.1 The SEM pictures of the La 0.7 (Ca 1-x Sr x ) 0.3 MnO 3 perovskites 154-155
Fig: 7.2 EDS of LCMO and LCSMO series 156
Fig: 7.3 DSC pattern of La 0.7 (Ca 1-x Sr x ) 0.3 MnO 3 (x=0.25) sample 157
Fig: 7.4 DSC pattern of La 0.7 (Ca 1-x Sr x ) 0.3 MnO 3 series 158
Fig: 7.5 TGA pattern of La 0.7 (Ca 1-x Sr x ) 0.3 MnO 3 (x=0.25) sample 158
Fig: 7.6 TGA pattern of La 0.7 (Ca 1-x Sr x ) 0.3 MnO 3 series 159
Fig: 7.7 X-ray diffraction patterns of La 0.7 (Ca 1-x Sr x ) 0.3 MnO 3 samples (12800 C) 160
with index number h, k, l
Fig: 7.8 The Enlarged view of the 2θ = 32.00-33.50 for X-ray diffraction patterns 161
of La 0.7 (Ca 1-x Sr x ) 0.3 MnO 3 series
Fig: 7.9 X-ray diffraction patterns of La 0.7 (Ca 1-x Sr x ) 0.3 MnO 3 samples (12000 C) 162
Fig: 7.10 Lattice parameter as a function of Sr content 162
Fig: 7.11 Volume of unit cell as a function Sr content 163
0
Fig: 7.12 Reitveld analysis of La 0.7 (Ca 1-x Sr x ) 0.3 MnO 3 samples ( 1280 ) from X - 164
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ray diffraction patterns with considering single phase
Fig: 7.13 Reitveld analysis of La 0.7 (Ca 1-x Sr x ) 0.3 MnO 3 samples (12800) from X - 165
ray diffraction patterns with considering double phase
Fig: 7.14 Bond angle as a function of Sr content 166
Fig: 7.15 Bond length (Mn-O P ) as a function of Sr content 166
Fig: 7.16 Bond length (Mn-O a ) as a function of Sr content 167
Fig: 7.17 Curie temperature as a function Sr content 167
Fig: 7.18 Tolerance factor as a function Sr content 168
Fig: 7.19 The the rmomagnetic F ield - Cooled ( FC) a nd Z ero – Field – Cooled 168
(ZFC) curves of the LCSMO series
Fig: 7.20 The thermomagnetic zero – field – cooled (ZFC) curves of the LCSMO 169
series
Fig: 7.21 Curie temperature as a function of ionic radius of A-site 170
Fig: 7.22 Curie temperature as a function of Bond angle 170
Fig: 7.23 Curie temperature as a function of tolerance factor 170
Fig: 7.24 Hysteresis loop of La 0.7 Ca 0.27 Sr 0.03 MnO 3 sample 171
Fig: 7.25 Hysteresis loop of LCSMO series 172
Fig: 7.26 Magnetization of LCSMO (x=0.25) series as a function Magnetic field 174
sintered at 12000C
Fig: 7.27 Magnetic entropy of LCSMO series (x=0.00, 0.10 and 0.25) sintered at 174
0
1200 C as function of temperature
sintered at 12800C
Fig: 7.29 Magnetic entropy as function of temperature at 1.35 T and 1 T (x=0.00) 175
sintered at 12800C
0
sintered at 1280 C
sintered at 12800C
sintered at 12800C
0
sintered at 1280 C
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sintered at 12800C
0
sintered at 1280 C
sintered at 12800C
sintered at 12800C
Fig: 7.38 Comparative studies on Magnetic entropy as a function of Sr content 180
Fig: 7.39 Comparative s tudies o n M agnetic entropy a s a f unction C urie 181
temperature
Chapter Eight
Fig: 8.1 The SEM pictures of the La 0.7 (Ca 1-x Ba x ) 0.3 MnO 3 perovskites 188-189
Fig: 8.2 EDS of LCMO and LCBMO series 189-190
Fig: 8.3 DSC pattern of La 0.7 (Ca 1-x Ba x ) 0.3 MnO 3 series 191
Fig: 8.4 TGA pattern of La 0.7 (Ca 1-x Ba x ) 0.3 MnO 3 series 191
Fig: 8.5 dTG pattern of La 0.7 (Ca 1-x Ba x ) 0.3 MnO 3 series 192
Fig: 8.6 X-ray di ffraction patterns of La 0.7 (Ca 1-x Ba x ) 0.3 MnO 3 samples ( 12800 193
C) with index number h, k, l
Fig: 8.7 The enlarged view of 2θ =320 to 33.5 0 for X-ray diffraction patterns of 193
0
La 0.7 (Ca 1-x Ba x ) 0.3 MnO 3 samples (1280 C)
Fig: 8.8 Observed (star) and calculated (solid line) X-ray diffraction pattern for 194-195
La 0.7 (Ca 1-x Ba x ) 0.3 MnO 3 series
Fig: 8.9 Lattice parameter as a function of Ba content 196
Fig: 8.10 Observed (star) and calculated (solid line) X-ray diffraction pattern for 197-198
La 0.7 (Ca 1-x Ba x ) 0.3 MnO 3 (with considering double phase Mn 3 O 4 ) series
Fig: 8.11 Unit cell Volume as a function of Ba content 199
Fig: 8.12 Bond angle as a function of Ba content 199
Fig: 8.13 Bond length (Mn-O P ) as a function of Ba content 199
Fig: 8.14 Bond length (Mn-O a ) as a function of Ba content 200
Fig: 8.15 Tolerance factor as a function of Ba content 201
Fig: 8.16 Ionic radiuses as a function of Ba content 202
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Fig: 8.17 Transition temperature as a function of Tolerance factor 202
Fig: 8.18 Hysteresis loop of LCBMO series 203
Fig: 8.19 Hysteresis loop of La 0.7 Ca 0.27 Ba 0.03 MnO 3 sample 203
Fig: 8.22 The thermo-magnetic zero field cooled curves of the LCBMO series 205
Fig: 8.23 The t hermo-magnetic field cooled (FC) and z ero – field – cooled 206
(ZFC) curves of the LCBMO series
Fig: 8.24 Curie temperatures as a function of Ba content 206
Fig: 8.25 Curie temperatures as a function of Ionic Radius of A-site 207
Fig: 8.26 Curie temperatures as a function of Bond Angle 207
Fig: 8.27 Arrot-plot from (M-H) curve for the sample x=0.05 207
Fig: 8.30 The t emperature d ependence AC s usceptibility (real pa rt) for x = 0.05 210
measured at different AC frequencies
Fig: 8.31 The t emperature d ependence AC s usceptibility (imaginary part) for 210
x=0.05 measured at different AC frequencies
Fig: 8.32 The t emperature d ependence AC s usceptibility (real pa rt) f or x = 0.10 211
Fig: 8.34 The t emperature d ependence AC s usceptibility (real pa rt) for x = 0.15 212
Fig: 8.36 The t emperature de pendence A C s usceptibility (real p art) for x = 0.25 213
Fig: 8.38 Magnetic isotherm of LCBMO series (x=0.05) at 5T 215
Fig: 8.39 Magnetic entropy change as a f unction of temperature for the samples 215
x= 0.05 at different applied magnetic fields
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Fig: 8.44 Comparative studies on Magnetic entropy as a function of Ba content 219
Fig: 8.45 Comparative studies on Magnetic entropy as a function of temperature 219
Fig: 8.46 Comparative studies on Magnetic entropy as a function of Ba content 221
and Curie temperature
Appendix A
Fig: A.1 Rietveld’s fit of a Gaussian with FWHM and Cagliottis fit of the half 231
Width at different 2θ angles
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Physical constants
Symbol Quantity Value Units
-19
e Electron charge 1.60218*10 C
-23 -1
kB Boltzmann’s constant 1.3807*10 JK
-7 -2
μ0 Vacuum permeability 4π *10 NA
-24 -1
μB Bohr magneton 9.27400899*10 JT
List of symbols
Symbol Name Units
B Magnetic flux density T
CP Specific heat capacity at constant pressure Jkg-1 K-1
C P,H Specific heat capacity at constant pressure and Magnetic Field Jkg-1K-1
Δ SM Isothermal Magnetic Entropy Change Jkg-1K
Δ T ad Adiabatic temperature Change K
2θ X-ray diffraction angle deg.
g Lande Factor dimensionless
G Conductivity Ω -1m-1
H Magnetic field strength Am-1
H0 Initial magnetic field Am-1
H1 Final magnetic field Am-1
m Magnetic moment Am2
M Magnetization per unit volume Am-1
μ Permeability NA-2
MR Magnetoresistance Relative
ns Spins per unit mass kg-1
P Pressure Pa
μr Relative permeability dimensionless
ρ density kgm-3
R Resistance Ω
ρ Resistivity Ωm
ρH Resistivity in an magnetic field Ωm
S Specific entropy Jkg-1K-1
SM Specific magnetic entropy Jkg-1K-1
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• Specific magnetization Am2kg-1
T Temperature K
TC Curie temperature K
Θ D Debye temperature K
V Volume m3
χ Magnetic susceptibility dimensionless
Glossary of Abbreviations
Abbreviations Meaning
AC Alternating Current
AFM Antiferromagnetism
AFMI Antiferromagnetic Insulator
a.u Arbitrary Units
CMR Colossal magnetoresistance
CW Curie Wiess
DC Direct Current
DSC Differential Scanning Calorimetry
DTA Differential Thermal Analysis
FC Field Cooled
FM Ferromagnetism
FMM Ferromagnetic Materials
FWHM Full width Half Maximum
GMR Giant Magnetoresistance
ICDD International Centre for Diffraction Data
IR Infrared
MCE Magneto-caloric effect
MPMS Magnetic properties Measurement System
MR Magnetoresistance
PMI Paramagnetic Insulator
PPMS Physical properties Measurement System
PVR Polyhedral volume ratio
SEM Scanning Electron Microscope
TEM Transmission electron Microscope
TGA Thermogravimetric Analysis
XRD X-ray Diffraction
ZFC Zero- Field Cooled
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ACKNOWLEDEGEMENTS
First a nd foremost, I would like to e xpress my s incere thanks to my supe rvisor P rof. Dr. Md. Feroz
Alam Khan for his excellent supervision. I am grateful to him for his continuous support during the
course of m y re search work. I w ould l ike t o e xpress m y c ordial t hanks t o hi m f or hi s c onstant
guidance, and encouragement during the difficult phase of my work. His important advices during my
study and research work have guided me through to the completion of this work. I express my deepest
sense of gr atitude f or hi s a ble gui dance a nd s upport i n hom e a nd a broad. I a m t hankful t o hi m f or
going extra miles to help me out to settle my academic and other related problems and for providing
me with the relaxed working atmosphere during the entire course of my research work
I would like t o express my pr ofound gratitude and sincere appreci ation to my Co-supervisor Dr.
A.K.M. Abdul Hakim Chief Engineer, MMSD, BAEC, Dhaka, Bangladesh, for his important advice,
continuous support, constant encouragement, during this research work.
I w ould l ike t o pa y my r egards t o Prof Nguyen Chau, E x-Director C MS, V ietnam f or hi s he lp a nd

assistance during my stay in Vietnam National University. I express my thanks to Prof. D. L. Minh,
Prof. N.H. Luong, Prof. B. T. Cong, Prof. Le Van Vu for their help during my research work at the
CMS. Thanks are also due to Mr. H.N Nhat, Mr. Hai. Mr. N.D. Thou, Mr. The, D. L. Hanh, T.D. Hiep,
Mr. N.D. Phu, Mr. N.H. Hai and all the research fellows, technical staffs, for their help at the Center
for Materials Science, Department of Solid State Physics, Vietnam University of Science.
I am thankful to P rof. Per Nordblad, P rof. P eter Svedlindh, Mathias Hudl, Roland Mathiu, Magnus,
and K las f or t heir assistance w ith Physical P roperties M easurement S ystem ( PPMS) and Magnetic
Properties Measurement System (MPMS) at the Dept. of Engg. Sciences, Uppsala University,Sweden.,
Prof. Roland Telgren and Mr Dahbi for helping in analyzing the XRD data with Rietveld refinement
technique a nd a ll t he r esearch f ellows, t echnical s taff, a nd s tudents i n Å ngström laboratory.
Department of S olid S tate Physics, Faculty of E ngineering S ciences, Ångström Laboratory, U ppsala
University, Sweden for their kind co-operation and heartiest assistance.
I am indebted to Dr. A.K.M. Akther Hossain, Professor and H ead , Dr. Md Abu Hasan Bhuiyan,
Professor, Dr. Jiban Podder, Professor, Dr.Nazma Zaman, Professor , Department of Physics, BUET,
for their valuable suggestion, inspiration to complete the thesis work.
I am very much grateful to the International Science Program (ISP), Uppsala University, Sweden for
providing me with financial support and cordial help to visit the Centre for Materials Science (CMS),
Hanoi, Vietnam and Solid State Physics Department, Uppsala University, Sweden for doing a part of
my experimental work. I a m thankful to Dr. Ernst v an G röningen, D irector I PPS f or hi s v aluable
assistance and constant cooperation. I would like to express my deep sense of thanks and appreciation
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to all the staffs of I SP for t heir so kind cooperation a nd a ssistance during m y s tay a t U ppsala
University.
I a m gr ateful t o t he c oncerned a uthority of E ducation Ministry, G ovt. of t he Peoples R epublic of

Bangladesh, and Principal, Government Bangla College, Mirpur for granting me the leave to carry out
this r esearch w ork dur ing my s tay a broad. I am al so grateful t o my C hairman and my col leagues,
Department of Physics, Government Bangla College, Mirpur for their so kind co-operation during this
work.
I w ould l ike t o e xtend m y s incere t hanks a nd gr atitude t o Professor M .Ali Asgar f or gi ving m e
valuable suggestions and encouragement during this research work.
With pr ofound gr atitude I e xpress m y c ordial t hanks t o P rofessor G olam M ohammed B huiyan a nd
Professor M esbahuddin Ahmed, P hysics D epartment, D haka University f or t heir v aluable a dvice,
suggestion, during my research work.
My thanks are due to Dr. Dilip Kumar Saha, Principal Scientific officer, MMSD, for helping me with
the program in XRD analysis. Special thanks are also due to all officers, research fellows and technical
staffs, MMSD, AECD, for their help during the sample preparation.
I would like to acknowledge the help of different staffs of Department of Physics, BUET, Dhaka.
I would like to express my deep regards to my mother, brothers, sisters, relatives who encouraged and
supported me during my research work. I would like to introduce here the cooperation of my wife. Her
lively inspiration and encouragement gave me the strength to persevere under difficult circumstances. I
offer an everlasting soft corner for my loving daughter who has been deprived of my company during
the research period.
Finally, I have had a lot of help with this thesis work from many individuals in various selfless ways
and I would like to take the opportunity here to express my gratitude to them.
Muhammed Shafiqul Islam
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ABSTRACT
This thesis presents the results of an experimental investigation of the structural, magnetic
properties and the magneto-caloric effect of three s eries of polycrystalline
La 0.7 (Ca 1-x M x ) 0.3 MnO 3 (M = Pb, Sr, Ba) with x = 0.00, 0.05, 0.10, 0.15, 0.20, 0.25) ,
samples. Scanning E lectron Microscope an alysis of t he s amples indicates that t he
crystallites of t he s amples ar e fairly homogeneous with varying grain sizes. The X-ray
diffraction pattern and Rietveld refinement confirmed that all compounds crystallized in
the orthorhombic s tructure with P bnm s pace group. The l attice pa rameters and unit cell
volume i ncreased with increasing doping l evel for a ll the s amples. The samples w ere
paramagnetic at the room temperature and have shown a paramagnetic to ferromagnetic
transition temperature (T c ) in the temperature range 252 K - 291 K, 252 K - 308 K, and
157 K - 205 K f or ve ry l ow s ubstitution of Pb, S r a nd B a r espectively. The t ransition
temperature changed with i ncreasing x content. The va riation of t he C a/Pb, C a/Sr a nd
Ca/Ba ratios were found to cause a transition from cubic to orthorhombic symmetry in all
compositions for very l ow s ubstitution of dopi ng l evel. The an alysis s uggested a s trong
correlation between the structural and the magnetic properties. A good correlation
between the ionic radius and the Curie temperature, the mean Mn–O–Mn bond angle and
the C urie t emperature has be en obs erved f or a ll t he s tudied s amples. T he M n–O–Mn
bonds m ediate f erromagnetism in these ma terials vi a the doubl e-exchange m echanism.
The m agneto-caloric effects of t he La 0.7 (Ca 1-x M x ) 0.3 MnO 3 samples were measured
indirectly from magnetization measurements. The samples with Pb=0.075 has shown the
highest va lue ( 5.98 J/kgK) a nd ( 3.47 J/kgK) of magnetic ent ropy change around 291 K
with applied magnetic f ield 5 T a nd 2 T r espectively. The s amples w ith Sr=0.075 has
shown the hi ghest va lue ( 5.00 J/kgK) of m agnetic ent ropy change around 293 K w ith
applied magnetic field 1.35 T. The samples with Ba=0.015 has shown the highest value
(5.99 J/kgK) a nd (3.92 J/kgK) of magnetic ent ropy cha nge around 205 K w ith a pplied
magnetic field 5 T and 2 T respectively. The grain sizes of the manganites seem to have
played a role in the observed magnetic properties. Qualitatively, the results obtained for
the La 0.7 (Ca 1-x M x ) 0.3 MnO 3 samples are cons istent with the s imilar s tudies b y ot her
authors.
A significant large magnetic entropy change, |Δ S m | max has been obtained for the studied
samples, which can be considered as t he pot ential candi dates f or giant ma gneto-caloric
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effect (GMCE) in the research on manganites perovskites. Specially, the compounds with
low Strontium (Sr) contents have s hown a GMCE comparable t o t hat of G adolinium,
which i s c onsidered a s a prototype and relatively ex pensive working m aterial for
magnetic refrigeration near room temperature.
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STUDIES OF STRUCTURAL AND THE GIANT
MAGNETO-CALORIC EFFECT OF SOME MANGANITES
PEROVSKITE
DEPARTMENT OF PHYSICS
BANGLADESH UNIVERSITY OF ENGINEERING & TECHNOLOGY (BUET)
JANUARY, 2011
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Chapter One Motivation and the Structure of this thesis
1.1 Introduction
This thesis explains the results of an experimental study on s tructural, magnetic and the
magneto-caloric properties of three series of Calcium – Lead; Calcium – Strontium; and
Calcium – Barium; doped L anthanum m anganese ox ides. T hese oxi des be long t o t he
broad family of materials known as the mixed – valence manganites, A 1-x A` x BO 3 , where
A is a rare – earth cation La, Pr, Y, Nd, etc., A` is an alkali or alkaline earth cation such
as Ca2+, Sr2+, Ba2+, Pb2+, Na1+, K 1+ etc, and B is manganese or cobalt. The designation
mixed - valence ma nganites or c obaltites a rise f rom the f act tha t the ma terials ma y
contain m anganese o r c obalt i n s everal va lence s tates, de pending on t he substitution
parameter x. The m aterials ar e cal led perovskite m anganites be cause t heir cr ystal
structure resembles that of the A cation with an A` cation may serve as hole doping. One
of the main features of these materials is the close relationship between the structural and
magnetism properties.
One of t he v ery i mportant pr omising a pproaches t o t he design of nove l ma terials tha t

have been under very active investigation in recent years is to combine different physical
properties i n one i nnovative c ompound. P erovskites a re capa ble of a ccommodating
different c ombinations o f c ations, s o l ong a s t he c rystal c harge i s ne utral. P erovskites
compounds a re f amily of na turally e xisting m inerals w ith ge neral f ormula of A BO 3 ,
which w as di scovered by Lev A lexseevich Von Perovskii in t he 19 th century. In i ts
idealized c ubic s tructure, t he bi g A c ations a re surrounded b y 12 f old o xygen and t he
small B i ons a re s urrounded b y 6 f old ox ygen. P erovskites ha ve r eceived i ntensive
attention starting from 1990. Usually when the A site cations are small size, an alteration
occurs as a result of tilting in the B octahedral axis with respect to its neibours. Generally,
perovskite ceramics can exhibit magnetic, electric, magneto-caloric, magneto-electric and
sometimes magneto-elastic properties, which would have a wide range of applications in
industry, hous ehold, s uch a s i n da ta s torage devices, refrigerators, e tc. Despite t he
interesting f eature of t he coe xistence of bot h magnetic and electric p roperties i n one
perovskite material, the search for such materials is not so simple, and there is still a need
to de velop s ome ne w techniques a nd c onduct m ore i nvestigations. Designing a nd
understanding a m aterial t hat ha s bot h magnetic and electric pr operties ar e s till
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challenging achi evements. Furthermore, controlling t he c oupling be tween di fferent
degrees of f reedom i n t hose pr operties i s a n e ven g reater pr oblem, w hich ne cessitates
acquiring knowledge of the relevant techniques through careful study of the phenomena.
Among the materials with perovskite type structure, the transition metal oxides with the
formula ABO 3 (A = rare earth trivalent and B = an ion of Mn), demonstrate a wide range
of int eresting pr operties, such as s tructural, giant ma gnetocaloric e ffect, magnetic,
electronic, metal ins ulator tr ansitions, hi gh t emperature s uperconductivity and m agnetic
phase t ransitions. In r ecent de cades, t he m anganites ha ve r eceived pa rticular attention
from P hysicist, C hemist, S cientist a nd R esearchers. T his i s be cause of t he di scovery of
high va lue of m agnetocaloric ef fect, negative m agnetoresistance and magnetic be havior
in the manganite based crystal systems. The unexpected change in the different properties
with doping, temperature dependent transitions, structural and magnetic features were the
main causes for this ex tensive i nterest i n recent years. In these m aterials, the de gree o f
freedom of electrons in the Mn – type ions plays a ve ry crucial role. The exploration of
these m anganites w ith perovskite s tructure h as r evealed a ve ry i mportant r ole f or t heir
magnetic properties and magnetocaloric effect, due to their intrinsic feature of structures.
There a re tw o distinguishable pe rovskite ma nganites, type O ne: f erromagnetic me tallic
(FMM) a nd paramagnetic ins ulating ( PMI) ma terials, type tw o: c onsisting of tw o
transition a nti-ferromagnetic ins ulating (AFMI), ferromagnetic m etallic ( FMM), a nd
paramagnetic insulating (PMI) materials.
Mn – based perovskite – type ABO 3 compounds have always been the focus of research
interest due to their f ascinating ph ysical pr operties. Both magnetic and the e lectric
properties of t he M n – based pe rovskite c ompounds de pend on s everal f actors : f irstly,
whether t he s pin s tate of M n2+, M n3+ and M n4+ take hi gh, i ntermediate or l ow s pin;
secondly, t he existence of an indirect ex change interaction [1,2]. T he M n i ons i nteract
through i ntermediate oxygen, where t he M n3+ - O2- - Mn4+ or M n4+ - O2- - Mn3+ and
Mn3+ - O2- - Mn3+ or M n4+ - O2- - Mn4+ systems ha ve f erromagnetic and anti-
ferromagnetic properties respectively [3-5]. In order to force the B – sites to have multi-
valences s uch as Mn3+ and Mn4+; the mos t e ffective w ay is to introduce the mix er of
divalent alkaline elements to replace rare earth (RE) elements on A – sites. At the same
time, the charge carrier concentration is induced due to the doping elements. Introducing
the dopa nt e lements i nto t he A – sites and M n b ased pa rent pe rovskite will c hange i ts
existing pr operties i n t he r esultant pr operties i n t he r esultant c ompounds. R eplacing C a
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with Pb, Sr, and Ba c ould r esult i n di fferent m agnetic f eatures, s uch as m agnetic and
magneto-caloric properties, a transition from paramagnetic (PM) to ferromagnetic (FM),
to a nti-ferromagtic (A FM), or i n cluster – spin – glass – like a nd i nhomogeneous
ferromagnets with specific Curie temperature. In some materials it shows highly saturated
magnetization whereas in some others it can display to an anisotropic magnetic state. The
substitution of Pb, Sr, and Ba could also create double – exchange ferromagnets, in which
the c onductive e lectrons a re m ore m obile t han t hose i n C a onl y. In or der t o i nduce t he
above m entioned m agnetic s tates, Pb, Sr, and Ba are s ubstituted i n L a 0.7 (Ca 1-
x M x ) 0.3 MnO 3 (where M = Pb, Sr, and Ba) (LCPMO, LCSMO, LCBMO) series. A t t he
same t ime, the cha rge c arrier de nsity can change c ompared t o t he pa rent M n – based
ABO 3 compounds.
Bearing t he f oregoing di scussion i n m ind, t he obj ective of t his t hesis w ill f ocus on t he
investigation of the structure, magnetic and the magneto-caloric properties of Mn – based
LCPMO, LCSMO, a nd LCBMO perovskites deliberately de signed c ompounds of nove l
manganite materials, which are studied with various dopants and doping levels of Pb, Sr,
and Ba. The principal structure of this thesis is designed to achieve the following:
1. A brief introduction on manganite perovskites is explained in chapter two.
2. Starting f rom a l iterature r eview of t he r elevant books , j ournals a nd c onference

papers, t he p roperties o f pe rovskite composites a re considered, a long with t he
behavior of c ertain pe rovskite – structured ma terials. The r esults of thi s r eview
have been highlighted in the chapter three, which also covers the governing laws
and theories to be used in the analysis of the results.
3. The theoretical aspects of m agnetocaloric ef fect ar e br iefly described in cha pter

four.
4. The method o f s ample’s pr eparation i s de scribed br iefly i n c hapter f ive. All

samples have been prepared by the conventional solid state reaction method. The
experimental techniques a nd m ethodologies t hat w ere d esigned have been
explained fully in chapter five. The prepared samples have been subjected to SEM
with EDS, DSC, TGA, X – Ray Diffraction (XRD) m easurement h ave be en
carried out . The s tructural ana lysis ha s be en pe rformed by X RD data. The
physical pr operties me asurement s ystems (PPMS), the ma gnetic pr operties
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measurement s ystems ( MPMS) XL-5 SQUID magnetometer a nd the vibrating
sample m agnetometer ( VSM) ( DMS – 880) h ave be en us ed t o e xamine t he
magnetic and magneto-caloric properties of the following perovskite materials:
La 0.7 (Ca 1-x Pb x ) 0.3 MnO 3 (x = 0.00, 0.05, 0.10, 0.15, 0.20 and 0.25) (LCPMO)
La 0.7 (Ca 1-x Sr x ) 0.3 MnO 3 (x = 0.05, 0.10, 0.15, 0.20 and 0.25) (LCSMO)
La 0.7 (Ca 1-x Ba x ) 0.3 MnO 3 (x = 0.05, 0.10, 0.15, 0.20 and 0.25) (LCBMO)
5. The r esults of the measurements, obs ervations a nd a nalysis on t he p repared

perovskite materials have been presented in the remaining ch apters of the thesis.
These chapters have provided the detailed information on ABO 3 (A = La, Ca, Pb,
Sr, and Ba; B = Mn) systems and our new findings.
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References
[1.1] C. Zener, “Interacraction between the shells in the transition metals”, Phys. Rev. 82
(1951) 403
[1.2] P.W. A nderson, H. H asegawa, “ Considerations on doubl e e xchange”, P hys. R ev.

100 (1955) 675
[1.3] P.M. R accah and J.B. G oodenough, “ A l ocalized-electron t o collective-electron

transition in the system (La,Sr)CoO 3 ”, J.Appl. Phys. 39 (1968) 1209.
[1.4] V.G. Bhide, D.S. Rajoria, C.N.R. Rao, G. Rama Rao and V.G. J adhao, “ Itinerant-
electron f erromagnetism in La 1-x Sr x CoO 3 : A M Össbaur study”, P hys. Rev. B 12
(1979) 2832
[1.5] John B . G oodenough, “ An i nterpretation of t he m agnetic pr operties of t he

perovskite-type mixed crystals La 1-x Sr x CoO 3-• ”, J. Phys. Chem. Solids 6 (1958) 287
5|Page
Chapter Two General Introduction
2.1 Introduction
Mixed va lence m anganites w ith t he pe rovskites structure ha ve be en s tudied f or a lmost
last 60 years [1]. The manganites perovskite offers a degree of chemical flexibility, which
permits the relation between the oxides, electronic structure and magnetic properties to be
examined in a systematic way. Research on the manganites has revealed new phenomena
such as colossal [ 2] a nd de nse granular m agneto resistance [ 3] a nd has l ed t o t he
formulation of i mportant ph ysical c oncepts s uch a s doubl e e xchange [ 4, 5] and J ahn-
Teller pol aron [ 6, 7 ]. E arly research w as m otivated b y a ne ed t o de velop i nsulating
ferromagnets w ith a l arge ma gnetization for hi gh frequency applications. More r ecent
work ha s be en dr iven by a de sire t o unde rstand a nd e xploit the l arge n egative m agneto
resistance effects, which appear near, and below Curie temperature. The manganites also
have potential as solid electrolytes, catalysts, sensors and novel electronic materials. Their
rich electronic ph ase di agrams r eflect the f ine ba lance o f int eractions, which determine
the e lectronic ground s tate. T hese c ompounds r epresent, i n m icrocosm, t he i nterplay o f
experiment, theory and application which is at the heart of solid state Physics.
The br oad f eatures of t he m ixed - valance m anganese pe rovskites w ere de scribed for
polycrystalline c eramic s amples b y J onker and Van Santen [1], V an S anten a nd J onker
[8] a nd Jonker [ 9] when they w ere working a t P hilips lab in t he l ate 1940s . T hey
discussed the preparation, crystal structure and magnetic properties of (La 1-x Ca x ) Mn O 3
series [ 1] and gave a s hort account o f t he electrical r esistivity [ 8]. Similar r esults w ere
found for the (La 1-x Sr x ) MnO 3 and (La 1-x Ba x ) MnO 3 series but the range of solid solution
was limite d to x<0.7 or x <0.5 respectively. Magneto-resistance and ot her t ransport
properties w ere f irst de scribed i n 1954 b y V olger [ 10] w ho s howed t hat t he m agneto
resistance of (La .8 Sr .2 ) MnO 3 is negative with a peak near the Curie temperature (figure-
2.1). A n e xtensive s tudy of f lux-grown single c rystals of ( La 1-x Pb x ) M nO 3 with
0.2<x<0.44 was carried out by Searle and Wang [11, 12], Morrish et al. [13] and Leung et
al. [ 14] i n 1969 a nd 1970. T hey found m etallic conductivity be low t he Curie poi nt T C ,
similar to that polycrystalline (La 1-x Sr x ) MnO 3 . The value of the magnetization suggested
that a fully spin-polarized d band is involved in the ferromagnetic ordering process.
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Interest in the mixed-valance manganites revived in the 1990s following the preparation
of high quality thin films with large magneto resistance by Von Helmholt et al. [15] and
Chahara e t al. [ 16] us ing a m ethod e mployed f or hi gh-temperature s uperconductors, t o
which the manganites are structurally related. Optimized films show remarkable magneto
resistance effects near T C which were epitomized by Jin et al. as the ‘Colossal Magneto
Resistance’ ( CMR) [ 2]. The C urie poi nt coincides with a m etal-insulator t ransition, and
there are as sociated anomalies in various ph ysical pr operties. Films m ay be us ed a s
sensors, and there are prospects for developing spin electronic devices based on thin –film
hetero - structures.
Fig: 2.1 (a) R esistivity, ( b) M agneto resistance i n 0.3 T a nd ( c) M agnetization of a

(La 0.8 Sr 0.2 ) Mn O 3 ceramic. [Reprinted from Physica, Volume 20, J. Volger, p. 49, 1954
[10]
The mixed-valance oxides can be regarded as solid solutions between end members such
as L aMnO 3 and C aMnO 3 with formal va lance s tates La3+Mn3+O 3 2- and C a2+Mn4+O 3 2- ,
leading to mixed-valance c ompounds s uch a s ( La 1-x 3+Ca x 2+) (M n 1-x 3+Mn x 4+)O 3 . T he
nominal electronic configurations of Mn3+ and Mn4+ are 3d4 and 3d3 respectively. Each of
the end members is anti-ferromagnetic and insulating, but the solid solutions with x ≈ 0.3
are f erromagnetic a nd c onducting. F or i nstance, ( La 0.7 Ca 0.3 )MnO 3 has a C urie
temperature T C = 220 K, and a low temperature resistivity ρ 0 ≈ 10-5 Ω m.
7|Page
Chemically, the s ystem i s cha racterized by t he w ide r ange of cat ions w hich can occupy
the A site in the perovskite structure, which may be set at the body – center or the cube
corner (Figure 2.2). A good way to regard the structure is as a cubic close-packed array
formed of O 2- anions a nd l arge A c ations, w ith t he s mall B c ations i n t he oc tahedral
interstitial sites. As discussed in structure section, the ideal cubic structure is distorted by
cation size m ismatch and the J ahn-Teller e ffect, w hereby a di stortion of t he ox ygen
octahedron surrounding the B site cation splits the energy levels of a 3d ion such as Mn3+,
thus lowering the energy. The distorted structures are frequently orthorhombic. Divalent
cations which can occupy the body-center A site include calcium, barium, strontium and
lead; trivalent cations include yttrium, lanthanum, praseodymium, neodymium and some
other rare earth’s (R).
Fig: 2.2 The i deal c ubic pe rovskite s tructure [H.D. M eggaw, A cta C ryst. 5( 1952) 739],
ABO 3. A i s a l arge c ation, similar in size to O2-; B is a s mall c ation such as M n3+ or
Mn4+, octahedrally-coordinated by oxygen.
Besides m anganese, many perovskites-structure o xides form with aluminum, gallium or

another 3d element such as chromium, iron, cobalt or nickel on the B sites. The rare-earth
orthoferrites RFeO 3 are one example of a series of perovskite-structure oxides. There are
many ot hers. A ny o f t he t rivalent 3d c ations c an s ubstitute pa rtially for m anganese. A n
exhaustive compilation of data on pe rovskites-structure compounds by Goodenough and
Longho [17] was published in a 1970 Landoldt-Börnstein volume.
The main effects of the various substitutions are to vary the number of electrons in the 3d
band and to alter the inter - atomic distances and bond angles. Whenever different ions of
the s ame 3d el ement w ith different num bers o f el ectrons oc cupy crystallographically
8|Page
equivalent B sites, say B 1 and B 2 , there is a partly-filled d band with a tendency towards
metallic conduction. The configurations 3d n (B 1 ) – 3dn+1 (B 2 ) and 3d n+1 (B 1 ) – 3dn (B 2 )
are degenerate provided that there is no charge ordering. The idea that mixed valence can
lead t o m etallic c onduction i s due t o V erwey a nd de B oer [ 18]. I t w as d eveloped w ith
particular r eference t o magnetite ( Fe 3 O 4 ) [ 19] i n N etherlands i n t he 1930s . T he
occupancy of the B sites in the spinel structure o f ma gnetite b y a mix ture of Fe3+ (3d5)
and F e2+ (3d6) l eads t o electrical condu ction and ferromagnetic B – B ex change
interactions. The idea of mixed-valence ferromagnetism was then applied to oxides with
the pe rovskites s tructure. The m ixed-valence manganites can exhibit m agnetic or der,
charge order a nd or bital or der. E xamples of c harge a nd or bital o rder are g iven l ater i n
figure 2. 5. Some o f the s implest ma gnetic mode s f or th e B s ites i n t he pe rovskites
structure are illustrated in figure 2.3. Mode B is ferromagnetic, but all the others are anti-
ferromagnetic and entail an enlarged magnetic unit cell.
Fig: 2.3 Some pos sible ma gnetic mode s [20] for t he B - site cat ions i n t he pe rovskite
structure.
Modes A, C and G consist of oppositely aligned ferromagnetic planes of the type {001},
{110}, and {111} respectively. Mode G, where each B-site cation is oriented antiparallel
to i ts s ix ne ighbors w ill be f avored b y ne gative B -O-B s uper exchange i nteractions.
Modes C and E each have four antiparallel and two parallel neighbours, whereas mode A
has four parallel and two antiparallel neighbours. A composite CE mode is composed of a
checquer board of alternating C and E blocks. The magnetic axis is usually indicated by a
suffix x, y, or z. Modes may be combined, so that A x B z for example represents a cant ed
anti-Ferro magnet w ith the a nti-ferromagnetic ax is al ong x (≡a) but w ith t he ne t
ferromagnetic moment along z (≡c).
9|Page
The crystallographic and magnetic structures for the ( La 1-x Ca x ) MnO 3 compounds were
determined in 1955 by Wollan and Koehler [20] in a remarkably complete neutron and X-
ray di ffraction s tudy a s a f unction of M n4+ content. In pa rticular, t he ne utron da ta
revealed a ve ry r ich m agnetic pha se di agram w here, f or di fferent dopi ng l evels, a nti-
ferromagnetism c an t ake di fferent configurations ( A, C , C E a nd G t ypes) a nd c an even
coexist w ith ferromagnetism ( B t ype). The m agnetic s tructures ar e i ndicated on figure
2.4. There ar e three main regions: f or s mall a mounts of M n4+ the c ompounds ha ve
essentially ant i-ferromagnetic pr operties. For x a round 0.3, t hey b ecome f erromagnetic
but, for x>0.5, they revert to anti-ferromagnetism up t o the end member CaMnO 3 . From
magnetization and susceptibility results, Jonker [9] concluded that the exchange is weakly
4
positive ( ferromagnetic) be tween t wo 3d Mn3+ ions, ne gative ( a nti-ferromagnetic)
between two 3d 3 Mn4+ ions and positive between a 3d 4 Mn3+ and a 3d 3 Mn4+ ion. These
measurements provided the first clear evidence for a ferromagnetic exchange interaction
in an oxide. Resistivity measurements also revealed a strong correlation between electron
transport a nd magnetic properties. The r esistivity is low est f or the x ≈ 0.3 c omposition
corresponding to the best ferromagnetism, whereas high resistivities are a ssociated with
the anti-ferromagnetic compositions.
Fig: 2.4 low-temperature ma gnetic mode s (letters) a nd f erromagnetic moment f or the

(La 1-x Ca x ) MnO 3 series compared with the electrical conductivity at 80 K (- - -): (- ‘ -),
the spin-only moment for a mixture of Mn3+ and Mn4+ (fu, formula unit). (After [20,25]).
10 | P a g e
Anderson a nd H asegawa [ 21] g eneralized t he doubl e e xchange mechanism b y
considering interactions between a pair of magnetic ions with general spin directions.
They calculated the transfer integral t to be

 θ ij 
t ij = t 0 cos  2.1
 2 
where t 0 is the normal transfer integral which depends on t he spatial wave functions and
the t erm cos (θ/2) i s due to t he s pin wave function; θ is t he angle between t he t wo s pin
directions. This is quite unlike super exchange where the coupling is proportional to cosθ.
They a lso c onsidered t he pr oblem of t he hi gh-temperature pa ramagnetic s tate of t he
manganites where the exchange energy will be much larger than the transfer integral and
predicted that the s usceptibility χ should be C urie l ike, w ith1/χ intercepting t he ax is at
zero, w hich c ontradicted t he e xperimental r esults s howing C urie-Weiss be havior. T his
point w as cor rected by DeGennes [ 22] who poi nted out t hat t he prediction i s erroneous
when the carrier bandwidth is large with respect to kT. Double exchange therefore leads
to normal Curie-Weiss behavior of the susceptibility, 1/χ = C/(T- θ p ) with θ p > 0.
Degennes [22] studied the case of low doping of the end member LaMnO 3 in more detail
and showed in general that mobile electrons in an anti-ferromagnetic lattice produce some
canting of t he s pin a rrangement. T aking a s a s tarting poi nt t he w ell e stablished a -type
planar anti-ferromagnetic order and a transfer (hopping) integral depending on the angle
between t wo n eighboring s pins va rying a s cos(θ/2), a s de monstrated b y A nderson,
DeGennes found t hat t he s table m agnetic configuration at l ow dopi ng s hould be an A B
canted state. He calculated the fixed angle between the magnetizations of adjacent planes
to be pr oportional t o t he c arrier concentration x . A lthough t his c onclusion ha s be en
questioned recently, he successfully explained the values of the saturation magnetization
and non-zero magnetic susceptibility at high fields and a canted structure was accord with
the neutron diffraction data. DeGennes also considered the case when the carriers were
not c ompletely m obile but l ocalized i n t he vi cinity of a di valent A -site i on. T he boun d
hole interacting with spins on the eight B sites neighboring the impurity produces a local
ferromagnetic di stortion of the s pin system; thi s is the c oncept of th e b ound magnetic
polaron. Charge ordering, also known as Wigner crystallization, is driven by inter atomic
Coulomb interactions. The mobile d electrons can be localized on certain manganese ions
11 | P a g e
to form a regular lattice for particular occupancies of the d band provided that the inter -
atomic C oulomb interaction is c omparable w ith the c onduction-electron ba ndwidth W
[23]. T he ef fect i s accent uated by s mall di splacements of t he ox ygen atoms t o
accommodate t he o rdered cation lattice. Charge o rdering i s m ost l ikely w hen the
temperature i s l ow a nd x is a r ational f raction, especially x = 1/ 8, ½, o r ¾. The ex tra
fourth d elecrons may then be localized on alternate manganese sites in a plane, as shown
in figure 2. 5(a). Kanamori [ 24] poi nted out t hat t he carriers i n mixed – valance
manganites ma y b e s trongly coupled to local l attice di stortions. Orbital o rdering can
occur at certain carrier concentrations when the d electrons occupy an asymmetric orbital,
as shown in figure 2.5(b). The driving force is partly direct electrostatic repulsion of the
charge clouds, but c oupled J ahn-Teller di stortions of a djacent oc tahedral s tabilize the
effect. F inally, figure 2 .5(c) i llustrates t he coup led charge and or bital o rder expected
when x = ½.
Fig: 2.5 (a) Charge ordering of Mn3+ and Mn4+ in a mixed crystal with x = ½. (b) Orbital
ordering of t he d z 2 orbitals of M n3+ when x = 0 . ( c) C ombined c harge a nd or bital
ordering when x = ½.
Goodenough [ 25] r ationalized t he m agnetic ph ase di agram obt ained by W ollen and
Koehler i n t erms of i ndirect e xchange b etween m anganese i ons pos tulating t hat t he
hybridization of t he M n3+ d orbitals w ith O2- p or bitals i s s quare a nd c oplanar a nd t hat
Mn4+ and O 2-
hybridize oc tahedral or bitals, he reviewed the i ndirect ex change
mechanisms between the different manganese ions and estimated the sign of the magnetic
interactions. Then, de pending on t he r atio of Mn3+ to M n4+, t he c harge and or bital
12 | P a g e
ordering of bonds d etermines bot h t he c rystallographic a nd t he m agnetic c onfiguration.
The compounds exhibit different kinds of anti-ferromagnetism: the x = 0 end member is a
planar ant i-ferro m agnet w here t he or dering i s f erromagnetic i n plane but a nti-
ferromagnetic out of plane (type A). The end member (x=1) is a pure near- neighbor anti-
ferro magnet where each manganese atom is antiparallel to its nearest neighbor (type G).
For intermediate concentration ranges (near x = 0.75) the compounds are chain anti-ferro
magnets w here the c oupling is f erromagnetic along on e-dimensional chains w hich are
ordered a nti-ferro m agnetically. In vi ew of t he s trong Hund c oupling i n t hese m aterials
and Zener’s double exchange, the largest mobility is found in the ferromagnetic domain
around x = 0.3. The negative sign of the Mn4+ - Mn4+ exchange interactions deduced from
paramagnetic C urie t emperature of C aMnO 3 [9] i s e xplained b y t he G oodenough –
Kanamori rule for d 3 - d3 overlap. The Mn3+ - Mn3+ interaction is mostly ferromagnetic,
although the magnetic order in LaMnO 3 is A – type anti-ferromagnetic. The interaction is
2
ferromagnetic for overlap of d z orbitals in the plane, and anti-ferromagnetic along the
perpendicular a xis [ 25]. To j ustify e quation ( 2.1), a nd t o de duce t he d ouble e xchange
Hamiltonian which is the ba sis of muc h recent theoretical mode ling, we le t J H be t he
Hund r ule c oupling b etween e ither of t wo i on c ores, S = S 1,2 = 3/2, a nd t he m obile
electron, s = ½. The Hamiltonian matrix H for the system of two ions and the electron is
written in block form
I − J H S1.s t0l 
 − J H S 2.s 
II  t 0 l
I II
where the 2×2 diagonal blocks I – I and II – II correspond to energy states of the electron
and a Mn4+ ion core at sites 1 and 2 respectively, and the off – diagonal blocks represent
electron transfer between them, where I is the 2×2 unit matrix. Diagonalization of the
Hamiltonian can be done in steps; first the terms I – I and II – II are expressed in their
respective diagonal representations, and then the I – II and II – I terms have to be
modified to connect the two representations. To diagonalize I – I or II – II, let S 1 ’ = S 1 +s;
S 0 = S 1 ’ +S 2 and S’ =  S 1 ’ =  S 2 ’ = for Mn3+. In the representation where S 1 ’ is
diagonal the eigen values of – J H S 1 . s, which correspond to the electron ↑ or ↓ with
respect to the core spin, are evaluated from the identity S 1 ’2 = S 1 2 + s2 + 2S 1 .s as –J H S/2
for S 1 ’ = S 1 + ½ and J H (S+1)/2 for S 1 ’ = S 1 – ½. Hence each of the blocks can be written
13 | P a g e
 JH S 
− 2 0 
2.2
 J H (S + 1) 
 0 
 2 
The two diagonal representations of these blocks are inclined at an angle θ, corresponding
to the cl assical an gle be tween the t wo Mn4+ core s pins. The I – II a nd II – I bl ocks are
modified to express the rotation of the electron spin between these two representations, by
replacing the unit matrix by the rotation matrix for angle θ, R θ (l) = exp(iθI x ) where I x is
the angular momentum operator for spin ½ about the x – axis. This may be written [26] as
 θ   θ 
cos 2  − sin  2 
    
 sin  θ  cos θ  
  2   2  
The total Hamiltonian expressed in terms of the basis states S 1 = S 1 ± ½ and S 2 ‘= S 2 ± ½
is
 JH S θ  θ 
 − 2 0 t0 cos  t0 sin   
 2  2 
 0
J H (S + 1 )  θ  θ 
− t0 sin   t0 cos 
 2 2  2 
 θ θ 
t0 cos  − t0 sin  
J S
− H 0 
 2 2 2 
 θ  θ  J H (S + 1) 
 t0 sin   t0 cos  0 
 2 2 2 
The qua ntity cos ( θ/2) can be written (S 0 +1/2)/(2S+1). S olving t he s ecular e quation
| H – E i | = 0 leads to the four eigen values of the system. In the case where J H >> t 0 there
are two low – energy solutions
JH S θ 
E=− ± t0 cos  2.3
2 2
These e igen s tates c orrespond t o t he s ymmetric and a ntisymmetric combinations of t he

localized orbitals with the electron spin parallel to the first or second Mn4+ ion core. The
physical impl ication is tha t the e ffective tr ansfer int egral is reduced by c os ( θ/2), as
indicated i n e quation ( 2.1). The doubl e exchange H amiltonian f or t he whole s olid is
therefore taken as
14 | P a g e
 θ ij  ÷
H = ∑ t0 cos ci c j − J H ∑ Si • si 2.4
<ij >  2  i
where c i †(c i ) creates ( annihilates) an electron on the site i with spin parallel to the ionic
core. This r eview g ives a n a ccount of t he l iterature on m ixed – valence m anganites
published up to mid – 1997, with a few later references. Emphasis is on experimental data
and physical models. Another review with a more theoretical approach has been written
by Nagaev [27], and there is a short review by Ramirez [28] that focuses on experimental
aspects of Colossal Magneto-Resistance (CMR). Since the field has recently become very
active, there is a need to set new work in the context of what was already known about
these m aterials and other m odel m agnetic s emiconductors. The s tructural, magnetic,
transport and other properties of mixed – valence manganites are discussed in detail later.
Some e mphasis i s pl aced on compounds w ith x ≈ 0.3, w hich us ually s how a
ferromagnetic ground state w ith metallic c onductivity and large ne gative ma gneto
resistance n ear T C . I ssues t o be a ddressed i nclude t he na ture of t he electronic ground
states, the metal – insulator transitions observed as a function of temperature or applied
field, the electronic transport mechanisms, magnetic localization, dielectric and magnetic
polaron f ormation, t he r ole of s tructure, c ation disorder a nd t he J ahn – Teller ef fect.
Sample preparation is treated in preparation section and applications in later. A summary
of results on related 3d oxides is given in later. Our understanding of magneto transport in
transition - metal c ompounds ow es m uch t o s tudies of t he r are – earth magnetic
semiconductors, w hich were s tudied i ntensively i n t he 1960s . W e t herefore be gin ou r
review in next chapter.
2.2 Crystal and Electronic Structure

The i deal p erovskite structure i s s hown i n f ig: 2.2, where a uni t c ell is c ubic w ith the
parameters a=b= c and α =β =γ=900. Considering t he perovskite s tructure of fi g: 2. 2 as a
cubic cl ose – packed array f ormed of O 2- anions a nd A 2+ or A 3+ cations w ith small B
cations in octahedral interstitial sites, the ideal cation radii r A and r B can be deduced. The
former must be the same as that of oxygen, r O = 0.14nm, while the latter is (21/2 - 1) r O =
0.058 nm . The s tability of t he bi nding be tween A, B a nd ox ygen i ons i s s hown b y a
tolerance factor which was defined by Goldschmidt [29] as follows
(rA + rO )
t= 2.5
2 (rB + rO )
1/ 2
15 | P a g e
which i s uni ty f or i deally sized i ons. T he A – site c ations radii ar e f or twelve – fold
oxygen coordination, where as the B site radii are for six – fold oxygen coordination. In
fact t he pe rovskites s tructure m ay f orm i n ox ides f or w hich 0.89 < t < 1.02. S tability
limits w ill be s lightly di fferent if ot her ioni c radii, such as G oldschmidt’s or iginal s et
based on r O = 0.132 nm, are used or if ionic radii appropriated for a different coordination
number chosen, 0.8<t<0.9 [30].
Table-2.1. Ionic radii in (Ca, Sr, Ba, Pb)-doped lanthanum manganite perovskites (in nm).
The A -site cation radii ar e given for t welve-fold a nd ni ne-fold ox ygen c oordination
(separated by com ma), w hile t he B -site c ation radii a re given for s ix-fold oxygen
coordination. Source: Shannon (1976).
A-site(nm) B-Site(nm) O-site(nm)

La3+ 0.136, 0.1216, 0.1032 Mn4+ 0.053 O2- 0.142
Ca2+ 0.134, 0.118, 0.10 Mn3+ 0.0645
Sr2+ 0.144, 0.131, 0.118
Ba2+ 0.161, 0.147, 0.135
Pb2+ 0.149, 0.135, 0.119
Table-2.1 s hows i onic radii us ed f or c alculation of t olerance f actors of l anthanum

manganites dope d w ith C a, S r, Ba a nd P b. In di storted pe rovskite s tructures t he
coordination num ber f or t he A -site ma y di ffer from the ide al tw elve. The ta ble a lso
includes i onic r adii f or ni ne-fold ox ygen coordination of t he A -site i ons. A r ough
estimate of the number of electrons in the d bands may be made from the Mn3+ to Mn4+
ratio ba sed on t he s toichimetric f ormula, a ssuming t hat A – site cat ions and O2- (2p6),
make no c ontribution. This num ber i s 4 -x f or di valent s ubstitutions a nd 4 -2x for
monovalent substitutions. O xide stoichiometry may be determined by refinement of site
of site occupancies by neutron diffraction or appropriate chemical analysis for Mn3+ and
Mn4+ [31], w hich of ten g ives s maller d – band oc cupancy ( more hol es or a l arger
effective x ) because fo the non – stoichiometry discussed above [20, 32]. Indications of
the t rue m anganese ch arge s tate a re pr ovided by el ectron – energy – loss s pectroscopy
[33], measurement of t he X – ray absorption ne ar – edge s tructure [ 34, 35] a nd
photoelectron spectroscopy [36].
16 | P a g e
2.2.1 Crystal Structure
Although all the manganites considered here have structures derived from the elementary
cubic pe rovskite cel l w here t he l attice pa rameter a 0 is 0.39 nm and the el ementary cell
contains one formula unit (Z = 1), few of them have precisely this structure because the
atoms a re di splaced f rom t heir i deal pos itions when t ≠ 1. T he pe rovskites s tructure
accommodates m isfit i n the i onic s izes and electronically i nduced de formations b y
various ki nds of di stortions to larger c ells w ith lower s ymmetry. If t is c lose to unity,
there may be a slight rhombohedral distortion involving cooperative rotation of the BO 6
octahedra in the structure of figure 2.2 about a 111 axis. When the misfit is larger, there is
a buckling of the network of octahedra corresponding to cooperative rotation about a 110
axis w hich may l ead to the O – type or thorhombic G dFeO 3 structure s hown i n f igure
2.6(a). This compound has t = 0.91 a nd a = 0.5346nm, b= 0.561nm and c = 0.7668 nm;
the B – O – B bond angle, which is sensitive to the size of the A cation, is reduced from
1800 to 161 0. It is t ypical of the O – type structure that a < c/21/2 < b. A different, O ` -
type, orthorhombic structure adopted by R MnO 3 (R = La – Dy) is shown in figure 2.6(b).
It is a variant with more severely – distorted octahedral environments where c/21/2 < a <b.
The r eason f or t he s evere di stortion i s t he Jahn – Teller ef fect of M n3+ [37-39], w hich
causes the octahedra to extend in one direction in the (a – b) plane.
Fig: 2.6 (a) T he O -type orthorhombic G dFeO 3 structure w hich i s a di storted ve rsion of
ideal pe rovskites s tructure of figure 2.2 with a buc kling o f t he ox ygen oc tahedra t o
accommodate a s maller than ideal A cation. (b) T he O ` - type o rthorhombic LaMnO 3
structure, which incorporates a Jahn – Teller distortion [17] of the oxygen octahedral.
17 | P a g e
Besides the orthorhombic O and O` structures with Z = 4, t here is bewildering variety of
cubic, t etragonal, rhmbohedral, orthorhombic and m onoclinic cells t o cells t o which t he
manganite structures are referred in the literature. These unit cells are closely related, and
rhombohedral or monoclinic angles are very near the ideal values α = 600 or 900 , β = 900.
Figure 2.7 sketches the relation between the various cells. The doubled cubic cell with a ≈
a 0 contains e ight f ormula uni ts ( Z = 8 ). T he r hombohedral c ell w ith a ≈ 2a 0 and α≈
90.40 is a de formed ve rsion, s lightly f lattened a long a 111 di rection. A s maller
rhombohedral cel l with a ≈ 21/2 a 0 and α ≈ 610 is similarly deformed but has Z = 2. As
usual f or r hombohedral c ell w ith s tructures, i t i s m ore c onvenient t o i ndex t hem on a n
hexagonal cell. A closely – related tetragonal cell has a ≈ 21/2 a 0, b ≈ 21/2 a 0, c ≈ 2a 0 have
Z = 4. A cl osely – related tetragonal c ell ha s a = b ≈ 21/2 a 0, c ≈ 2a 0 . Finally, the
monoclinic cells a re slightly – deformed ve rsions of t he s mall cubic c ell ( Z = 1) or t he
orthorhombic cells (Z = 4). In the case where a = b, the monoclinic cell is equivalent to a
larger orthorhombic cell [40, 41].
Fig: 2.7 Relation between the cells used to describe manganese perovskites.
The m onovalent A c ations ha ve a na rrow range of s olid s olubility i n t he r are e arth

manganites, up t o about x 0.2 [42]. The divalent A 2+ cations will substitute to a greater
extent for the rare earth. The calculated energies of solution are lowest for strontium and
calcium [43], and these ions most frequently form an extended or complete range of solid
solution. With increasing di valent A -site s ubstitution ( i.e. i ncreasing M n4+ content) a
sequence of crystallographic and magnetic pha ses ens ues. These are s ummarized for
(La 1-x Ca x )MnO 3 in figure 2.8 and for (La 1- x Sr x )MnO 3 in figure 2 .9. Substitution o f
trivalent A 3+ cations f or l anthanum doe s not a lter t he m anganese va lence, but bismuth,
18 | P a g e
yttrium or a he avier r are ear th reduces t , and increases t he di stortion of the pe rovskite
lattice.
The sequence of phases, O` O R, C, found on increasing the Mn4+ content by A-site

substitution in these s olid solutions is s imilar to that f ound by cation vacancies i n
(LaMn) 1-δ O 3 . The same sequence from distorted to less distorted phases may be seen on
increasing t emperature, or cha nging t he ox ygen s toichiometry [44]. In addition to t he
Mn-O distance, the other important structural parameter in solid solutions is the M-O-Mn
bond a ngle [ 45], w hich i s r elated t o t he A -site c ation radius and the t olerance factor t .
Variations f rom 156 0 to 168 0 are r eported for (R3+ 0.7 A2+ 0.3 )MnO 3 with different cat ions
[46], and from 155 0 to 164 0 in non-stoichiometric LaMnO 3 . Substitution of different rare
earth combinations in ((R 1-y R` y ) 0.67 Ca 0.33 )MnO 3 , for example, allow for variation in
the Mn-O-Mn bond angle without changing the Mn-O distances [47].
Fig: 2.8. M agnetic phases i n (La 1-x Ca x )MnO 3 . The s haded l ine represents t he i nsulator-
metal tr ansition. The r egions indi cated are a s follows: A I, antiferromagnetic -insulator;
CI, canted antiferromagnetic ins ulator; F I, ferromagnetic ins ulator; F M, ferromagnetic
metal; PI paramagnetic insulator [20, 50].
19 | P a g e
A structural study of a (La 0.7 Sr 0.3 )MnO 3 crystal as a f unction of temperature shows it to
be rhombohedral above and below T C (378 K) with a=0.3876 nm and α =90.460 at room
temperature. There is li ttle c hange in the di stortion of the M nO 6 octahedra or t he
Mn-O-Mn bond angle at T C [48]. However, in other compounds with x≈ 0.3 which have
an or thorhombic s tructure a nd s how a l arge r esistivity pe ak there is a m ore s ignificant
change in the distortion of the MnO 6 octahedron near T C [49].
In s ummary, three b road trends evident i n the cr ystal and electronic s tructures o f
manganite solid solutions are firstly passage from static to dynamic Jahn-Teller distortion
of t he ox ygen o ctahedra s urrounding t he M n3+ on i ncreasing x or T (O` O, R
transition), secondly passage from charge-ordered states at certain values of x to charge-
disordered s tates on i ncreasing T or c hanging x a nd t hirdly passage f rom l ocalized to
delocalized electronic states in the vicinity of x≈ 0.3 on decreasing the temperature below
the Curie point.
Fig: 2.9. C rystallographic a nd m agnetic pha ses i n ( La 1-x Sr x )MnO 3 [51]. T he s ymbols
have t he s ame m eanings as i n figure 2 .8 except that the r egions l abelled O `, O a nd R
separated by broken curves refer to the crystal structures.
20 | P a g e
2.2.2 Crystal Field
The c rystal f ield at the c ation sites in the pe rovskites s tructure ha s a f ar – reaching
influence on the electronic and magnetic properties of the oxides. In the i deal structure,
both sites have cubic point symmetry m3m. However, in the real distorted structures, the
point symmetry is much lower.
2.2.2.1 A Site: The crystal field at the A- site in the perovskites structure is conveniently
investigated i n compounds with a non – magnetic trivalent B – site i on s uch as Al3+ or
Ga3+. The r are – earth energy l evels i n crystals of P rGaO 3 [52] and NdGaO 3 [53] have
been i nvestigated b y i nelastic n eutron s cattering. T hese compounds a re bot h
orthorhombic, w ith s pace group P bnm a nd P bn2 l respectively. The environment of t he
rare earth is c onsiderably distorted with low poi nt s ymmetry: m in PrGaO 3 and C 2 in
NdGaO 3 . The nine fold degeneracy of the ground state Pr3+ is entirely lifted by the crystal
field; where as the 4 I9/2 multiplet of Nd3+ is split into five Kramer’s doublets, as shown in
figure 2.10. The ground state has mainly ± ½ > character, giving rise to x – y type easy
anisotropy [ 54]. T he r educed hi gher – order c rystal f ield parameters A n 0, n = 4, 6, a re
similar f or aluminates and gallates of p raseodymium a nd ne odymium. There is no
magnetic down to about 1 K in these oxides; NdGaO 3, for example, orders magnetically
at 0.97 K [54].
2.2.2.2 B Site: The cr ystal f ield here ha s pr edominantly cubic cha racter. Insofar as t he
delocalization of m anganese el ectrons can be ne glected, which is ce rtainly t he c ase t he
end members, x = 0 and x = 1 the strong intra – atomic interactions mean that the energy
of t he M n3+ or M n4+ ions be r epresented b y a cr ystal f ield energy l evel f rom t he
spectroscopic term.
(a) (b)
21 | P a g e
Fig: 2.10 Crystal-field energy l evels i n (a) P rGaO 3 and ( b) NdGaO 3 determined by
inelastic neutron scattering. [52, 53]
For M n3+ in oc tahedral coordination t he g round s tate i s 5

E g, issuing 5D (fi g 2.1 1). In
purely cubic s ymmetry t he ground state is a magnetic singlet [55]. For M n4+ it is 4
A 2g,
4 5 5
issuing from F. The transition from the E g, ground state to the T 2g excited state of
Mn3+ in RMnO 3, which corresponds to promoting an electron from a t 2g to an e g orbital,
was found from optical spectra to be at about 2.1 eV for light rare earths and at 2.3 eV for
heavy rare earths [56].
In L aMnO 3 films, t wo a bsorption ba nds a ppear, namely a s trong ba nd at 1.8 e V a nd a

weaker ba nd at 2 .3 eV; the splitting has b een attributed to t he J ahn – Teller ef fect [ 57]
The d 4 5E g ion in octahedral coordination t 3 2g e1 g is a strong Jahn – Teller ion because it
lowers its e nergy in proportion to the s plitting o f the e g levels b y a uni axial d istortion.
This wa s f irst di scussed b y Kanamori [ 56]. C omparison w ith s pectra of M n3+ in ot her
distorted octahedral environments [58] leads to an estimate of ∆ cf = 10 Dq ≈ 1.5 eV and
2δ JT = 1.0 eV. T he J ahn – Teller s tabilization energy is the refore δ JT , which w as
independently estimated from optical phonon frequencies [59] to be about 0.6 eV [60].
Fig: 2.1 1 Optical tr ansitions f or M n3+ in (a) a f ree i on, (b) an octahedral s ite and (c) a
uniaxially distorted octahedral site [56]
2.2.3 Electronic Structure

The pe rovskites – structure ox ides w ith a c losed – shell i on on B s ites a re t ransparent
insulators. Examples a re C atiO 3, SrTiO 3, LaAlO 3, LaScO 3, and LaGaO 3. The Ti 4+ and
Sc3+ cation have a d 0 configuration, where as that of Ga3+ is d10. In LaAlO 3 there is a gap
of 5.6 eV between the top of the valence band which is derived from the filled oxygen 2p
orbitals of O 2- and the bottom of the empty conduction bands which are derived from the
22 | P a g e
unoccupied 5d – 6s orbitals of the La3+ or 3s orbitals of the Al3+. Empty d 0 levels usually
lie near the top of this 2p – ns gap, where as filled 3d 10 levels lie below the top of the 2p
band. T he d l evels f all at pr ogressively l ower e nergy on pa ssing a long t he 3d s eries
because of the increasing nuclear charge. LaScO 3 is a transparent insulator with a gap of
about 6 e V b etween t he ox ygen 2p v alence b and a nd t he bot tom of the e mpty 3d
conduction band [61] the gap in CaTiO 3 or SrTiO 3 is less, about 3 eV.
For 3d n cations, the Fermi level falls in the narrow d ba nd, and very interesting physics
arises be cause of t he s trong e lectron c orrelations i n t his ba nd. T he t raditional a pproach
has be en t o r egard t ransition – metal ox ides a s ionic c ompounds w ith well de fined 3d
configurations i ncorporating a n i ntegral num ber o f l ocalized e lectrons pe r i on. T his
approach ha s be en s uccessful i n accounting f or m any aspects of t heir be haviour,
including magnetic moment formation. The model has considerable predictive power, and
it is po ssible to r elate the pa rameters in the model t o spectroscopic m easurements.
However e lectron t ransfer a nd or bital a dmixtures a re m ore pr operly t reated i n a ba nd
model. B and s tructure determinations i nvolve e xtensive c omputations, a nd i t i s more
difficult t o bui ld up a n i ntuitive unde rstanding of t he r elation between electron number
and ph ysical pr operties. R ecent de velopments, pa rticularly t he l ocal s pin de nsity
approximation [62], offer access to magnetic ground – state properties via a workstation
and provide insight into the extent of orbital mixing which is considerable in all transition
– metal oxides. Most difficult to treat accurately are the inter-atomic correlations.
Transitions – metal ox ides ar e m aterials w hose electronic p roperties are de termined by

interplay of s everal i nteractions of c omparable m agnitude, a ll o f or der 1 eV.
Schematically, these are as follows:
(i) the M ott – Hubbard i nteraction U dd , w hich i s t he c ost of creating a dn+1dn-1
charge excitation in an array of dn ions;
(ii) the cha rge – transfer int eraction U pd , w hich i s t he cos t of t ransferring an
oxygen p e lectron t o t he ne ighbouring d i on t o c reate a p 5 dn+1 charge
excitation from p6 dn;
(iii)the transfer integral t which determines the d – electron bandwidth W;
(iv) the Hund rule on – site exchange interaction U ex which is the energy required
to flip a d – electron spin;
(v) the crystal – field interactions ∆ cf and δ JT.
23 | P a g e
Besides the classical Bloch – Wilson insulators where the Fermi level falls in a gap in the
one – electron de nsity of s tates, transition – metal ox ides ma y b e M ott – Hubbard or
charge – transfer i nsulators w hen t he e lectron c orrelations a re s uch t hat U dd > W or
U pd >W r espectively [ 63,64]]. M ost o xides of t he e arly 3d t ransition m etals a re M ott –
Hubbard insulators and many oxides of the late 3d transition metals are charge – transfer
insulators. A t t he e nd of t he 3d s eries, t he c harge t ransfer gap m ay go t o z ero, a nd t he
oxides then become metals.
2.2.4 Ionic Model
It is considered further the e lectronic s tructure of ma nganese ions in B s ites of the
perovskites structure, where they are coordinated by an octahedron of oxygen neighbors,
assuming for th e mom ent tha t the re is an integral num ber of d e lectrons pe r s ite. It is
useful t o f ocus he re on the one – electron e nergy levels r ather t han on t he m ultiple –
electron states, although they are closely related for the d 4 ion Mn3+. The inter electronic
correlations w hich give r ise t o t he Hund r ules f or t he free i on are pe rturbed b y the
crystalline electrostatic field due to the oxygen anions. The five d orbitals, each of which
can accommodate one e lectron of s pin, a re s pilt b y the o ctahedral c rystal f ield i nto a
group of three t 2g (≡ d ε ) –d xy : d yz : d zx orbitals which have their lobes oriented between
2 2
the ox ygen neighbours and a group of two e g (≡ d γ ) – d x -y , d z 2 orbitals which are
directed t owards t he ox ygen ne ighbours. T he former obvi ously ha ve a l ower energy
because of t he electrostatic repulsion of electrons on ne ighbouring s ites, and t he crystal
field splitting ∆ cf (≡ 10Dq) between the t 2g and e g orbitals is of the order 1.5 eV. The intra
– atomic correlations which give rise to the Hund first rule ( maximum S ) is represented
on one – electron energy di agram by i ntroducing a n e nergy s plitting U ex of ↑ and ↓
orbitals, which is greater than ∆ cf. Good evidence that U ex and ∆ cf are quite similar in
magnitude i n t he p erovskites – structure ox ides i s pr ovided b y t he t rivalent c obalt i n
LaCoO 3 which does not follow the Hund first rule; it is in a low – spin state, 3d6, t 2g 6 with
S = 0 . T rivalent nickel in nickel – substituted manganites is also of a low – spin nature
[28]. Manganese ions generally have a high spin; the divalent ion Mn2+ has a ve ry stable
3d5 configuration, a ha lf – filled s hell t 2g 3↑ e g 2↑ S = 5/ 2 and a s pherically s ymmetric
electron density. Trivalent manganese is 3d 4 t 2g 3↑ e g ↑ with S = 2, w here as quadrivalent
manganese is 3d3, t 2g 3↑ with S = 3/2. The spin – only moments of these ions are 5µ B, 4µ B
and 3µ B respectively.
24 | P a g e
A distortion of the oxygen octahedron lowers the s ymmetry of the cubic crystal field in
such a way that the centre of gravity of the t 2g levels and the centre of gravity of the eg
levels is unchanged. There is therefore nothing to be gained by Mn2+ or Mn4+ from such a
distortion, but M n3+ [65,66] can lower i ts en ergy will s cale as t he d istortion s quared,
hence we have the marked tendency of d 4 ions to distort their octahedral environment in
order to lower their energy. This is the Jahn – Teller effects. For example, the tetragonal
elongation of the octahedron found in the O` - type structure will stabilize the d z 2 orbital
relative to the d x 2 - y2 orbital, as shown in figure 2.12. The t 2g orbitals overlap relatively
little with the orbitals of nearby ox ygen or lanthanum ions (fig. 2.13) so these electrons
tend to form a localized t 2g 3↑ ion core. However the e g orbitals overlap directly with the p
orbitals of the oxygen neighbours, so they tend to form a σ* anti-bonding band.
Fig: 2.1 2 Occupancy o f one – electron energy l evels f or M n4+, M n3+, a nd M n2+ in
octahedral coordination. T he e ffect o f a t etragonal di stortion i s t o l ower t he e nergy of
Mn3+ by δ JT , but it leaves the others unchanged [66].
The end member compounds such as LaMnO 3 have a distorted perovskite structure where
the F ermi l evel f alls i n a gap be tween t he t wo Jahn – Teller s plit e g bands. H owever,
intermediate compositions such as (La 1-x Ca x )MnO 3 with a cubic structure have a partly –
filled σ* band, extending in three dimensions. These band electrons, which we refer to the
Zener e lectrons, hop from one m anganese s ite t o a nother w ith s pin m emory. T hey are
both conduction electrons and mediators of the ferromagnetic exchange. Direct overlap of
the t 2g core electrons of adjacent manganese ions leads to anti-parallel exchange coupling,
since only the ↓ orbitals are empty [38].
25 | P a g e
The e nergies i nvolved i n t he i onic m odel c an be d educed f rom s pectroscopic
measurements. The octahedral crystal field splitting ∆ cf decreases with increasing Mn – O
distance. Typical values for Mn4+, Mn3+ and Mn2+ in oxides are 2.5 eV, 1.8 eV and 1.0 eV
respectively [ 59]. Estimates f or m anganese pe rovskites f rom s oft X – ray s pectroscopy
are 2.4 eV fo r M n4+ and 1.5 e V f or M n3+ [67]. A ctually M n3+ has a t endency t o
disproportionate into a mixture of Mn2+ and M n4+, for instance in aqueous solution, but
the ion can be stabilized in octahedral sites by the Jahn – Teller distortion.
Fig: 2.13 Illustration of the orbital overlap in a plane of the perovskite structure. The d xy
orbital (a t 2g orbital) has little overlap with 2p orbitals of the oxygen neighbours, whereas
the d x 2 and d y 2 orbitals (e g orbitals) overlap strongly with the oxygen p x or p y orbitals to
form a σ * band. Displacements of the oxygen atoms in the plane are indicated by arrows.
EF
1–x [2] eg ↑ (Mn) : σ* 0
1
[3] t 2g ↑(Mn) 2
3
[18] 2p (O) eV
(La 1-x Ca x )MnO 3

Fig: 2.14 Schematic energy band structure of (La 1-x Ca x )MnO 3
26 | P a g e
The Jahn – Teller splitting of the e g levels is in the range 2δ JT = 0.5 – 1.5 eV in various
Mn3+ minerals [59]. In LaMnO 3 , attribution of the broad feature in the optical absorption
spectrum ne ar 2 e V t o t he 5E g → 5T 2g transition of M n3+ gives a value of ∆ cf which i s
consistent w ith ot her estimates; t he a bsorption edge a t 3.1 e V i s a scribed t o 2p → 3d
charge transfer [57]. This then places the t 2g levels above the top of the oxygen 2p b and,
in a ccord w ith m olecular or bital c alculations f or t he ( MnO 6 ) cluster [ 68]. X – ray
photoemission s tudies, opt ical c onductivity and electron – energy – loss s pectroscopy,
however, place the t 2g levels below the top of the 2p band [69,70].
The H und r ule e xchange s plitting U ex between t he s tates w ith t otal s pin 2 a nd 1 i s
evaluated from equation (2.2) taking s = ½ and S = 3/2 as the spins of the e g electrons and
the t 2g 3 ion core. The result U ex = J H (S+ ½) gives 2J H as the splitting. The value of U ex is
found from optical conductivity data to be 2.0 e V [60] which is slightly greater than ∆ cf,
as ex pected. Hence J H = 1.0eV. A s omewhat l arger va lue w as i nferred f rom s canning
tunneling s pectroscopy [ 71-73].The ef fective e xchange pa rameters J ij (= J 1, J 2 ) for
neighbouring m anganese i ons i n the H eisenberg Hamiltonian – 2 J ij S i .S j are of or der
t2/U, where t is the transfer integral which gives rise to the bandwidth W.
2.2.5 Band Model: Unlike the ionic 4f levels, which are little broadened by overlap and
hybridization, t he 3d i onic l evels a cquire a s ubstantial ba ndwidth, of or der 1 e V, f rom
overlap with t he neighbouring o rbitals. The bandwidth W = 2 Zt, where t i s t he t ransfer
integral and z is t he num ber of m anganese ne arest ne ighbours. T his i s i ndicated i n t he
modified one – electron energy levels of figure 2.14. The e g bandwidth W is sensitive to
Mn – O distances and Mn – O – Mn bond angles [74]. In the double – exchange model it
also depends on m agnetic or der, vi a equation (2.1). Band s tructure c alculations t ake
account of intra – atomic correlations in an averaged way and they reproduce the one –
electron energy le vel s plitting of the c rystal – field t heory b y a dmixture of p a nd d
electron orbital. One that has proven quite successful in reproducing the density of states,
the ordered magnetic structures and even the magneto crystalline anisotropy of 3d metals
and alloys is the local spin density approximation (LSDA). Sarma et al. [61], Pickett and
Singh [ 63-64], S atpathy et a l. [ 75-76] a nd S olovyev e t al. [ 77] ha ve a pplied t he LSDA
method to LaMnO 3 and related oxides such as LaBO 3 , where B = Fe, Co, or Ni. Both the
linear au gmented plane wave [ 78-81], a nd l inear m uffin – tin orbital – atomic s phere
approximation give nearly identical results [63]. The unrestricted Hartee – Fock method
27 | P a g e
has also been successfully applied to the perovskite oxides [82, 83], and there have been
calculations using the Korringa–Rostoker method.
Before di scussing the electronic s tructure of m aterials, which exhibit l arge n egative
Magneto-resistance, it is appropriate to consider first the end members. With this method,
it i s pos sible to t ake di fferent c rystallographic unit c ells ( orthorhombic or c ubic) a nd
different m agnetic ar rangements ( ferromagnetic, ant i-ferromagnetic or p aramagnetic) i n
order t o calculate t he free ene rgy as sociated with each of t hem and thereby t o evaluate
which is the ground state. For a case, an electronic density o f states is o btained and the
character of the wave functions (s, p, d) can be evaluated. The different calculations agree
very w ell on the ma in features. Sarma et al . [61] w ere abl e t o predict the m ost s table
magnetic a rrangements f or t he four ox ides t hat t hey studied, n amely LaCoO 3 , LaFeO 3 ,
LaNiO 3 and L aMnO 3 . The i mportance of t he crystal s tructure i s de monstrated b y t he
result that, without the Jahn – Teller distortion (i.e. for a cubic cell), LaMnO 3 would be a
ferromagnetic metal rather than A – type anti-ferromagnetic insulator [62, 74-76, 78]. The
same c onclusion ha d b een dr awn from s usceptibility m easurements a bove 750 K b y
Jonker [ 83]. T he J ahn T eller e ffect r esponsible f or t he O ` or thorhombic distortion a lso
leads to the stabilization of the A type anti-ferromagnetism. The splitting of the e g bands,
due to the Jahn – Teller distortion, leads to a small indirect gap of order 0.1 eV between
the e g1 (≈ d z 2) and e g2 (≈ d x 2 – y 2) bands, each about 1 eV wide. The other end member,
CaMnO 3 is c ubic w ith the G – type a nti-ferromagnetic structure, as obs erved
experimentally without any splitting of the e g bands. The exchange splitting U = 3.0 eV
and a 0.42 eV gap opens between the t 2g ↑ and a band of mixed t 2g ↓ and e g ↑ character [75].
For bot h e nd m ember c ompounds, S atpathy e t a l. [76] fo und t hat t he ionic de scriptions
La3+Mn3+O 3 2- and Ca2+Mn4+O 3 2- are good approximations to reality. In order to account
for the difficulty where two electrons occupy the same manganese ion, a strong on – site
Coulomb i nteraction U dd be i ntroduced i nto t he LSDA c alculation [76, 84, 85]. T he
valence band is originally composed of the Mn 3d a nd O 2p ba nds with the Mn 3d-band
center above the O 2p-band center. In this case, the density of states near the Fermi level
would become mainly of O 2p character. The calculated magnetic moments for LaMnO 3
are in quite good agreement with the experimental values of (3.7-3.9) µB . [39, 85].
28 | P a g e
For their Hartree-Fock calculations, Mizokawa and Fujimori [80, 81] take realistic values
U dd = 5 .5eV a nd U pd = 4.0e V from phot oemission s pectroscopy a nd show t he a nti-
ferromagnetic order in LaMnO 3 is related to orbital order and the Jahn-Teller distortion.
29 | P a g e
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35 | P a g e
Chapter Three Literature Review
3.1 Introduction
Modern society relies very much on r eadily available refrigeration. Until now the vapor
compression refrigerators have been mainly used for cooling applications. However, the
compressing and expanding processes of a gas in these refrigerators are not very efficient
because the refrigeration accounts for 25% of residential and 15% of commercial power
consumption [1]. In addition, the usage of gases such as chlorofluorocarbons (CFCs) and
hydrochloric fluorocarbons (HCFCs) are damaging to our living environment.
Recently, the development of a new magnetic refrigeration (MR) technology, based upon
the magnetocaloric effect (MCE) [2], has brought an alternative to the conventional gas
compression (CGC) technique [3,4]. The MR technology shows several advantages over
the CGC technology [3]. First, the cooling efficiency in magnetic refrigerators is higher
(the magnetic cooling efficiency can be reached up to 30–60% of a Carnot cycle, whereas
it is on ly 5 –10% for CGC refrigeration) even at a s mall scale, enabling the development
of por table, b attery-powered products. Second, magnetic r efrigerators can be m ore
compactly bui lt w hen us ing s olid s ubstances a s w orking m aterials. T hird, t he M R doe s
not u se oz one-depleting or g lobal-warming gases a nd t herefore i s a n e nvironmentally
friendly c ooling t echnology. It i s i mportant t o m ention t hat M R ha s f ound w ide
applications i n e nergy-intensive i ndustrial and commercial r efrigerators s uch as l arge-
scale ai r c onditioners, heat pum ps, s upermarket r efrigeration uni ts, w aste s eparation,
chemical processing, gas l iquefaction, l iquor di stilling, s ugar refining, grain dr ying, and
so forth [3, 4].
MR ha s l ong be en e mployed t o c ooling be low 1K us ing pa ramagnetic s alts ( e.g.,

Gd2(SO4)3.8H2O) [5], bu t i ts a pplications a t t emperatures a round r oom t emperature are
not yet commercially available [3], although this technology is believed to be a great new
global business [3,4]. Until recently a gadolinium (Gd) rare-earth metal with large MCE
has be en c onsidered a s t he m ost a ctive m agnetic r efrigerant i n r oom-temperature
magnetic r efrigerators [3], but its us age is s omehow c ommercially limite d because the
cost of G d i s qui te e xpensive ∼$4000/kg. T herefore, research i n t he m agnetic c ooling
field has be en focused on the s earch for ne w m aterials t hat ar e che aper but di splaying
larger M CEs [6–10]. A s a r emarkable b reakthrough oc curred i n 1997, P echarsky and
36 | P a g e
Gschneidner [6] discovered that the giant magneto-caloric (GMC) effect in a Gd5Si2Ge2
alloy was t wice l arger t han i n Gd. M ore i mportantly, t his alloy could n ot onl y i mprove
the efficiency of large-scale magnetic refrigerators but also open the door to new small-
scale a pplications, s uch as hom e a nd a utomotive a ir c onditioning [3]. Nonetheless, t he
Curie temperature of Gd5Si2Ge2 is about 276 K , which is much lower than that of Gd of
294 K, making this alloy difficult to be used in room-temperature magnetic refrigerators
[4]. In t his c ontext, f urther e fforts t o s eek f or ot her a lternative ma terials, e specially the
materials w ithout r are-earth elements, for example, Ni–Mn–Ga al loys [7], M n–As–Sb
alloys [8], La–Fe– Co–S a lloys [9],Mn–Fe–P–As a lloys [10], La–Ca–Sr–Mn–O
manganites [11] and e xhibiting l arge M CEs i n t he r oom-temperature r ange, are also of
practical importance.
This review aims to provide a through understanding of the magneto-caloric nature of a

new class of manganites and their potentials for active MR (AMR). The advantages and
disadvantages of such magneto-caloric manganites are analyzed and discussed, in order to
nominate pot ential m agneto-caloric m anganites f or f uture M R t echnology. A
comprehensive comparison of the MCE of the manganites with other magnetic refrigerant
candidate materials is given. The fundamental aspects of MCE as well as the criteria for
selecting magnetic refrigerants for AMR are also discussed.
3.2 Fundamental Aspects

When a magnetic material is subjected to a sufficiently high magnetic field, the magnetic
moments of t he atoms b ecome reoriented. If t he magnetic field is applied adiabatically,
the temperature of the material rises, and if the magnetic field is subsequently removed,
the temperature decreases. This warming and cooling in response to the application and
removal of an external magnetic f ield is c alled the ‘ MCE’. Since the MCE is di rectly
related to the m agnetic ent ropy cha nge and the adi abatic t emperature cha nge, it i s
important to understand the relation between these two quantities.
3.2.1. Relation between Magnetic Entropy and Adiabatic Temperature change

The change of entropy (S) of a magnetic material upon the application of a magnetic field
(H) is related to that o f magnetization (M) w ith respect to temperature ( T) thr ough the
thermodynamic M axwell r elation. T he m agnetic ent ropy cha nge, ∆SM (T, H), is
37 | P a g e
calculated from magnetization measurements m ade at di screte f ield and temperature
intervals, ∆SM (T, H) can be approximately calculated by the following expression:
M i +1 (Ti +1 , H ) − M i (Ti , H )
∆S M (T , H ) = ∑ ∆H 3.1
i Ti +1 − Ti
On t he ot her ha nd, ∆SM (T, H ) c an be obt ained from c alorimetric me asurements of the
field dependence of the heat capacity and subsequent integration:
C (T , H ) − C (T ,0 )
∆S M (T , H ) = ∫ dT 3.2
T
where C(T, B) and C(T, 0) are the values of the heat capacity measured in a field H and in
zero field (H = 0), respectively. Therefore, the adiabatic temperature change (∆Tad) can be
evaluated by integrating Eq. (3.2) over the magnetic field, which is given by
T  ∂M 
H
∆Tad = − ∫   dH 3.3
0
C P,H  ∂T H
From Eqs. (3.1) and (3.3) it is easy to state that a material should have large MCE (i.e.,
large ∆SM and ∆Tad) when (∂M/∂T)H is large and C(T, H) is small at the same temperature
[3,4]. Because (∂M/∂T)H peaks the magnetic ordering temperature, a large MCE is often
expected close to this magnetic phase transition, and the effect may be further maximized
as t he change i n magnetization with respect t o temperature o ccurs i n a n arrow
temperature i nterval [4]. I t s hould be not ed t hat a lthough e valuating ∆SM from
magnetization measurements using Eq. (3.1) has been a useful tool for a rapid screening
of potential magneto-caloric m aterials [3–11], a precise comparison of t he M CE among
the exiting magneto-caloric materials can onl y be realized by evaluating ∆Tad instead of
∆SM [3, 4]. This is because the magnitude of heat capacity may be much different from a
magneto-caloric material family to another, for example, the heat capacity of a G d-based
alloys system is much smaller than that of a manganite type materials system [3].
3.2.2 Relation between Magnetic Entropy and Resistivity

In manganites, both CMR (Colossal magneto resistive) and MC (magneto-caloric) effects
are of ten obs erved around t he m agnetic-ordering pha se t ransition t emperature ( i.e., t he
Curie temperature) [11–13] and this evidently suggests that there exists a definite relation
between magnetic entropy and resistivity [14–17]. In this case, Xiong et al. [17] proposed
38 | P a g e
a ne w m ethod t hat a llows e valuating t he relation be tween t he m agnetic e ntropy and
resistivity (ρ) of a manganite material by means of
 ∂ ln (ρ ) 
∆S M (T , H ) = −α ∫  dH 3.4
 ∂T  H
with α= 21.72 emu/g. It is clear that a larger a leads to a more sensitive dependence of ∆S
- ρ. M agnetic di sorder, w hich is ch aracterized b y ∆S, affects m agnetic pol arons t hat
influence the electric transport property thereby leading to the relation of ∆S - ρ. [14,17].
This relation is only valid in a narrow temperature interval, where the magnetic-ordering
phase transition occurs [17]. The deviation of Eq. (3.4) occurring in the low temperature
range is because the magnetic polarons are significantly depressed when the system is at a
relative ma gnetic-ordered state [16, 17]. I n general, t he r elation ( 3.4) pr ovides a n
alternative m ethod to determine the ma gnetic e ntropy change in perovskite ma nganites
from resistive measurements.
3.2.3 Magneto-caloric behavior and Magnetic Transition

It is pointed out that the magnitude of the magnetic entropy change and its dependence on
temperature and magnetic field are strongly dependent on the nature of the corresponding
magnetic pha se tr ansition. A f irst-order f ield-induced paramagnetic t o f erromagnetic
transition, which is a magnetic disorder-to-order transition, can give rise to a GMC effect,
for example, in Gd–Si–Ge and Mn–Fe–P–As systems [3, 4]. However, the field-induced
first-order transition, which is a magnetic order-to-order transition, results in a relatively
small M CE, f or example, i n R TiGe and M n5Si3 systems [3]. M ost f erromagnetic
materials show a s econd-order magnetic phase transition. It should be noted that a first-
order t ransition i s able t o concentrate t he M CE i n a na rrow t emperature range, whereas
second-order t ransitions a re us ually s pread ove r a br oad t emperature range, w hich i s
beneficial for AMR [3, 4, 11]. In addition, there are large thermal and field hystereses for
any fi rst-order t ransitions, w hich f or pr actical A MR a pplications s hould be a s s mall as
possible [4].
Furthermore, it is stated that the magnitude of the MCE depends not only on the magnetic
moments but also on ∂M/∂T. These larger these values, the higher the MCE. This is the
reason why not only rare-earth elements and their compounds have large MCEs [6], but
also 3d-based transition–metal compounds can have large MCEs in case o f a first-order
39 | P a g e
transition [10]. In the case of manganite materials, it is the rapid change of magnetization
with respect to temperature in the magnetic-ordering phase transition range that causes a
large m agnetic ent ropy change, i.e., the l arge MCE [11]. Indeed, T erashita e t a l. [16]
recently revealed that a first-order structural transition in close proximity to the magnetic
transition has only little influence on the MCE in doped manganites.
3.2.4 Magnetic Cooling Efficiency

The m agnetic cooling efficiency o f a m agneto-caloric m aterial can be , in simple cas es,
evaluated b y considering t he m agnitude of ∆SM or ∆Tad and i ts full-width at ha lf
maximum (δTFWHM) [3,18]. It is easy to establish the product of the ∆SM maximum and
the full-width at half maximum (δTFWHM = T2 - T1) as
RCP (S) = - ∆SM (T, H) × δTFWHM, 3.5
which s tands for t he s o-called relative c ooling pow er ( RCP) ba sed on t he m agnetic
entropy change. Similarly, the pr oduct of t he maximum adi abatic t emperature cha nge
∆Tad and the full-width at half-maximum δTFWHM is expressed by
RCP (S) = ∆Tad (T, H) × δTFWHM, 3.6
which stands for the so-called RCP based on the adiabatic temperature change.
In short, it is pos sible to e valuate the ma gnetic c ooling e fficiency of a ma gneto-caloric
material b y c alculating RCP ( S) us ing E q. (3.5) or R CP (T ) us ing E q. (3. 6). In t his
review, we will evaluate the RCP of magneto-caloric manganites using RCP (S).
3.3 Magneto-caloric Measurements

It is possible to measure MCE directly or to calculate MCE indirectly from the measured
magnetization or field dependence of the heat capacity, both as a function of temperature
and magnetic field [3, 4]. It has been shown that, for direct measurement techniques, the
accuracy is in the range of 5–10% and depending on t he errors in thermometry, errors in
field setting, the qua lity of the rmal ins ulation of the s ample, the quality of th e
compensation scheme t o eliminate t he ef fect of t he cha nging m agnetic f ield on the
temperature s ensor r eading [18–21]. F or i ndirect m easurement t echniques, M CE
calculated from m agnetization da ta ha s qui te hi gh e rrors ( ∼20–30%), w hereas M CE
calculated from h eat capacity data shows a better accu racy than any other techniques at
low t emperatures. N ear r oom t emperature, ho wever, due t o t he a ccumulation of
experimental e rrors in the tot al e ntropy f unctions, the e rrors a rising in M CE e valuation
40 | P a g e
become approximately the same as those from direct techniques or indirect magnetization
measurements [19, 21].
It should be noted that, for first-order phase transition materials, it is not easy to precisely
measure MCE. In this case, the MCE calculated from heat capacity should be compared
with t hat m easured directly und er equilibrium c onditions or c alculated f rom
magnetization data to ensure th at the pot entially d eleterious effects of int rinsically
inaccurate h eat capacity ha ve be en el iminated or m inimized [18,19]. F or t he case of
manganite materials, beside the above-mentioned techniques, MCE can also be evaluated
from resistive measurement [17].
3.4 Manganite Materials

In view of the recent literatures, most manganite materials with respect to their magneto-
caloric pr operties ha ve been e xtensively s tudied i n C hina, S pain, B razil, U SA, U K,
Vietnam a nd S outh K orea. In or der t o c larify w hether s uch m anganites c an be us ed a s
active ma gnetic r efrigerants in magnetic r efrigerators, in this s ection, we w ill first
describe briefly the formation of such a manganite structure that is related directly to its
magnetic and magneto-caloric behavior and will then analyze systematically the magneto-
caloric properties of this material family. Finally, the MCE features of the manganites are
compared with those of other magnetic refrigerant candidate materials.
3.4.1. Structure
Manganites (or the so-called manganese oxides) have a general formula of R 1-x MxMnO3,
where R stands for trivalent rare-earth elements such as La, Pr, Nd, Sm, Eu, Gd, Ho, Tb,
Y, e tc., a nd M s tands f or di valent a lkaline e arth i ons s uch a s S r, C a, B a, a nd P b or f or
Na1+, K 1+, Ag1+, etc. The (R, M) site (i.e., the so-called perovskite A-site) can be in most
cases f ormed f rom ho mogeneous s olid s olution [22]. It ha s be en f ound t hat t hese
perovskite-based structures occasionally show lattice distortion as modifications from the
cubic structure. One of the possible origins in the lattice distortion is the deformation of
the MnO6 octahedron arising from the Jahn–Teller effect that is inherent to the high-spin
(S = 2) Mn3+ with double degeneracy of the eg orbital. Another lattice deformation comes
from t he c onnective pa ttern of t he M nO6 octahedra i n t he pe rovskite s tructure, f orming
rhombohedral or orthorhombic lattice. In these distorted perovskites, the MnO6 octahedra
show alternating buckling. Such a lattice distortion of the perovskite in the form of ABO3
41 | P a g e
(here A = R 1-xMx and B = M n for t he present m anganites) i s governed b y t he s o-called
tolerance factor t, which is defined as t =(rA+rO)/√2(rB+rO) . Here r A, rB and rO represents
the ave raged i onic s ize of ea ch element. The t olerance f actor t m easures, by definition,
the lattice matching of the sequential AO and BO2 planes. For t ≈1, the cubic perovskite
structure is realized. As r A or t decreases, the lattice structure can be transformed into the
rhombohedral ( 0.96<t<1) a nd t hen i nto t he or thorhombic s tructure ( t<0.96), w here t he
B–O–B bond a ngle θ is be nt a nd de viated from 180 0. A nother i mportant f eature i n t he
perovskite and related structures is that the compounds are reasonably appropriate for the
carrier-doping pr ocedure ( filling c ontrol) s ince t his s tructure i s ve ry robust a gainst
chemical modifications on the A-site. It is important to mention that because the magnetic
properties of m anganites, Curie t emperature and s aturation magnetization, are s trongly
doping-dependent, t hese m aterials m ay be good candi dates f or MR at va rious
temperatures.
In general, t he c onventional s olid-state r eaction m ethod ha s be en us ed t o s ynthesize

polycrystalline ma nganite ma terials. Stoichiometric s amples a re us ually pre-sintered i n
the t emperature r ange o f 700 –9000 C for 10 –20 h f ollowed b y grinding i nto mixed
powders. The mixed powders are then pressed into pellets and sintered at 900–13000 C for
15–30 h to give the finished samples. Besides, the sol–gel method has recently been used
to synthesize such ceramic materials.
3.4.2. Magneto-Caloric Effect

For a quick comparison of the MCE of existing manganites, the magnetic entropy change,
∆SM, the Curie temperature, TC, the magnetic field change, ∆H, and the relative cooling
power, RCP (S), may be analyzed.
3.4.2.1. (La1-xMx) MnO3 where M = Na, K and Ag

A number of works reported the MCEs in lanthanum manganites with doping M1+ ions in
the La-site, that is, La1-xMxMnO3 with M = Na, K and Ag. Zhong et al. [23–25] showed
that the MCE peak temperature could be tuned in the temperature range of 195–334 K for
La1-xNaxMnO3 compounds and in the temperature range of 230–334K for La 1-xK xMnO3
compounds. Because these materials also exhibited relatively large MCEs, they could be
appropriate for MR in the corresponding temperature ranges. More interestingly, Tang et
al. [26] found the large MCEs in La1-xAgxMnO3 (0≤x≤0.3) manganites. They showed that
42 | P a g e
for ∆H = 1T , ∆SM reached a m aximum of -3.4 J /kgK f or La0.8Ag0.2MnO3; thi s va lue is
obviously l arger t han t hat obs erved i n G d, ∆SM = -3.1 J/kg K . B y va rying A g
concentration of La1-xAgxMnO3, Hien et al. [27] revealed that the MCE peak temperature
could be tuned in the room temperature range and the ∆SM value was the highest for x =
0.22 composition. This indicates that La1-xAgxMnO3 (x = 0.2, 0.22) materials are potential
for room temperature MR. However, the non-uniform distribution of the MCE curve was
observed i n t hese s amples, w hich i s not de sirable f or an E ricsson-cycle m agnetic
refrigerator.
3.4.2.2. (La1-xMx) MnO3 where M = Ca, Sr, Ba, Cd and Pb

3.4.2.2.1. (La1-xCax) MnO3
The M CEs of La1-xMxMnO3 (M = C a, Sr, Ba) m anganite f ilms w ere first re ported by
Morelli et al. [28]. However, the obtained ∆SM values were not very large except that the
MCE peak temperature could be tuned in the temperature range of 250–350 K by varying
the doping concentration. More interestingly, Guo et al. [29,30] found the large MCEs in
La1-xCaxMnO3 polycrystalline s amples w ith 0.20 ≤x≤0.33. I t w as s hown t hat, f or
∆H = 1.5 T, t he ∆SM reached a m aximum of ab out -5.5 J /kgK a t 230 K , -4.7 J /kgK at
224K and -4.3 J/kgK at 260K for x = 0.2, 0.25, and 0.33 compositions, respectively [29].
These values are larger than that of Gd, ∆SM = -4.2 J/kg K, for the same field change of
1.5 T [3]. I n t his c ase, t hat t he l arge m agnetic e ntropy c hange pr oduced b y t he a brupt
reduction of ma gnetization was be lieved to be a ttributed t o t he a nomalous t hermal
expansion j ust a round t he C urie t emperature [29, 30]. D ue t o t his e ffect, t he na rrow
FWHM of t he M CE c urve ( δTFWHM) for La1-xCaxMnO3 (0.20≤x≤0.33) s amples w as
observed [29]. In contrast, Zhang et al. [31] found a smaller value of ∆SM of -0.6 J/kgK
for ∆H = 1T and a wider breadth of the MCE peak, δTFWHM = 62 K, in La0.67Ca0.33MnO3
(x = 0.33) t han w hat G uo e t a l. [29] reported. This di screpancy c ould arise f rom t he
differences i n t he s ample pr ocessing r outes a nd/or f rom t he di fferently che mical
composition. I n fact, L a0.67Ca0.33MnO3 was f ound t o s how t he l argest M CE a mong t he
compositions investigated [32–34]. Lin et al. [34] measured the MCE of La0.67Ca0.33MnO3
and found the ∆Tad of 2.4K for ∆H = 2.02 T. This value of ∆Tad is smaller than that of Gd.
It was suggested that the large magnetic entropy change be produced by the abrupt jump
in magnetization that is associated with a f irst-order m agnetic pha se t ransition [32,33].
Because o f t his f act, a d rop of t he M CE, which is r elated to the change from f irst - to
43 | P a g e
second or der ph ase t ransition w as obs erved [33]. Note t hat, while t he MCE de creased
significantly, the M CE cure be came m ore br oadening w hen the m aterial t ransformed
from a first-order phase magnetic transition to a second-order one, which is beneficial for
MR [11,33]. The MCEs were also reported in several deficient manganites. Xu et al. [35]
showed that the La0.54Ca0.32MnO3-δ deficient manganite had a large ∆SM of -2.9 J/kgK for
∆H = 0.9T [35]. Interestingly, the Curie temperature of this sample is ∼272 K, about 10K
higher than that of the La0.67Ca0.33MnO3 compound. This indicates that La0.54Ca0.32MnO3-δ
could be us ed as active m agnetic r efrigerants i n sub-room-temperature m agnetic
refrigerators. In another investigation, Hueso et al. [36] revealed the possibility of tuning
the MCE peak temperature without suppressing large MCE values of La0.67Ca0.33MnO3-δ
nano-particles s ynthesized b y s ol–gel t echniques. It s hould be , how ever, noted t hat t he
magnitude of ∆SM was found to be inversely proportional to the grain size [36]. Phan et
al. [37,38] also investigated the ma gnetic a nd magneto-caloric pr operties o f
(La1-x) 0.8Ca0.2MnO3 (x = 0.05, 0.10, 0.20, and 0.30) with deficient La-site vacancies. It is
interesting that the increase in La-deficiency favored not only the MCE but also lifted the
Curie t emperature up to hi gher va lues, w hich i s be neficial for M R a t va rious
temperatures. Recently, Hou et al. [39] also investigated the MCEs of La0.67-xCa0.33MnO3
(x = 0, 0.02, 0.06, and 0.1) deficient samples. The largest ∆SM value was obtained to be
-2.78 J/kgK at 277K for ∆H = 1T for the x =0.02 sample. This material could be good for
sub-room-temperature MR.
3.4.2.2.2. (La1-xSrx) MnO3

In o rder t o t ailor M CEs i n t he r oom-temperature r ange, several ef forts w ere m ade t o
explore the MCEs of La1-xSrxMnO3 manganites [12,20,21,33]. Szewczyk et al. [20] first
reported the MCE of a La0.845Sr0.155MnO3 polycrystalline manganite, which underwent a
magnetic phase transition at 234 K. The ∆SM and ∆Tad reached, respectively, -6.6 J/kgK
and 3.3K for ∆H = 7T. Later on, these authors [21] measured systematically the MCEs of
La1-xSrxMnO3 (x = 0.120, 0.135, 0.155, 0.185, a nd 0.200) manganites. It was shown that
the MCE increased with increasing Sr-doped content, expect for x = 0.120 compositions.
The ∆Tad reached the highest value of 4.15K for ∆H = 7T for x = 0.20 compositions [21].
In an analogous manner, Demin and Koroleva [40] also found that the MCE increased in
La1-xSrxMnO3 (0.1<x<0.3) single crystals with Sr addition. For ∆H = 0.82 T, the obtained
∆Tad values were 0.2K at 175K for x = 0.1, 0.37K at 180K for x = 0.125, 0.7 at 160K for
44 | P a g e
x = 0.175, and 0.78K at 346K for x =0.3. Mira et al. [33] found the ∆SM of -1.5 J/kgK at
370K f or ∆H = 1T i n t he La0.67Sr0.33MnO3 polycrystalline s ample. This r esult is qui te
similar to that of Xu et al. [41]. Most interestingly, the large ∆SM value of -2.12 J/kgK at
305K for ∆H = 1T was reported by Phan et al. [13] in La0.65Sr0.35MnO3. This material is
potential for room temperature MR.
3.4.2.2.3. (La1-xBax) MnO3

The MCE of a La0.7Ba0.3MnO3 polycrystalline manganite was first measured by Phan et
al. [42]. They found the ∆SM of -1.6 J/kgK at 336K for ∆H = 1T. Zhong et al. [43] studied
the ef fects of ox ygen s toichiometry on t he m agnetic a nd m agneto-caloric pr operties o f
La2/3Ba1/3MnO3-δ (δ = 0, 0.02, 0.05, 0.08, and 0.1) samples. They observed a considerable
reduction of the MCE in the samples with oxygen deficiency. It is interesting to note that
the La 2/3Ba1/3MnO3-δ (δ = 0.0) s ample ex hibited a l arge ∆SM of -2.7 J /kgK a t 350K f or
∆H = 1T [43]. This r esult is qui te di fferent f rom tha t r eported b y X u et al. [41] on t he
La0.67Ba0.33MnO3 composition. This discrepancy could be caused by the differences in the
sample preparation and the chemical composition [41,43]. In general, the La2/3Ba1/3MnO3
material is suitable for room temperature MR.
3.4.2.2.4. (La1-xCdx) MnO3

Luong e t a l. [44] investigated t he M CEs of ( La1-xCdx) M nO3 (x = 0.1 , 0.2, a nd 0.3)
manganites. It w as s hown t hat, for ∆H = 1.35 T, ∆SM reached -2.88 J /kgK at 140K for
x = 0.3 a nd -1.01 J / kg K at 150K for x = 0. 2. N o M CE w as r eported f or x = 0.1
composition. It was noted that the temperature at which the ∆SM peaked did not coincide
with the ma gnetic o rdering ph ase tr ansition temperature ( TC), unl ike other m agneto-
caloric m anganites [11,13]. I n addition, t he r esistivity of t he s ample increased w ith
increasing C d concentration. T hese a nomalous f eatures c ould be a ttributed t o t he non -
uniform distribution of grains in these samples.
3.4.2.2.5. (La1-xPbx) MnO3

Chau et al. [45] investigated systematically the electrical, magnetic and magneto-caloric
properties of La1-xPbxMnO3 (x = 0.1, 0.2, 0.3, 0.4 , and 0.5) manganites. They found that
the ∆SM increased with i ncreasing Pb-doped concentration up t o x = 0.3 a nd t hen
decreased for hi gher P b-doping l evel. T he l argest ∆SM was -1.53 J /kgK a t 358K f or
45 | P a g e
∆H=1.35 T for La0.7Pb0.3 MnO3 (x = 0.3) sample. In turn, Min et al. [46] measured both
∆SM and ∆Tad of La 1-xPbxMnO3 (x = 0.1, 0.2 a nd 0.3) samples and showed that, among
the c ompositions inve stigated, the la rgest ∆SM value w as obt ained f or x = 0.2
composition. However, for ∆H = 1.5T, the ∆Tad was obtained to be about 0.68 and 1K for
x = 0.2 a nd 0.3 a t 292 a nd 349 K, respectively. In this case, the authors [46] stated that,
because t he he at cap acity of P b is l arger compared to La, the ∆Tad was l arger f or t he x
=0.3 sample than for the x = 0.2 sample. It is clear that, though the ∆SM and ∆Tad could be
obtained in the room-temperature range, these values were quite small and therefore not
desirable for room temperature AMR.
3.4.2.3. (La–Ca–M) MnO3 where M = Sr, Ba, and Pb

La1-xCaxMnO3 phases e xhibited t he l argest M CEs a mong t he e xisting m anganites, but
their C urie t emperatures ar e qui te be low room t emperature, for example, the m aximum
TC = 267K f or La0.67Ca0.33MnO3 [29–34]. This pr obably l imits t he us age of
La1-xCaxMnO3 materials f or A MR i n the r oom t emperature r ange. In t his c ontext, s uch
substitution of Ca by other elements with larger ionic radius such as Sr, Ba, and Pb could
be of significant importance, because this could allow increasing T C while still retaining
relatively l arge M CE v alues. Indeed, i t w as s hown t hat t he s ubstitution of Sr s mall
amount for Ca in La1-xCaxMnO3 could tune the MCE peak temperature in the temperature
range of 150 –300 K , w hile r etaining r elatively large M CE va lues [11, 13, 33, 47–51].
Most int erestingly, Phan e t a l. [11,51] reported t he r oom t emperature l arge M CEs of
La0.7 Ca0.3-xSrxMnO3 (x = 0.05, 0.10, 0.20, a nd 0.25) s ingle crystals. For ∆H = 5T , t he
∆SM reached a maximum value of -10.5 J/kgK at 275K for x = 0.05 composition, which is
larger than that of Gd, ∆SM = -10.2 J=kgK at 294 K. In addition, the large values of ∆SM
were obtained for the remaining samples in the room temperature range. Therefore, these
single crystals are attractive candidate materials for room temperature AMR. For the case
of La 2/3(Ca1-xSrx)1/3MnO3 (x = 0, 0.05, 0.15, 0. 25, 0.50, 0.75, and 1) pol ycrystalline
samples, the drop of the MCE value was observed as the Sr-substituted content increased
[33]. For ∆H = 1T, the ∆SM decreased from -3.7 J/kgK for La2/3Ca1/3MnO3 to -1.5 J/kgK
for L a2/3Sr1/3MnO3. T his i s pr obably be cause t he s ystem c hanged f rom or thorhombic
(Pbnm) to rhomboheral (R3c) structure accompanying b y the respective magnetic phase
transition from f irst to s econd-order [33]. T o this e xtent, G uo e t a l. [47] also pr oposed
that, in a fixed crystal structure with orthorhombic or rhombohedral phase, the magnetic
46 | P a g e
entropy change d ecreased with increasing t he A -site i onic ave rage r adius, <rA>. W hen
substituting Ba partially for Ca, Phan et al. [42] found the large magnetic entropy changes
above 300K i n La0.7Ca0.3-xBaxMnO3 (x = 0.12, 0.2 4, a nd 0.3) c ompounds. It w as found
that the ∆SM decreased w ith increasing B a-doping l evel. For ∆H = 1T , t he ∆SM was
-1.85 J/kgK at 298K for x = 0.12, -1.72 J/kgK at 320K for x = 0.24, and -1.6 J/kgK at 336
K f or x = 0.3. These m aterials a re s uitable f or r oom t emperature M R. F urther
investigation i nto t his w ork [42], Chen e t a l. [52] substituted Nd f or La i n
La0.7-xNdxBa0.3MnO3 (x = 0, 0.05, 0.07, 0.1 a nd 0.15) s amples. It was s hown t hat, w ith
increasing Nd-doping level, the ∆SM significantly increased, while the Curie temperature
gradually d ecreased. Because t he C urie t emperatures r ange f rom 269 to 333 K, these
materials coul d be us ed as m agnetic r efrigerants f or M R i n the s ub-room a nd r oom
temperature r ange. Sun et al . [14] investigated the M CE of L a2/3(Ca,Pb)1/3MnO3, w hich
underwent a tr ansition from pa ramagnetic ins ulator to ferromagnetic me tal te mperature
around 290 K. They found the ∆SM = -7.5 J=kgK and the ∆Tad = 5.6K for ∆H = 7T. This
∆SM value is s maller th an that of La2/3Ca1/3MnO3, for t he s ame m agnetic f ield change
[3,14]. More interestingly, Phan et al. [53] investigated the MCEs of La0.6Ca0.3Pb0.1MnO3,
La0.7 Ca0.2Pb0.1MnO3, a nd La0.7Ca0.1Pb0.2MnO3 samples a nd f ound t he l argest ∆SM of -
3.72 J/kgK at 337K for ∆H = 1.35T for the third sample. The large ∆SM of -2.26 J/kgK at
354K f or ∆H = 1T w as a lso obs erved f or La0.6Sr0.2Ba0.2MnO3 [13]. Such materials are
promising for room temperature AMR.
It is s tated that a ny s ubstitution of M ( = Sr, Ba a nd Pb) f or C a in ( La–Ca–M) MnO 3

manganites usually leads to an increase in TC but to a reduction in the MCE. However, a
proper combination of both the MCE and the Curie temperature can produce appropriate
magnetic r efrigerants f or r oom-temperature m agnetic r efrigerators. Furthermore, the
increase i n the ave rage A -site i onic radius could be attributed t o t he i ncrease of t he T C,
while the slight decrease in the maximum ∆SM probably originates from the decrease of
spin–lattice interaction. Following this hypothesis, Phan et al. [54] used successfully the
electron pa ramagnetic r esonance ( EPR) m ethod t o s tudy t he e ffects of t he s pin–lattice
coupling on changes of the m agnetic ent ropy i n t he m agnetic-ordering phase t ransition
range in doped manganites.
47 | P a g e
3.4.2.4. (La–M–Ca) MnO3 where M = Nd, Cd, Bi, Tb, Dy, Gd and Ce
It w as s hown t hat M CE c ould be i mproved i n ( La–M–Ca) M nO3 manganites w ith La
substituted b y ot her elements s uch a s M = N d, B i, T b, G d, a nd C e. Wang e t al. [55]
investigated the M CEs of La0.7-xNdxCa0.3MnO3 (x = 0, 0.05, 0.1, 0,15, a nd 0.2)
compounds with Nd substitution for La. The largest ∆SM value was obtained to be -2.31
J/kgK at 213K for ∆H = 1T for x = 0.2 c ompositions. The Nd addition in the precursor
La0.7Ca0.3MnO3 sample shifted the MCE peak towards lower temperatures, which are well
below room temperature. This perhaps limits the usage of La0.7-xNdxCa0.3MnO3 materials
for the purpose of room temperature MR. However; these materials are good for MR in
the temperature range of 210–270 K.
In an analogous manner, the substitutions of Bi (5at%) for La in La0.67Ca0.33MnO3 was

found t o s ignificantly i mprove t he M CE [56]. F or ∆H = 1T , t he La0.62Bi0.05Ca0.33MnO3
(x = 0.05) s ample ex hibited a l arge ∆SM of -3.5 J /kgK a t 248 K . T his v alue of ∆SM is
slightly larger than that of the precursor sample of La0.67Ca0.33MnO3 (x =0). In this case, it
should be not ed t hat t hough t he M CE w as enhanced, t he r emarkable dr op of T C could
make it difficult to be used in room-temperature magnetic refrigerators. In another work,
Zhang et al . [32] revealed that the p artial s ubstitution of La by Y in the
La0.67-xYxCa0.33MnO3 (x =0.07) sample resulted in a decrease of both the MCE and TC.
Another study of the magneto-caloric properties of (La1-xMx) 2/3Ca1/3MnO3 (M = Gd, Dy,

Tb, Ce) compounds was made by Chen et al. [57]. It was shown that partial substitution
of La b y r are-earth elements caus ed a de crease i n TC, a nd t he hi ghest ∆SM value w as
obtained f or a ll x = 0.1 r are-earth dopa nts. T he ( La1-xRx) 2/3Ca1/3MnO3 materials ar e
suitable f or MR i n t he t emperature r ange of 80 –260 K . M ore i nterestingly, W ang e t a l.
[58] recently reported a large M CE w ith broadened FWHM i n ( La0.47Gd0.2) S r0.33MnO3
polycrystalline nano-particles. This material could be appropriate for sub-room AMR.
3.4.2.5. (La–M)(Mn–Mo) O3 where M = Ca, Li, Sr and M' = Ti, Cr, Cu, Co, Ni
Since the magnetic property is also governed by the strength of double-exchange
interaction of Mn3+–O–Mn4+, doping at the Mn-site could be of interest in modifying the
double-exchange s trength and hence t he m agnetic and magneto-caloric be havior of a
doped manganite. Bohigas et al. [59] first showed that, when substituting Ti partially for
Mn i n L a0.65Ca0.35Ti1-xMnxO3 and L a0.5+x+yLi0.5-3yTi1-3xMn3xO3-z systems, the M CE pe ak
48 | P a g e
temperature coul d be tuned i n t he w ide t emperature r ange of 35 –263K a nd t his i s
desirable for the active magnetic refrigerator materials suggested by Barclay [60]. Sun et
al. [61] found a de crease of bot h M CE a nd T C in La0.67Sr0.33Mn1-xCrxO3 (x = 0, 0.1)
manganites with Cr partial substitution for Mn. For ∆H = 6T, La0.67Sr0.33 Mn0.9Cr0.1O3 has
the maximum ∆SM of -5.8 J/kgK at ∼337 K. Nonetheless, this value is quite large and is
therefore s uitable f or M R a bove r oom t emperature. F urthermore, i t w as not ed t hat a
shoulder pe ak obs erved at ∼337K de veloped und er hi gh m agnetic f ields. Consequently,
the magnetic entropy peak was broadened, which is beneficial for an Ericsson-cycle MR.
The shoulder peak could imply that the microscopic magnetic structure above TC was not
simple paramagnetic state due to the complex magnetic interactions induced by Cr doping
[61].
Recently, Chau et al. [62] investigated the influence of Cu partial substitution for Mn on
the MCE of La0.7Sr0.3Mn1-xCuxO3 (x = 0.05, 0.1) manganites. They showed that, for ∆H =
1.35 T , t he ∆SM reached values of -1.96 a nd -2.07 J /kgK f or x = 0.05 a nd 0.1
compositions, respectively. Later on, P han et al. [63] significantly improved the MCE of
these samples by optimizing the annealing conditions. For ∆H = 1T, the maximum ∆SM
of t he C u-doped s amples w as found t o b e -3.05 J /kgK a t 345 K f or x = 0.05 a nd -3.24
J/kgK a t 347K f or x = 0.10, w hile i t i s -2.8 J /kgK at 294K for G d m etal [3]. T hese
materials are promising for AMR above room temperature. In another work, Phan et al.
[54] also found the large magnetic entropy changes in La0.845Sr0.155Mn1-xMxO3 (M = Cu,
Co) Cu -doped manganites. The C urie t emperatures of t hese s amples w ere r educed well
below room temperature, which is not desirable for room temperature AMR.
The i nfluence of N i p artial s ubstitution f or M n on t he M CE of L a0.7Sr0.3Mn1-xNixO3

(x = 0.01, 0.02, 0.03, a nd 0.05) manganites was investigated by Choudhury et al. [64]. It
was ex perimentally obs erved that f or ∆H = 1.3 5T, t he ∆SM values w ere -2.67, -3.15,
-3.54, and -2.33 J /kgK for x = 0.01, 0.02, 0.03, a nd 0.05, r espectively. Obviously, t he
x = 0.02 s ample e xhibited t he hi ghest ∆SM among t he c ompositions i nvestigated. In
addition, the large magnetic entropy change of this sample was obtained at 320 K . This
indicates t hat t he x = 0. 02 s ample ha s pot ential for r oom t emperature A MR. In a m ore
detailed investigation, Phan et al. [65] revealed that the ∆SM of the La0.7Sr0.3Mn1-x NixO3
(x =0.02) sample could reach a value as high as -7.65 J/kgK at 350K for ∆H = 7T . It is
interesting t o not e t hat, e ven unde r hi gh m agnetic f ields, t he ∆SM distribution of t his
49 | P a g e
material w as muc h more uni form tha n that o f G d [3] and several polycrystalline
perovskite manganites [13], which is desirable for an Ericson-cycle magnetic refrigerator.
It is also suggested that such a small amount (∼2%) of substitution of Mn3+ by a magnetic
ion (Ni3+, or Co3+) in the perovskite manganite could favor the spin order and hence the
MCE. This investigation opens a window to explore the active MR at high temperatures.
3.4.2.6. (La–Nd–Ca)(Mn–M ') O3 where M ' = Cr and Fe

The MCEs of La0.65Nd0.05Ca0.3Mn0.9M0.1O3 (M = Cr, Fe) compounds were investigated by
Wang et al . [66]. I t w as s hown t hat t he s ubstitution of C r or F e f or M n r esulted i n a
significant d ecrease i n both the M CE and the C urie t emperature. In this cas e, it i s
suggested t hat t he s ubstitution of C r or F e f or Mn c ould g reatly weaken t he doubl e-
exchange f erromagnetic i nteraction of M n3+–O–Mn4+ and hence reduce t he ∆SM. In
general, these materials are not suitable for AMR.
3.4.2.7. (Nd1-xMx) MnO3 where M = Ca and Sr

A num ber of works i nvolving M CEs were conducted on N d1-xMxMnO3 (M = C a or S r)
manganites with charge order, which underwent two successive phase transitions; one is
the first-order anti-ferromagnetic to ferromagnetic transition at lower temperature and the
other be longs t o t he s econd-order fe rromagnetic–metallic-to-paramagnetic –insulator
transition at higher temperature [67,68]. Sande et al. [67] first observed the large ∆SM of
2.8 J / kgK at t he ch arge-ordering t emperature of 155 f or ∆H = 1T i n Nd0.5Sr0.5MnO3.
They showed that the magnitude of ∆SM obtained around the first-order transition is about
three times larger than those obtained around the second order one. This is likely related
to t he s uppression of c harge or dering, w ith a n i ncrease of a ccessible s tates due t o t he
enhancement of e lectron m obility, unde r a n a pplied m agnetic f ield. Later on, C hen a nd
Du [68] reported a larger MCE value of Nd0.5Sr0.5MnO3. They showed that for ∆H =1T.
This value of ∆SM is much larger than that of Gd. In contrast to the works [67, 68], Chau
et al. [69] reported a much smaller value of ∆SM of 1.9 J/kgK at ∼155K for ∆H = 1.35T in
the same composition of Na0.5Sr0.5MnO3. This discrepancy could arise from the different
sample preparation (i.e., the annealing temperature and annealing time). In fact, it should
be not ed t hat t he c hange i n m agnetization w ith r espect t o t emperature occurred m uch
more sharply in the cases [67, 68] than in the case [69] and this is the reason leading to a
larger variation in the ∆SM [67, 68]. The authors [69] also found a significant decrease in
50 | P a g e
the MCE of Nd0.5Sr0.5Mn1-xCuxO3 (x = 0.02, 0.1) manganites with Cu substitution for Mn.
This could be understood due to the fact that the charge-ordering behavior was drastically
modified by Cu doping.
It i s generally t hought that t he c harge-order t ransition temperature of charge-ordered

manganites c ould be m odified b y dopi ng a nd t his a llows making a ctive m agnetic
refrigerants fo r m agnetic r efrigerators [67, 68]. It s hould b e not ed t hat, a lthough t he
charge-ordering ma nganite ha s la rge ∆SM induced b y l ow m agnetic f ield c hange, t his
charge-ordering state is strongly doping- and magnetic field dependent [67–69]. When an
applied magnetic field is sufficiently high, the charge-ordered state will be melted and an
insulator–metal t ransition i s i nduced. Indeed, t he c harge-ordered state w as s trongly
modified or even disappeared, unde r hi gh m agnetic f ields (∼3T) [22]. It i s t herefore
difficult to apply hi gh f ields ( ∼5T) t o achi eve t he hi gh magnetic cool ing efficiency. In
addition, e ven i f t he c harge-order tr ansition temperature o f the ma terial is tune d by
doping, a sharp charge-ordering magnetic transition will be modified thereby leading to a
considerable r eduction i n t he M CE [69]. A nother di sadvantage i s t hat t he F WHM of
MCE peak is only several K, followed by large thermal and field hysteresis, which is not
beneficial for AMR.
3.4.2.8. (Pr1-xMx) MnO3 where M = Ca, Sr and Pb

Gomes et al. [70] investigated the MCEs of Pr1-xCaxMnO3 (0.3≤x≤0.45) manganites, who
showed the large positive and negative changes of ∆SM. It was experimentally observed
that Pr0.68Ca0.32MnO3 exhibited, respectively, the positive and negative ∆SM of 24 J /kgK
at 21.5K and -27 J/kgK at 31K for ∆H = 5T. This material could be good for MR at low
temperatures. In addition, these authors [71, 72] studied the charge-ordering contribution
to the m agnetic ent ropy change of P r1-xCaxMnO3 (0.2≤x≤0.95) m anganites. T hey
suggested that the ∆SM of Pr1-xMxMnO3 (0:3<x<0:90) charge-ordered manganites around
the cha rge-ordering t emperature w as r elated t o a ne gative c ontribution f rom t he s pin
ordering ∆Sspin, w hich was s uperimposed t o a positive c ontribution due t o t he c harge-
ordering ∆SCO.
In a nother w ork, t he MCEs of P r1-xSrxMnO3 (x = 0.3, 0.4, a nd 0.5 ) pol ycrystalline

manganites were investigated by Chen et al. [73], who found the largest ∆SM of 7.1 J/kgK
51 | P a g e
at 160K for ∆H = 1T for the x = 0.5 sample. This value of ∆SM is much larger than that of
Gd, ∆SM = -2:8 J/kg K f or ∆H = 1T . T his m aterial c ould be g ood f or M R i n t he
corresponding temperature range. More interestingly, Phan et al. [74] found a large MCE
in a single crystal of Pr0.63Sr0.37MnO3, which underwent a very sharp ferromagnetic- to-
paramagnetic phase transition at ∼300 K. The ∆SM of -8.52 J/kgK and the ∆Tad of 5.65K
for ∆H = 5T were found to occur around 300 K , thereby allowing water to be used as a
heat transfer fluid in the room-temperature MR regime. In addition, the ∆SM distribution
is very uniform and therefore desirable for an Ericsson-cycle magnetic refrigerator. The
large m agnetic ent ropy change i nduced by a r elatively l ow m agnetic f ield change i s
beneficial for household application of active magnetic refrigerant materials. These make
the Pr0.63Sr0.37MnO3 single crystal a competitive candidate for commercial applications of
room temperature MR.
Recently, t he ne w r esponding of l arge l ow-field MCEs in polycrystalline P r1-xPbxMnO3

(0.1≤x≤0.5) m anganites was r eported b y P han e t a l. [75]. I t w as s hown t hat, f or ∆H =
1.35 T, the ∆SM reached values of -3.91, -3.68 and -3.34 J/kgK for x = 0.1, 0.4 a nd 0.5
compositions, r espectively. T hese va lues a re l arger t han t hat o f G d (-3.32 J /kg K ) a nd
were a ttained b y a low a pplied magnetic f ield that c an be generated b y permanent
magnets. These superior magneto-caloric features together with a relatively low material
cost make Pr1-xPbxMnO3 attractive candidate materials for MR in the temperature r ange
of 150–270 K.
3.4.2.9. (La1-xMx) 3Mn2O7 where M = Ca and K

The giant MCEs were discovered in the new two-layered manganites of La1.6Ca1.4Mn2O7
[76] and La1.6Ca1.4Mn2O7 [77]. Zhou et al. [76] showed that, for ∆H = 1.5T, the ∆SM of
La1.6Ca1.4Mn2O7 reached a m aximum of -3.8 J/kgK at 168 K . More interestingly, Zhu et
al. [77] found a l arge ∆SM of -17 J /kgK a t 270K f or ∆H = 5T i n the La1.4Ca1.6Mn2O7
compound. T his va lue o f ∆SM is m uch l arger t han t hat o f G d ( -10.2 J /kg K) [3] and i s
close t o t hat of G d5Si2Ge2 [11] or M nFeP0.45As0.55 (∼18 J /kg K ) [16] for ∆H = 5T .
Another advantage is that the two-layered manganites have a broad FWHM of the MCE
peak, r esulting i n t he hi gh c ooling c apacity. Indeed, t he r efrigerant c apacity of
La1.4Ca1.6Mn2O7 is larger than that of Gd [77]. This material could be ideal for sub-room
temperature M R. Zhong et al . [78] investigated t he M CEs of La2.5-x K0.5+xMn2O7
52 | P a g e
(x = 0.05, 0.15, 0.25, 0. 35, a nd 0.45) t wo-layered m anganites a nd f ound a n i ncrease i n
both ∆SM and TC with increasing K-doped content up to x =0.35. For ∆H = 1T, the largest
∆SM was obt ained t o b e -2 J /kgK at 250K f or x = 0.35 c ompositions. In ge neral, t hese
materials could be used as magnetic refrigerants for MR in the intermediate temperature
range of 150–270 K.
3.5 Concluding remarks of review

Progress i n magnetic r efrigeration t echnology, e specially i n room-temperature ma gnetic
refrigeration, ha s be en recognized w orldwide. This e nabling t echnology w ill f irmly
replace t he C ompressor Gas Cooling ( CGC) technology i n t he ne ar f uture. T he
discoveries of outstanding magneto-caloric materials have provided new opportunities to
use the m a s a lternative w orking materials in active ma gnetic r efrigerators a t va rious
temperatures. It is b elieved that the ma nganite ma terials w ith the s uperior ma gneto-
caloric pr operties i n addition t o c heap m aterials pr ocessing c ost w ill be t he opt ion of
future magnetic refrigeration technology.
53 | P a g e
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site va cancies on the magnetic entropy change a nd t he C urie t emperature of
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resistance a round r oom t emperature i n La0.7Ca0.3MnO3, La0.7Sr0.3MnO3”, J. A ppl.
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magnetic properties of Tb0.9Sn0.1MnO3”, Physica B 357 (2005), 326,
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entropy change abov e r oom t emperature i n t he col ossal m agnetoresistance
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radius on complex permeability of perovskite manganite La0.65Nd0.05(Sr,Ba)0.3MnO3”,
J. Magn. Magn. Mater. 234 (2001), 371,
58 | P a g e
[3.67] P. Sande, L.E. Hueso, D.R. Miguens, J. Rivas, F. Rivadulla, M.A. Lopez-Quintela,
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59 | P a g e
Chapter Four Theoretical Aspects of the Magneto - Caloric Effect
4.1 Introduction
The magneto caloric effect (MCE) is the heating or cooling of magnetic materials when
subjected t o m agnetic f ield va riation, or a diabatic t emperature ch ange ( ∆Tad ) w hich i s
detected as the heating or cooling of a magnetic material due to a varying magnetic field,
or it is characterized by the temperature change ( ∆Tad ) in an adiabatic process and by the
entropy ch ange ( Δ Siso) i n an isothermal pr ocess, The r enewed i nterest i n the
magnetocaloric e ffect can be a ttributed t o Brown’s w ork concerning the ne ar r oom
temperature m agnetic r efrigerator and Pecharsky and Gschneidner’s di scovery of t he
giant magnetocaloric effect near room temperature in Gd5Si2Ge2. After these pioneering
works, t he m agnetocaloric e ffect ha s b een i ntensively s tudied i n a great num ber of
magnetic materials. The MCE firstly was discovered by Warbourg [1] in 1881, when he
observed it in iron. The origin of the MCE was independently explained by Debye [2] and
Giaque [ 3]. T he he ating or c ooling pr ocess t hrough t he m agnetic f ield v ariation c an be
roughly described in the following way: when the magnetic field is adiabatically applied
to a us ual f erromagnetic material, their m agnetic mom ents be come or dered, so that the
magnetic part of the total entropy is reduced. Therefore, in order to keep constant the total
entropy in the adi abatic pr ocess, t he crystalline l attice entropy s hould increase. As a
result, the material heats up. A n opposite effect occurs, i.e. the materials cools down, if
the magnetic field is adiabatically removed.
The magnetocaloric potential ∆Tad can be directly measured by using a t hermometer, or

indirectly by us ing s pecific he at da ta. O n t he ot her ha nd, t he m agnetocaloric pot ential
Δ Siso can onl y be obt ained i ndirectly b y us ing s pecific he at or m agnetization da ta. I t
should be noted that the determination of (Δ Siso) using magnetization data via the relation
∆S iso = ∫ (∂M / ∂T )dB is e ffective for c ompounds w ith s econd or der pha se t ransition.
However, t here i s m uch c ontroversy over t he us e of t his r elation t o de termine t he

isothermal entropy change in compounds with first order phase transition. This aspect is
addressed in the next section.
The MCE can be used for some technological applications. For instance, the MCE can be
applied for the physical treatment of some types of cancer [4]. Such an application relies
60 | P a g e
on t he e xistence of bi ocompatible m agnetic n anoparticles t hat are m ainly abs orbed
cancerous c ells. Thus, it i s s upposed these m agnetic na noparticles he ated vi a m agnetic
field va riation, c an ki ll t he c ancerous cells w ithout da mage t o t he h ealthy on es. T his
application of the ma gnetocaloric effect s till ne eds much multidisciplinary e ffort to be
used i n hum ans. A t t he present t ime, t he m ain a pplication of t he m agnetocaloric i s i n
magnetic r efrigeration. Magnetic r efrigeration is an environmental friendly t echnology;
because magnetic compounds are used as the cooling materials and water non poi sonous
fluids are used as heat exchanger. It is expected that magnetic refrigerators operate with
an e nergy s aving of u p t o 30% a s c ompared w ith t he c onventional va por c ycle
refrigerators. T he pr ocess of c ooling us ing m agnetic f ield va riation w as i ndependently
proposed i n 1926 or 1927, b y D ebye [ 2] a nd G iaque [ 3], t hrough a pr ocess c alled
adiabatic de magnetization. This pr ocess w as f irst de monstrated for the f irst time in the
history of P hysics, a few years l ater w hen 193 3 G iaque and MacDougall [ 5] r eached
temperatures a s l ow a s 0.25K . H owever, t he great s tep t owards r oom t emperature
magnetic r efrigeration w as onl y given i n 1976, when Brown [ 6] de veloped a m agnetic
refrigerator us ing m etallic g adolinium as a m agnetic r efrigerant. I n hi s prototype
magnetic refrigerators, Brown obtained a temperature reduction from 319 K to 272 K for
a m agnetic f ield va riation f rom 0 t o7 tesla. A fter B rown’s w ork m uch e ffort ha s be en
done in order to make room temperature magnetic refrigeration feasible.
The magnetocaloric effect has been intensively studied in the last sixty years, and much
experimental da ta ha ve be en r eported i n t he l iterature. F or a n ove rview on t he
experimental da ta o f t he m agnetocaloric effect, it i s s uggested to observe t he r eference
[7-8]. The m agnetocaloric ef fect ha s b een mostly studied in rare earth metals and their
alloys. The r eference ma terial f or ma gnetocaloric pot entials is me tallic g adolinium. In
this ma terial, the ma gnetocaloric pot entials Δ Siso and ∆Tad , at the t ransition temperature
around 292 K , upon m agnetic f ield va riation f rom 0 t o 5 t esla a re a pproximately
10 J /((kgK) and 10 K r espectively. In 1997, P echarsky and G schneidner [ 9-12]
discovered a ve ry large value of t he m agnetocaloric pot ential Δ Siso in the c ompound
Gd5Si2Ge2, w hich unde rgoes a f irst or der pha se transition ne ar r oom t emperature. T hey
have shown that the peak in the isothermal entropy change in Gd5Si2Ge2 around 273 K ,
upon m agnetic f ield va riation f rom 0 t o 5 t esla i s a bout 20 J/(kgK) . D ue t o t his l arge
value of t he i sothermal e ntropy c hange, a s compared w ith t he one found i n m etallic
gadolinium, the s earch f or ne w ma gnetic ma terials w ith large va lues of the
61 | P a g e
magnetocaloric pot entials h as a ttracted the attention of s cientist a ll o ver the w orld.
Pechersky a nd Gschneidner s howed t hat t he s eries of c ompounds G d5(SixGe1-x)4 for
x<0.5 a lso e xhibit t he g iant m agnetocaloric e ffect [ 13,14]. M any ot her pa pers [ 15-19]
have been published on the magnetocaloric effect in the series compounds Gd5(SixGe1-x)4
and Tb5(SixGe1-x)4.
The be havior of m agnetocaloric pot entials Δ Siso depends on t he pa rticularity o f t he

magnetic s tate. F or i nstance, i n us ual f erromagnets unde rgoing a s econd or der pha se
transition, s uch a s G d; RAl2; a nd R Ni2 (R= r are ear th), the m agnetocaloric pot entials
Δ Siso exhibits a peak around the magnetic ordering temperature and goes down smoothly,
outside t he r egion o f t he m agnetic ph ase t ransition. In f erromagnets un dergoing a first
order phase transition, such as Gd5Si2Ge2; MnAs; MnFeP0.45As0.55 and La(FexSi1-x)13, the
magnetocaloric pot entials Δ Siso exhibits a s harp pe ak a round t he m agnetic or dering
temperature a nd goes do wn qui ckly, f arther w ay. T he M CE ha s a lso be en s tudied f rom
the theoretical poi nt of view and m uch experimental da ta ha ve b een explained [20-26].
Important aspects of the magnetocaloric effect such as: crystalline electrical field [27-28,]
magnetoelastic c oupling [ 29], s pins f luctuations [ 30-31] a nd e lectron c orrelations [ 32]
have be en already addressed in the l iterature. However, despite t he great success of t he
theoretical pa pers i n explaining t he ex perimental da ta, the P hysics be hind the
magnetocaloric effect is not completely understood.
In t his c hapter, w e t heoretically di scuss the m agnetocaloric e ffect in crystalline bul k

compounds, taking into account the origin of their magnetism. The magnetocaloric effect
in r are e arth ba sed c ompounds i s de scribed by m odel Hamiltonians of l ocalized
interacting magnetic moments, in which the mean field approximation is used to treat the
two-body e xchange i nteraction. O n t he ot her ha nd, t he t heoretical de scription of t he
magnetocaloric effect in transition metal based compounds is made in the framework of
the band t heory, b y considering the electron-electron interaction and the magnetoelastic
coupling. T he MCE is intrinsic to all magnetic materials and cause by the coupling of
the magnetic sub-lattice with the magnetic field, which changes the magnetic part of the
entropy of a solid. N owadays, t his i s a great d eal of i nterest i n us ing t he M CE a s a n
alternative te chnology for r efrigeration from r oom te mperature to the temperature of
hydrogen a nd he lium l iquefaction. T he m agnetic r efrigeration of fers t he pr ospect of a n
energy efficient and environment friendly alternative to the common gas refrigeration.
62 | P a g e
4.2 Thermodynamic Theory of the Magneto-Caloric Effect
In or der t o e xplain the origin of M CE, w e us e t he t hermodynamics, w hich r elates t he
magnetic variables (magnetization and magnetic field) to entropy and temperature and it
is i mportant t o know t he t otal e ntropy unde r the a ction of applied magnetic f ield.
Generally, the total entropy of a magnetic material is made up of the contributions from
the crystalline lattice (Slat), from the conduction electrons (Sel), from the atomic magnetic
moments (Smag) and from the atomic nucleus (Snuc). The contribution from the nucleus to
the m agnetocaloric ef fect can be ne glected, since i t i s onl y i mportant at ve ry l ow
temperature. So as a good approximation, the total entropy of a solid can be written as
S(T,H,P) = Sel(T,H,P) + Smag(T,H,P) + Slat(T,H,P) 4.1

In t he general c ase, t he c ontributions S el, S mag, a nd S lat are s upposed to de pend on
temperature, magnetic field and pressure. However, for the simplicity it is supposed that
the c rystalline la ttice a nd t he e lectronic e ntropy do not de pend on t he a pplied m agnetic
field and pressure. It is well known that for a given magnetic field, the total entropy of a
usual ferromagnet increases with increasing temperature. On the other hand, for a given
temperature, the t otal entropy o f a us ual f erromagnet d ecreases w ith increasing applied
magnetic f ield. In fig.4.1 the tot al e ntropy (S) of a us ual f erromagnet is pl otted as a
function of temperature, for two values of the applied magnetic field H0 and H1 under the
condition H1>H0.
The m agnetocaloric pot ential Δ Siso is obt ained b y t aking t he di fference be tween the
entropy in the f inal a nd ini tial s tates of a ny is othermal pr ocess. For i nstance, i n t he
isothermal process represented by the path in the diagram of fig.4.1, the entropy change is
Δ Siso = S B – SA<0 since SB<SA. The sign of Δ Siso is opposite, i.e. Δ Siso>0 if the magnetic
field is is othermally r emoved from th e initial s tate B to final s tate A . According to the
entropy versus temperature diagram shown in fig 4.1, the isothermal entropy change Δ Siso
upon magnetic field variation from H0 to H1 is determined by
Δ Siso(T, H1-H0, P) = S(T, H1, P) – S(T, H0, P) 4.2
The magnetocaloric pot ential Δ Tad is obt ained by t aking t he di fference be tween the
temperature of the final and initial states in any adiabatic process. For instance, when the
magnetic f ield is adi abatically appl ied in the pr ocess r epresented by t he pa th CB i n
fig.4.1, the temperature change is positive, (Δ Tad>0) and the material heats up.
63 | P a g e
S(T,H0,P)
H1>H0
Total Entropy
S(T,H1,P)
A
Δ Siso
C Δ Tad B
T0 T1
Temperature
Fig: 4.1 Entropy versus Temperature diagram for two values of applied magnetic field.
When the magnetic field is adiabatically removed in the process represented by the path
BC in fig. 4.1, the temperature change is negative, (Δ Tad<0) and the material cools down.
According t o t he e ntropy versus t emperature di agram s hown i n f ig.4.1, t he a diabatic
temperature change, upon magnetic field from Ho to H1 is determined by
Δ Tad(T, H1-H0, P) = T1(H1) – T0(H0) 4.3
under the adiabatic condition S(T1, H1, P) = S(T0, H0, P).
There are two relevant processes in the diagram to understand the thermodynamics of the
MCE, (i). When the magnetic f ield is a pplied adiabatically (i.e. the tot al e ntropy of the
systems remains constant during the magnetic field changes) in a reversible process, the
magnetic entropy decreases, but the total entropy does not change
S(To, Ho) = S (T1, H1) 4.4
then, the t emperature i ncreases. This adi abatic t emperature c an be vi sualized as t he
isotropic difference between the corresponding S(T, H) function as shown in Fig 4.1 b y
the horizontal arrow and it is a measure of the MCE in the material:
∆Tadi = T1 – To 4.5
(ii). When the ma gnetic f ield is a pplied isothermally ( T remains constant), the tot al
entropy change in the process is defined as:
∆S m S (To , H o ) − S (To , H1 )
= 4.6
In this case the magnetic entropy change is equal to the isothermal difference between the
corresponding S(T,H), functions as shown in fig 4.1 by vertical arrow. Both the adiabatic
temperature cha nge, ∆Tad and the is othermal ma gnetic e ntropy ch ange, ∆S m are t he
64 | P a g e
function of ini tial te mperature T o and the m agnetic f ield variation ∆H = H1 − H o . It is
easy t o see t hat i f t he m agnetic f ield is i ncreased, the m agnetic or der i ncreases ( i.e.
decreases m agnetic entropy), t hen ∆Tad (T , ∆H ) is pos itive a nd the ma gnetic bod y is
heated up, while ∆S m (T , ∆H ) is negative. In contrary if the field is reduced, the magnetic
order de creases and ∆Tad (T , ∆H ) is thus ne gative, a nd ∆S m (T , ∆H ) is pos itive, g iving

rise to a c ooling o f th e ma gnetic s olid. The Δ Tad and Δ Sm are correlated with the
magnetization (M), the magnetic field strength (H), the heat capacity at constant pressure
(Cp) and the absolute temperature by one of the fundamental Maxwell relations [33]:
 ∂S (T , H )   ∂M (T , H ) 
  = −  4.7
 ∂H  T  ∂T H
Integrating equation (4.7) for an isothermal (and isobaric) process, we obtain
H2
 ∂M (T , H ) 
∆S m (T , ∆H ) = - ∫  ∂T  dH
H1 
4.8
H
This equation indicates that the magnetic entropy change is proportional to the derivative
of ma gnetization with respect to temperature a t c onstant f ield and to the magnetic f ield
change. Using the following thermodynamic relations [33]:
 ∂T  (∂S / ∂H )T
  =− 4.9
 ∂H  S (∂S / ∂T )H
 ∂S 
and CH = T   4.10
 ∂T  H
where C H is the heat capacity at constant field and taking into account equation(4.7), the
infinitesimal adiabatic temperature change is given by:
 T   ∂M (T , H ) 
dT = -     dH 4.11

 C (T , H )  H  ∂T H
hence the adiabatic temperature rise is directly proportional to the absolute t emperature
and to the derivative of magnetization with respect to temperature at constant field and to
the m agnetic f ield change, and it i s i nversely p roportional t o the he at capa city. After
integrating this equation, we obtain other expression that characterizes the MCE
 T  2 ∂M (T , H ) 
H
∆Tad (T , ∆H ) = −  ∫   dH 4.12

 C (T , H )  H H1 ∂T H
By analyzing t he e quations ( 4.8) a nd ( 4.12) we ha ve a guide f or t he r esearch of ne w
materials with large MCE
65 | P a g e
(i) Since the ma gnetization at c onstant f ield in both paramagnets and simple
 ∂M 
ferromagnets de creases with increasing t emperature, i.e.   < 0, he nce
 ∂T  H
∆Tad (T , ∆H ) should be pos itive, w hile ∆S m (T , ∆H ) should be ne gative f or
positive field changes ∆H >0

(ii) In f erromagnets t he a bsolute va lue of t he de rivative of m agnetization w ith
 ∂M 
respect t o temperature,   is ma ximum a t T c, a nd t herefore
 ∂T  H
∆S m (T , H ) should be shown a peak at T = Tc
(iii) Although i t i s not s traight f orward f rom e quation ( 2.12) be cause t he heat
capacity at constant field shown an anomalous behavior near T c, the adiabatic
temperature ∆Tad (T , ∆H ) in ferro-magnets s hows a pe ak at T c when
∆H tend to zero [34]

(iv) For t he s ame ∆S m (T , H ) value, t he ∆Tad (T , ∆H ) value w ill be l arge at
higher T (working temperature) and lower heat capacity.

(v) In paramagnets, the ∆Tad (T , ∆H ) is only significant at temperatures close to
 ∂M 
absolute zero, since   is other wise small only when the heat capacity
 ∂T  H
 ∂M 
is al so very s mall t he s ame or der as   , can a r elevant ∆Tad (T, ∆ H)
 ∂T  H
value be obt ained, w hich a lso ha ppens onl yclose t o a bsolute z ero. I f w e a re
interested is sizable ∆Tad (T, ∆H ) values at higher temperatures, we thus need
a solid that orders spontaneously.
4.3 Perovskites Framework and General Remarks

The perovskite materials have a wide range of variation in their framework [35, 36] and
properties. All the m anganites cons idered here h ave a crystal structure d erived from the
elementary cubic pe rovskite c ell in fig: 4. 2 and s chematically s hown i n f ig: 4.3 . T he
elementary cell contains one formula unit, but few of them have precisely this structure,
because t he at oms ar e d isplaced from t heir i deal pos itions w hen t ≠ 1. T he perovskite
66 | P a g e
structure accommodates the mis fit in the ioni c s izes a nd electronically indu ced
deformations by various kinds of distortion to larger cells with lower symmetry.
y
x
Fig: 4.2 Cubic Perovskites framework
When the misfit is large, there is a buckling of the network of octahedral, which may lead
to the O-type orthorhombic GdFeO3 structure as shown in fig: 4.4a, in which the B-O-B
bond angle is sensitive to the size of the A cation, and is reduced from 1800. It is a typical
O-type s tructure for a < c/√2 < b. A di fferent case i s O`-type o rthorhombic s tructure
adopted b y R 3+ MnO3 such as LaMnO3 (Fig:4.4b). It is a va riant w ith mor e s everely
distorted octahedral environments where c/√2 < a < b. the reason for the severe distortion
is the Jahn - Teller effect of Mn3+, which causes the octahedral to extend in one direction
in the a-b plane.
Divalent c ations, w hich c an oc cupy t he bod y - center A - site inc lude c alcium, barium,
strontium a nd l ead; t rivalent c ations i nclude yttrium, l anthanum, pr aseodium,
neodymium, and s ome o ther rare e arth's (R). Besides m anganese, m any p erovskite t ype
oxides are formed b y aluminum, gallium, or other 3d elements such as chromium, iron,
cobalt or nickel on the B - sites. Any of the trivalent 3d cations can substitute partially for
manganese. The m ain effects o f the va rious s ubstitutions a re t o va ry t he num ber o f
electrons in the 3d band and to alter the inter-atomic distance and bond angles.
67 | P a g e
O B A
Fig: 4.3 Schematic framework of perovskite crystals
(a) (b)
Fig: 4.4 (a) T he oc tahedral i n O - type o rthorhombic G dFeO3 structure w hich is a
distorted version of the ideal perovskite structure in fig; 4.2 with a buckling of the oxygen
octahedral to accommodate a s maller ion than ideal A - site cation. (b) The octahedral in
O-type orthorhombic LaMnO3 structure, which incorporates a Jahn - Teller distortion of
the octahedral oxygen.
Following J ahn - Teller ( JT) t heory, a non -linear mol ecule ( or pol yatomic ions ) w ith
degrading of state will be distorted to reject the degrading and to decrease the symmetry
and available energy. A distortion of the oxygen octahedron lowers the symmetry of the
cubic crystal field in such a way that the center of gravity of the t 2g levels and the center
68 | P a g e
of gravity of the eg levels are unchanged. There is therefore nothing to be gained by Mn4+
from such a distortion, but Mn3+ can lower its energy in proportion to the distortion, and
the corresponding penalty in elastic energy will scale as the distortion squared. Hence we
have t he m arket t endency of d 4 ions t o di stort t heir oc tahedral e nvironment i n or der t o
lower their energy. Usually, JT effect happens with metal ions, in which has odd number
of electrons in e g state. However, this effect can happen in the case of compound having
octahedral structure, in which the T 2g state of metal ions contains 1, 2, 4 , or 5 e lectrons,
but it is very weak.
In an octahedral site, the five d orbitals, each of which can accommodate one electron of
each spin, are s eparated b y o ctahedral cr ystal f ield into a g roup of t hree ( dxy, d yz, d zx)
orbitals, having their lobes oriented between the oxygen neighbors, and a group of two eg
(dz2, dx2 - y2) orbitals directed towards the oxygen neighbors. The d 4 ion in octahedral
coordination t 2g3 eg1 is a strong Jahn-Teller ion, because it lowers its energy in proportion
to the splitting of the eg levels by a uniaxial distortion.
dx2-y2
eg
2Δ JT
E
d4 (3)
dz2
(2)
A free ion t2g
(1)
Fig: 4.5 Energy levels splitting for Mn3+ ion in octahedral crystal-field Jahn-Teller effect.
(1) t he m ove of energy caused b y di pole i nteraction, (2) energy l evels s plitting i n
octahedral cr ystal-field, w here ∆ are cr ystal-field i nteractions, ( 3): J ahn-Teller l evels
splitting, 2∆JT, which is JT stabilization energy.
69 | P a g e
Figure 4.5 shows the splitting of energy level for Mn3+ ion in octahedral crystal-field. If
one electron in e g state locates on dz2 orbital, the electrostatic repulsion between O2- and
Mn3+ following z - direction i s s tronger t han t hat of x y di rection, a nd t he m ovement of
2-
electron is be tter pr otected. Thus, in x y - plane O displaces ne ar M n3+, a nd t he
octahedral is distorted from ideal perovskite structure and Mn - O distance in z - direction
is longer than that in xy - plane. This case is a type - I JT distortion as shown in fig: 4.6a.
If the electron in eg state locates on dx2 - y2 orbital, the distortion is a type - II JT as shown
in fig: 4.6b. On the other hand, the distortion of structure is effect to orbital in t2g State, in
which it is split to dxy, dyz and dzx states.
O2-
Mn3+
(a) Type - I distortion (b) Type - II distortion
(c) Insulator polaron (d) Magnetic (spin) polaron

Fig: 4.6 J ahn -Teller di stortion of t ype – I, type - II (JT pol aron) and of i nsulator or
magnetic polaron.
In ABO3 perovskite, be sides J T di stortion, ot her ki nds of d istortions a re be ing s uch a s

insulator polaron (fig: 4.6c), magnetic polaron (fig: 4.6d) or GdFeO3 - type distortion. In
70 | P a g e
manganite ma terials, GdFeO3 - type di stortion ( fig: 4.4a) i s us ually o bserved, called
orthorhombic s tructure d istortion. If t he phe nomena ha ve bot h t ype - I an d type - II J T
distortions, it is R3+ MnO3 - type distortion (fig: 4.4b).
In m anganites pe rovskite, t rivalent m anganese follows t he H und f irst rule, w here 4

electrons in d band is always arranged in the orbitals so as that total spin is maximum. In
octahedral f ield, Mn3+ (3d4) ha s onl y c onfiguration t 2g3eg1 and S = 2, w hich i s hi gh-spin
state, where as M n4+ (3d3) ha s t 2g3eg0 with S = 3/ 2 a s s hown in f ig: 4.7a. H owever,
trivalent cobalt (3d6) in cobalt perovskite does not follow the Hund first rule; there are the
low-spin t 2g6eg0 with S = 0, intermediate-spin state t 2g5eg1 with s pin S = 1 a nd hi gh s pin
state t2g4eg2 with spin S=2 as shown in fig: 4.7b.
Coiii(t2g6eg0) Coiv(t2g5eg0)
S=0 S=1/2
Mn4+ (t2g3eg0)
S=3/2
Coiii (t2g5eg1) Coiv(t2g4eg1)
S=1 S=3/2
Mn3+ (t2g3eg1)
S=2
Co3+ (t2g4eg2) Co4+ (t2g3eg2)
S=2 S=5/2
(a) (b)
Fig: 4.7 Schematic electron configuration in d band of trivalent and quadrivalent Mn and
Co, (a) - Ma ion case, (b) - Co ion case.
Thus, the difference between trivalent and quadrivalent Co and Mn ions is that Co ion has
the different spin states, which is determined by the differential energy between low-spin
and high-spin, where as Mn ion has only 1 s pin state due to the splitting of crystal-field.
71 | P a g e
The abs ence o f pol aron [ 37-39] c onduction i n va lence cobalt pe rovskites is indi rect
evidence in favor of JT polarons in manganites, since neither low-spin nor high-spin Co4+
is a strong JT ion.
4.4 Double Exchange and Super Exchange

When a s ufficient p roportion of M n4+ is a vailable i n t he pe rovskite ox ides, t he oxide
materials be come ferromagnetic a nd exhibits metal like c onductivity. T he ins ulator –
metallic transition occurs around TC, the Curie temperature. This interaction is formed as
Mn3+ - O2- - Mn4+ Mn4+ - O2- - Mn3+ 4.13
and it is called double exchange, as explained by Zener [40]
Zener [ 40] of fered a n e xplanation of this be havior i n 1951 i n t erms of hi s t heory of

indirect magnetic exchange between 3d atoms. He considered that the inter - atomic Hund
rule exchange was strong and that the carriers do not change their spin orientation when
hopping from one i on t o t he next, s o t hey c an onl y hop i f t he s pins of t he t wo i ons are
parallel. On minimizing the tot al f ree e nergy of the s ystem, Zener f ound that
ferromagnetic interaction are favored when the magnetic atoms are fairly well separated
and c onduction e lectrons a re pr esent. T he t heory w as a pplied t o t he m anganese
perovskites [4] with the aim of explaining the strong correlation between conductivity and
ferromagnetism, a nd t he va lue of t he z ero-temperature s aturation magnetization, which
corresponds t o t he s um of a ll t he unpa ired electron s pins. S tarting f rom t he i nsulating
anti-ferromagnetic L aMnO3 end member where el ectrons ar e l ocalized on the at omic
orbitals, Z ener s howed how t he s ystem s hould gradually be come m ore f erromagnetic
upon hol e dopi ng ( introduction of M n4+). H e c onsidered t he pr oblem of e xchange
between Mn3+ and M n4+ ions vi a a n ox ygen i on a nd i ntroduced t he c oncept of
simultaneous transfer of an electron from the Mn3+ to the oxygen and from the oxygen to
the neighboring Mn4+ (figure 4.8). Such a transfer was called double exchange.
In the case of magnetic atoms, the configurations Mn3+ - O2- - Mn4+ and Mn4+ - O2- - Mn3+
are d egenerate if the spins of the two-d shells are parallel, and the lowest energy o f the
system at low temperature corresponds to parallel alignment of the spins of the adjacent
cations. D ouble exchange i s a lways f erromagnetic, unl ike s uper e xchange, w hich
involves vi rtual e lectron t ransfer and i s f requently anti-ferromagnetic. If t he m anganese
spins a re not pa rallel or i f t he M n–O–Mn bond i s be nt, t he e lectron t ransfer be comes
72 | P a g e
more di fficult a nd the mobi lity de creases. It f ollows tha t the re is a d irect c onnection
between c onductivity and f erromagnetism a nd a qu antitative r elation with C urie
temperature w as pr oposed: σ = (x e2/ah)(Tc/T) [ 40], where x i s t he dopi ng and a i s t he
Mn – Mn distance, which agreed with the available experimental result of Jonker and van
Santen [8] in the limited region 0.2<x<0.4.
The recent discovery of magnetocaloric and magnetic properties in rare earth perovskite
manganites [ 41-45] w ith t he general f ormula Ln1-xAx MnO3 (Ln = Rare ear th trivalent
rare ear th, A = divalent al kaline ear th) h as at tracted a hu ge i nterest i n studying t heir
structure, transport, electric and magnetic properties.
(a)
Mn3+ (or Mn4+) O2- Mn3+ (orMn4+)
e-
(b)
Mn3+ O2- Mn4+
d4 p6 d3
e-
(c)
Mn4+ O2- Mn3+
d3 p6 d4
Fig: 4.8 The schematic diagram of the SE (a) and DE (b), (c) interactions. The two states
Mn3+-Mn4+ and Mn4+-Mn3+ are degenerate if the manganese spins are parallel
Obviously, the different types of substitution lead to different crystal structures and thus
different magnetic and transport properties. Replacing the trivalent elements by divalent
elements or divalent elements by divalent elements result in a mixed manganese valence
of Mn3+ and Mn4+. This modification can be explained by the double exchange interaction
of M n3+ and M n4+ cations [ 46-47]. In t he m eantime, t here a re ot her i nterations, s uch as
super-exchange, or bital or dering, c harge or dering, s pin or dering a nd t he Jahn-teller
interaction, which compete with the double exchange interation.
73 | P a g e
The doubl e e xchange m echanism e xplains t he c oupling be tween t he m obile hol es a nd
localized t32g electrons [ 48-49], w hich i s c ontrolled b y t he t ransfer i ntegral t ij between
Mn3+ and Mn4+ cations and depends on the angle spanned by Mn – O – Mn. The degree
of distortion of the lattice determines the Mn – O bond l engths and Mn – O – Mn bond
angles, thus indirectly influencing the magnetic properties. The degree of distortion of the
lattice increases in small particles, which leads to an increase in the mean deviation of the
Mn – O – Mn angle and the Mn – O length, as shown in fig.4.9.
(a) (b)
Fig: 4.9 S chematic c omparison of ( a) a non -distorted pe rovvskite w ith ( b) a di storted
perovskite structure due to Mn-O-Mn angle and Mn3+- O2- - Mn4+ interaction.
The double exchange theory is based on the assumption of strong interatomic ex change
between localized t2g spins and localized eg electrons, as shown in fig.4.9. In this situation
the f erromagnetic s tate appears as a r esult of k inetic ef fects, where i n many cases, a
concentrated transition into the f erromagnetic s tate coi ncides w ith a tr ansition into the
metallic s tate. In non -metallic c ompounds, a n a dditional i ndirect e xchange i nteraction
may a lso a ppear be tween m agnetic i ons w hich i s know n a s s uper-exchange i nteraction
and results in the antiferromagnetic state. Goodenough [50] showed that super-exchange
interactions through the oxygen in Mn3+ and Mn3+ or Mn4+ and Mn4+ are ferromagnetic in
the cas e o f a d ynamic J ahn-Teller ef fect. Removal of t he coope rative J ahn-Teller
distortions in LaMn3+O occurs under doping, due the dilution of the degenerate orbitals of
74 | P a g e
Mn3+ ions b y a non – Jahn – Teller i on e.g. M n4+. F rom t his poi nt of vi ew, t he
ferromagnetic be havior is not di rectly connected with metallic c onductivity in the
substituted m anganites. It i s a lso t o be not ed a c oncentrated transition into the me tallic
state cannot coincide (or cannot develop at all) with the transition into the ferromagnetic
state.
4.5 Magnetic Refrigeration

In this s ection, the appl ication of m agnetocaloric ef fect on magnetic r efrigeration was
discussed br iefly. It i s not i ntention t o pr ovide t he t echnical de tails of m agnetic
refrigeration. In a conventional vapor c ycle refrigerator, the refrigeration process occurs
due to the compression and decompression of a fluid working in a given thermodynamic
cycle. T he fluids c ommonly us ed i n t his t ype of r efrigerator a re da ngerous t o t he
environment a nd c ause t he de pletion of t he oz one l ayer. In a m agnetic r efrigerator, t he
refrigeration process oc curs due t o t he application and removal of a m agnetic field i n a
magnetic ma terial, called the ma gnetic r efrigerant. In ma gnetic r efrigerators, water o r
fluids a re not ha rmful t o t he e nvironment a nd a re us ed a s he at e xchangers. In or der t o
extract heat from a cold reservoir and release it to the hot sink, the magnetic refrigerant
should work in a given thermodynamic cycle. The main thermodynamic cycles suitable to
implement ma gnetic r efrigeration are ( i) C arnot c ycle, ( ii) E ricsson cycle a nd ( iii)
Brayton cycle. The Carnot cycle, which is made up of two isothermal and two adiabatic
processes i s s hown i n f ig 4.10. In t his c ycle, t he m agnetic m aterial a bsorbs he at i n t he
isothermal process CD, while it releases heat in the isothermal process AB.
The Ericsson cycle is composed of two isothermal and two isofield processes. A sketch of
this c ycle i s s hown i n fig 4.11. In t he i sofield pr ocess BC a t constant f ield H 1, t he
magnetic refrigerant releases heat, while in the isofield process DA at constant magnetic
field H0, the m agnetic refrigerant abs orbs he at. T he E ricsson cycle [51-53] e xhibits
optimal pe rformance w hen t he e ntropy curve of the m agnetic r efrigerant in t he i sofield
process BC is parallel to the entropy curve in the isofield process DA. The Brayton cycle,
formed b y two adiabatic a nd t wo i sofield pr ocesses, i s s hown in f ig.4.12. A s imilar
discussion about the isofield processes discussed in the Ericsson cycle holds also for the
Brayton cycle [ 51-53]. In order to illustrate the pr inciple of ma gnetic refrigeration, the
fig.4.13 is drawn which contains a magnetic material used as the magnetic refrigerant, a
75 | P a g e
coil to provide the magnetic field and two thermal switches to connect and disconnect the
magnetic refrigerant with the cold reservoir (volume to be refrigerated) and the hot sink.
S(T,H0,P)
Total Entropy
S(T,H1,P)
A B
D C
Temperature
Fig: 4.10 C arnot cycle: two i sothermal ( AB and C D) a nd t wo a diabatic ( DA a nd BC)
processes.
S(T,H0,P)
Total Entropy
S(T,H1,P)
A
D
B
C
Temperature
Fig: 4.11 Ericsson c ycle: t wo i sothermal ( AB a nd C D) a nd t wo i sofield (BC a nd DA)
processes.
Here, it is supposed for the sake of convenience, a magnetic refrigerator operating in the
Carnot c ycle s hown i n f ig.4.10. In t he f irst s tep of t he pr ocess, t he t hermal s witch 1 i s
turned on to connect the ma gnetic ma terial w ith hot s ink and the ma gnetic f ield is
isothermally applied. In this isothermal process, which can be represented by the path AB
in fig. 4.10, the entropy of the magnetic material is reduced, so that the entropy change is
less than 0, i .e. dS<0. Thus according to the thermodynamic relation dQ = TdS one gets
dQ<0, so that an amount of heat is released from the magnetic material to the hot sink.
In the second step, the thermal switch 1 i s turned off to disconnect the magnetic material
from the hot sink and the magnetic field is adiabatically reduced. In this adiabatic process,
this can be r epresented b y t he pa th BC i n f ig.4.10, t he t emperature o f t he m agnetic
76 | P a g e
material de creases. In t he t hird s tep, t he t hermal s witch 2 i s t urned on to c onnect t he
magnetic material with the cold reservoir and the magnetic field is isothermally reduced.
S(T,H0,P)
Total Entropy S(T,H1,P)
A B
D C
Temperature
Fig: 4.12 Brayton c ycle: t wo i sofield ( BC a nd DA) a nd t wo adiabatic (AB and C D)
processes.
In this is othermal process, w hich c an be r epresented b y t he pa th C D i n f ig. 4.10, t he

entropy of the magnetic material is increased so that the entropy change is greater than 0,
i.e.dS>0. Thus according to the thermodynamic relation dQ = TdS one gets dS>0, so that
an amount of heat is absorbed by the magnetic refrigerant from the cold reservoir. As a
consequence, the temperature of the cold reservoir and the magnetic field is adiabatically
increased.
Hot sink
switch 1
coil
switch 2
cold resevoir
Fig: 4.13 Scheme to illustrate the magnetic refrigeration
In this adiabatic process, represented by the path DA in fig: 4.10, the temperature of the
magnetic ma terial inc reases a nd the the rmodynamic c ycly is c ompleted. It s hould be
emphasized that this qualitative discussion about magnetic refrigeration, is just illustrative
and does not constitute a real prototype of magnetic refrigerator operating in the Carnot
cycle.
77 | P a g e
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“Calculation of t he giant m agnetocaloric e ffect i n the M nFeP0.45As0.55 compound”,
Phys. Rev. B 70, (2004) 094410
[4.32] A.H. Morrish, “The Physical principles of Magnetism”, (Wiley, new York), (1965)
Chapter 3
[4.33] A .M. T ishin, K .A. G schneidner, J r., V .K. Pecharsky, “Thermodynamics o f the
magnetocaloric effect”, Phys.Rev. B 64 (2001) 144406
[4.34] Jonker, G., and Van Santen, “Giant oxygen isotope shipt in the magneto resistive
perovskite”, J., Physica, 16, (1950)337,
[4.35] J. M . D . C oey, M.Viret, S. V on M olnar, “ Noise pr obe of t he dynamic ph ase
separation in La2/3 Ca1/3 Mn O3”, Adv. Phys. 48, (1999)167,
[4.36] G oodenough, J . B., “Theory of t he r ole of covalence i n t he p erovskite t ype
manganites LaM(II) MnO3”, Phys. Rev.100,(1955) 564,
[4.37] E dmonds, A. R .., “ Angular M omentum i n Q uantum M echanics”, ( Princeton
University Press), 1960,
[4.38] N agaev, E . L.., “ Large m agneto r esistance i n a n i nhomogeneous m agnetic
semiconductor”, Phys. Usp.. 38, (1996)781,
oxide La0.7Ca0.3MnO3”, J. Phys. Condens. 9,(1997) 8171,
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[4.41] T .Terai, T . K akeschita, T . F ukuda, M . Y amamoto, T . S aburi, H . K itagawa,
K.Kindo, M .Honda,, “ Magnetoresistance of L a0.7Ca0.3MnO3 single cr ystal and
polycrystalline”, Trans. Mater. Res. Soc. Jpn, 26 (2000) 217
[4.42] W . B oujelben, M . E llouze, A . C heich-Roihou, J.Pierre, Q .Cai, W .B. Y elon, K .
Shimizu, C .Dubourdieu, “ Neutron di ffraction, N MR a nd m agneto-transport
properties i n t he P r0.6Sr0.4MnO3 perovskite m anganite”, J.Alloys C ompd. 334
(2002)1
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transition and giant magnetoresistance in La1-xSrxMnO3”, Phys.Rev. B 51(20) (1995)
14103-14109
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L627
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81 | P a g e
Chapter Five Preparation of Manganites Perovskite and Experimental Techniques
5.1 Introduction
Lanthanum m anganites perovskite ( manganites in general) can be p repared b y m any

different s ynthesis t echniques a nd i n va rious f orms, i ncluding s ingle crystals,
polycrystalline ceramics and thick or thin films. Single crystals can be grown in several
ways, for i nstance b y t he f loating-zone m ethod [1]. Polycrystalline s amples can be
prepared by solid state mixing, involving repeated steps of mixing, grinding and heating
of oxides until a single-phase manganite is obtained. Polycrystalline manganites can also
be s ynthesized b y various w et-chemical m ethods [ 2-4]. T hick m anganite f ilms c an be
produced b y s praying t echniques a nd w ell-defined 2D -patterns c an be obt ained us ing
screen p rinting t echniques [5]. T hin f ilms a re us ually grown b y l aser ablation ( pulsed
laser deposition) or sputtering using sintered polycrystalline targets [6]. Depending on the
substrate, thin films can be prepared in epitaxial as well as polycrystalline forms [7].
The Ca and Pb, Ca a nd S r, C a a nd B a, dope d three l anthanum m anganite pe rovskite

samples under investigations in the present work were polycrystalline ceramics prepared
by the so-called solid state reaction technique. This chapter gives a detailed description of
the sample preparation, followed by a discussion on sample composition and morphology
and experimental measurements.
5.2 Target Compositions and Sample Designation
Three series of lanthanum-calcium-Strontium manganites perovskite, lanthanum-calcium-

Barium manganites perovskite and lanthanum-calcium-Lead manganites perovskite with
the g eneral c omposition La0.7(Ca1-xMx)0.3MnO3 (where M = Pb, Sr, Ba) were pr epared
for this investigation. The formula indicates that the manganites should be considered as
Pb substituted L a–Ca m anganites pe rovskite, as Sr substituted L a–Ca m anganites
perovskite, and as Ba substituted La–Ca manganites perovskite. This is unintended since
they could equally well be regarded as Ca substituted La–Pb manganites perovskite, as Ca
substituted La–Sr manganites p erovskite a nd a s C a s ubstituted La–Ba manganites
perovskite. The three La0.7(Ca1-xMx)0.3MnO3 (where M = Sr, Ba, Pb) series consisted of
sixteen samples with target compositions given by x = 0, 0.05, 0.10, 0.15, 0.20, and 0.25,
corresponding t o C a/Pb, C a/Sr, a nd C a/Ba ratios of 100: 0, 95: 5 90: 10, 85: 15, 80: 20,
82 | P a g e
75:25, and respectively. Thus, the variation of x corresponded to an equidistant exchange
of Ca and Pb, Ca and Sr, Ca and Ba.
Both c omplete f ormulas a nd a bbreviated s ample not ation w ill be us ed t hrough out t he
following chapters and sections. For e xample, the s ample w ith x = 0.10 will be w ritten
La0.7Ca0.27Pb0.03MnO3, or sometimes designated the x = 0.10 sample.
5.3 Sample Preparation Technique

The m agnetic and el ectric pr operties o f perovskite-type m anganites can b e ex plained in
terms of t he correlation between Double E xchange ( DE) and S uper Exchange (SE)
interactions or Mn3+/Mn4+ ratio. In addition to that, the influence of the homogeneity and
stability of structures are considered. Hence, the preparation technique plays the decisive
role i n t he i nvestigation on t he p erovskite m anganites. A mong t he di fferent m ethod
including t he s olid s tate r eaction t echnique m ethod [ 8], r f s puttering m ethod, l aser
ablation m ethod, a nd s ol- gel t echnique, e tc…. t ill now , t he s olid s tate r eaction m ethod
remains the most popular methods because it is simple process and inexpensive costs.
The solid – state reaction method is based on t he penetration of various solid atoms into
each other, which is c alled di ffusion pr ocess. W hen s olid m aterials are s intered at
temperature around two thirds of melting temperature, the diffusion process is fastened. If
initial s tate of mix ture is c hemical inhom ogeneity, the p roduct compound will be come
more homogeneous due to the diffusion of atoms. In diffusion process, the atom interacts
with each other and form new chemical interaction; this means that a new material can be
formed. T herefore, t he di ffusion pr ocess c hanges not onl y t he hom ogeneity l evel of
materials but a lso its c hemical f ormula; tha t a re w hy thi s me thod is c alled solid – state
reaction method [8].
The s olid - state r eaction method usually occurs at s low r ate de pending t emperature,
heating rate, particles size of powder and the ability of forming the phase between those
particles. In the case that particle size is small enough and the diffusion time is suitable, a
new solid particle can be homogeneously created. To increase the diffusion rate of ions,
the temperature is must high and particle size of mixed [9] powder is to be reduced. To
increase t he hom ogeneity of m aterials [ 9, 11-15,], t he g rinding, p ressing a nd s intering
process should be repeatedly carried out. However, the solid – state reaction method has
some disadvantages; hardly produces homogeneous materials with high mass density and
83 | P a g e
consumes more energy. In order to overcome those disadvantages, the important thing is
to shorten the diffusion length. It can be obtained by reducing the particle size and mixing
the compounds in atomic scale. In particular, the investigated samples in this thesis with
the following compositions:
La0.7 (Ca1-xPbx) 0.3MnO3 (where x = 0.00, 0.05, 0.10, 0.15, 0.20, 0.25) LCPMO
La0.7(Ca1-xSrx)0.3MnO3(where x=0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.50) LCSMO
La0.7 (Ca1-x Bax) 0.3MnO3 (where x = 0.05, 0.10, 0.15, 0.20, 0.25) LCBMO
were pr epared b y t he c onventional s olid – state reaction t echnique, w hich i ncludes t he
following steps.
Step-1:
The a mounts o f r aw ma terials w ith high purity (La2O3, CaCO3, BaCO3, P bO, PbCO3,
SrCO3 and MnCO3) were stoichiometrically calculated and weighed. The raw materials of
the samples were supplied by the Center for Materials Science (CMS), Vietnam National
University of Science, Hanoi, Vietnam. The compounds were then mixed and grounded
in ARE magnetic heating motors for 6 hou rs [10]. This is an important step for making
materials to be homogeneous, leading to complete the solid – state reaction by diffusion
of particles.
Step-2:
The mixed and grounded compounds were dried and again mixed by hand for 2 hours and
then pressed into pellets form. The pellets were pre-sintered at 900 0 C or 10000 C for 5, 8
or 10 hour s t o i nduce the s olid – state r eaction. Generally, there ar e f our ph ysical
processes involved in pre-sintering
⇒ Linear expansion of particles ⇒ Solid - state reaction
⇒ Contraction of compounds and ⇒ Growth of particles
Step-3:
In t his s tep the s ame procedure was followed as de scribed above. In t his cas e t he
compounds were pre-sintered at 10000 C for 5, 8, 10 hours.
Step-4:
After regrinding and mixing, the compounds were again pressed into pellets and sintered
at temperatures of 12000, 12500, 12700, 12800 or 13000 C [14] respectively.
The s amples w ere c ooled i n a ir and t hen pr ocessed for t he measurements. T he pr e-

sintering a nd s intering p rocesses w ere c arried o ut on c arbolate f urnace w ith a utomatic
84 | P a g e
temperature-controlled programmer at the Center for Materials Science (CMS), Vietnam
National University, Hanoi, Vietnam.
The f irst mix ing The fi rst The fi rst

and stirring process drying a nd Pressing,
Raw at 1500 -2000 C i n milling in air Presintering
for 3 or 4
ARE m agnetic hours
at 1000 0 C
Materials
heating motor for 8 for 5, 8, 10
hours with normal hours w ith
speed
The second mixing
The second drying and
Mixing, P ressing,
presintering a gain milling or grinding for
and grinding process
if s ingle pha se ha s
in air for 2 hours
not f ormed a t 2 hours
10000C with and then 6 hours in
heating rate 20/m
Pressing, sintered
Product
The t hird at t emperatures
0
mixing a nd around 1250 , Samples
0 0
grinding 1270 , 1280 ,
0
process for 1300 C
Fig: 5.1 S chematic di agram of s olid – state reaction technique u sed for p reparing
investigated samples
10000C
2.50C/min
8000C …………………………………………………………………………
2.50C/min
Turn off power
2000C
20C/min Room temperature
2h 15h Time t(h)
Fig: 5. 2 Pre-sintering process for the samples
85 | P a g e
12000, 12500, 12800, 13000 C
2.50C/min
7000C ………..….. 2.50C/min
Turn off power
2000C
20C/min Room temperature
2h 30h 1h t(h)
Fig: 5.3 Sintering process for the samples
5.4 Elemental Analysis
The e lemental c omposition a nd hom ogeneity of t he pr epared m anganite pe rovskite

samples w ere i nvestigated b y m eans of qua ntitative E nergy D ispersive S pectroscopy
(EDS) using a JEOL-5410LV scanning electron microscope. For composition detection
the m icroscope was op erated at 1 2 kV. The surface m icrostructure a nalyses of t he
samples w ere don e i n a JEOL-5410 LV S canning E lectron M icroscope a t C MS, H anoi
University of Science, Hanoi, Vietnam.
5. 5 Experimental Techniques and Measurements

5.5.1 Introduction
To s tudy t he m anganite pe rovskite s amples i n this t hesis, a num ber of e xperimental
techniques ha ve be en e mployed. T he m ain a im of t he s tudy i s t he obs ervation a nd
understanding of magnetic and magnetocaloric behavior as a function of temperature. All
samples were prepared by solid state reaction method through pre-sintering and sintering
steps. The pr epared samples f irstly w ere s ubjected to X-ray di ffraction (XRD)
measurements prior to other experiments being carried out. The details will be described
in t he i ndividual chapters. The ex periments t hat were pe rformed in this thesis are D SC,
TGA, SEM, EDS, XRD, DC a nd A C magnetization, hysteresis loop , thermomagnetic
FC/ZFC curves and magnetic isotherm curves.
86 | P a g e
The overall experimental stages and procedures are shown in fig: 5.4.
Starting Materials
Solid State Reaction DSC, TGA
Pre-sintering, Sintering
Physical Properties
XRD
Magnetic Magneto-caloric
Phase
Purity? Structure
Yes
No
No Yes
SEM
Fig: 5.4 The experimental stages and procedures
5.5.2 Fabrication of the Sample

The pow der m aterials t hat ar e us ed in this i nvestigation had a p arent A (Á1-xÁx)MnO3
perovskite structure, where A is rare earth element, Á is a di valent element, (Ca, Sr, Ba,
Pb). The c hemicals us ed f or m aking t hese s amples a re s hown i n T able 5.1. Enough
precursors to make approximately 10 grams of sample material were weighed out with a
precise 0.001 mg air flow protected electric balance and well mixed by means of a mortar
and pestle. The well mixed powder was then pelletized in a rectangular (L=20 mm, W=5
mm) a nd cylindrical di e ( 8-10 mm) to make th e pr oper pe llet. T he pe lletizing pr essure
was generally about 5kPa.This pressure was varied, depending on the compound strength,
and a djusted t o a chieve a w ell s haped f ine s ample, w hile a voiding a ny collapse or
breakage of t he s ample as a c onsequence o f pr essing. A ll br oken or collapsed s amples
were s imply crushed, r emixed, a nd pe lletized a gain. In general hi gh p ressure was not
applied, since it would limit and slow down the oxygen reaction of the compounds during
the sintering. The pelletized sample was then heat-treated for the first step of presitering
in a muffle furnace in air.
87 | P a g e
The m ethodology a nd equipment e mployed t o prepare t he s amples and experimental
measurements are schematically shown in fig.5.5.
Methodology of the sample fabrication Equipments used for the sample

fabrication and for measurements
Sample design …………………… Calculator & Periodic Table
Powder weighing
……………………… Air flow protected
Electronic Balance
………………………….......... Pestle & Mortar
Powder mixing
….
Powder for DSC, TGA ….. .. STD 2960
Pelletizing …….……………… Rectangular & Cylindrical Die
Pre-sintering
……………………… Carbolated Muffle Furnace
in air flow
Crushing …………………………. Pestle & Mortar
XRD Phase
……………………… XRD Philips D5005, D-8
purity?
…………………….… Rectangular & Cylindrical Die

Re - pelletizing
……………………… Carbolated Muffle Furnace

2nd Sintering
in air flow
XRD
SEM ………………………
Phase purity? XRD Philips D5005, D-8
Measuring the physical

properties ……………………… VSM, MPMS-XL & PPMS,
CMS, VNUS Hanoi, Vietnam, SSP,
Angström Lab, Uppsala University,
END
Sweden
Fig: 5.5 Schematic ex planations of t he m ethodologies a nd e quipment e mployed i n t he

fabrication of the sample and for the measurements.
88 | P a g e
The ge neral r ange of pr esintering t emperatures was va ried between 9000 C - 11000 C,
depending on t he class of samples. Then the samples were again taken for grinding and
pelletizing. In t he s econd s tep t he pe lletized s amples w ere t aken f or s intering a nd the
temperature r ange w as varied between 12000 C -13000 C, de pending o n t he na ture o f
samples. T he s intering t emperature m ainly d epends on t he m elting poi nt of t he
compounds in the sample mixture.
Table 5.1 – The chemicals employed for preparation of the samples:
Chemicals Formula Purity
Lnathanum Oxide La2O3 99.97%
Strontium Carbonate SrCO3 98%
Manganese Carbonate MnCO3 99.95%
Manganese Oxide MnO 98.9%
Calcium Carbonate CaCO3 99%
Lead Carbonate PbCO3 99%
Barium Carbonate BaCO3 99%
Lead Oxide PbO 99%
Calcium Oxide CaO 99%
There w as a w ide r ange of m elting t emperatures i n the di fferent pr ecursors f or t he

prepared samples, and the s intering t emperature w as opt imized by a trial and error
method, with guidance from t he l iterature. The s intered samples were t hen crushed i nto
powders in order to carry out XRD examination to assess the purity, in accordance with
the ICDD s tandard. The de tail ex planations of m easuring pr ocess ar e de scribed in
individual section.
89 | P a g e
5.6 Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA)
Measurements
Differential Scanning Calorimetry (DSC) is a thermal analysis technique, which is used to
measure t he t emperatures and heat f lows as sociated with t he s tructural a nd pha se
transition in materials as a function of time and temperature. Such measurements provide
qualitative and quantitative information about physical and chemical changes that involve
endothermic and exothermic processes or changes in heat capacity.
Thermo gravimetric A nalysis ( TGA) m easures the changes i n weight of a s ample w ith
increasing t emperature. M oisture cont ent and pr esence o f vol atile species c an be
determined w ith t his t echnique. C omputer c ontrolled gr aphics can calculate w eight
percent losses.
Fig: 5.6 DSC, and TGA, equipment Fig: 5.7 Scanning Electron Microscope
Differential T hermal A nalysis ( DTA) m easures t he di fference i n temperature be tween a

sample and a t hermally i nert r eference as t he t emperature i s r aised. The pl ot of t his
differential th ermal a nalysis pr ovides information on e xothermic a nd e ndothermic
reactions taking place in this sample. Temperatures for phase transitions; melting points;
crystallization can all be de termined by using the computer controlled graphics
package.The f igure 5.8, 5.9, 5.10, 5.11, 5. 12 a nd 5.13 s how t he D SC, T GA a nd dT G
graphs of raw materials what is used for making the perovskite samples. All the measured
samples s how one or m ore t emperatures w here the s amples h ave gone t horough s ome
exothermic a nd e ndothermic c hanges. La2O3 has sh own t wo absorption pe aks around
4120 C and 6860 C, CaCO3 around 9000 C MnCO3 around 4500 C, BaCO3 around 8500 C.
SrCO3 has not shown any changes upto around 9000 C. PbCO3 has even higher temp of
absorption.
90 | P a g e
15
Weight/(%), dTG/%/min, HeatFlow/(µV)

10
1140C
5
0
565.420C 8.16% loss
-5
-10 2.76% loss

La2O3 2.54% loss
-15
DSC
-20 0 TGA
412.19 C
0 200 400 600 800 1000
Furnace Temperature/0C
Fig: 5.8 DSC, TGA, dTG of La2O3
15
Weight/(%), dTg/%/min, Heat Flow/(µV)
-15 CaCO3
-30
DSC
TGA
dTG
-45
0 300 600 900

Fig: 5.9 DSC, TGA, dTG of CaCO3

15
-15
MnCO3
TGA
-30 dTG
DSC
0 300 600 900
Fig: 5.10 DSC, TGA, dTG of MnCO3
91 | P a g e
15
12
9
DSC
TGA
6
dTG
0
BaCO3
-3
0 300 600 900
Fig: 5.11 DSC, TGA, dTG of BaCO3

12
TGA
6
dTG
DSC
3
-3 SrCO3
0 300 600 900

Fig: 5.12 DSC, TGA, dTG of SrCO3
16
Weight/(%),dTG(/%/min), Heat flow/(µV)
12
8 DSC
TGA
dTG
4
PbCO3
0 300 600 900

Furnace temperature /(0C)
Fig: 5.13 DSC, TGA, dTG of PbCO3
92 | P a g e
There is a thermodynamic correlation between the magnetic phase transition temperatures
of all the studied materials and the temperatures where this thermal absorption has taken
place. An absorption peak means that some thermal energy has flown into the system in
order to achieve some ordered structure. A suitable sample for magnetocaloric use should
show a good correlation between the thermodynamic entropy and the ferromagnetic Curie
temperature. DSC and TGA measurements of studied samples were carried out at CMS,
National University of sciences, Hanoi, Vietnam.
5.7 Microstructure Observation and Composition Determination (SEM/EDS)

The photograph of surface microstructure indicates whether a sample is well prepared or
not. In t hese m easurements, t he e lectron be am w ith an wavelength of ∼ 100 Å i s
accelerated at 12kV toward the surface of the sample, interacts to the surface atoms and
emits secondary electrons and then the surface microstructure of samples can be seen.
Fig: 5.14 Information obtained by electron beam irradiation
In this measurement, the electron beam with diameter of 100 Å is accelerated toward the
surface of the sample, interact with surface atom and emit secondary electron. A detector
collected the s econdary el ectron and then we can see t he s urface m icrostructure of
sample. The ene rgy di spersion spectra m easurement pr ovides t he i nformation a bout t he
presence and content of the elements i n t he s tudied s amples. S imilar t o t he principle o f
the SEM, the energy of secondary electrons was collected and it depends on the kind of
element in materials. Therefore, based on energy spectra of secondary electrons, we can
determine the c hemical c omposition of the s amples a nd their e lement c ontent. The
Energy Dispersion S pectrum m easurements of s tudied s amples w ere c arried out i n a n
Energy Dispersion Spectrometer (EDS) included in SEM at CMS, National University of
sciences, Hanoi, Vietnam.
93 | P a g e
5.8 X-Ray Diffraction Analysis
When t he x -ray b eam with given the energy and the w avelength irradiates int o the
sample, i t w ill be r eflected on va rious c rystal pl anes a nd i nterfaces. T he di ffraction
intensity o f x -ray b eam depends on t he i ntensity a nd t he pos ition of s pectrum l ine, t he
lattice pa rameters, t he s ymmetry as w ell as t he cr ystal ph ases can be obtained. The
structure of the studied samples was examined in a BruKer D5005 X-ray diffractometer at
CMS, i n a B ruker D 8 X-ray Diffractometer a t I IC a nd Chemistry de partment of
University o f C hemical T echnology, w hich uses t he C u - K α radiation with
λ = 1.54056Å.
Fig: 5.15 Advanced D8 XRD at chemical department and D5 XRD at CMS and Uppsala.
5.9 Magnetic Measurement

5.9.1 The Zero Field Cooled (ZFC) and Field Cooled (FC) thermo-magnetization
measurements
To investigate t he ef fects of m agnetic i nteraction, Zero Field Cooled (ZFC) and Field
Cooled (FC) methods of the samples can provide the required information. In ZFC, first
the s amples a re cooled to 30 K , 50 K , 100 K and 110 K while no m agnetic f ield i s
applied. After lowering the sample’s temperature down to that of required temperature, a
small external filed is applied. The sample is then heated up at a constant rate while the
net m agnetization i s m easured. W hile t he s ample i s being cooled i n z ero applied fields,
the pa rticles te nd to magnetize a long a pr eferential c rystal di rection in the la ttice to
minimize the ma gnetocrystalline e nergy. The ne t mom ent of the s ystem w ill be z ero,
since the or ientation of e ach crystal va ries. This w ill s till be the s ame w hen a s mall
94 | P a g e
external field is applied, as is seen in the low temperature portion of the ZFC curves. With
an i ncrease i n t emperature, m ore e xtra e nergy i s i ntroduced i nto the s ystem, s o t he
magnetic mom ents w ill be di sordered from the crystal di rection and will a lign in the
external field direction to minimize the magnitude of the Zeeman energy.
Fig: 5.16 VSM equipment at CMS
Signal Pickup Coils

Fig: 5.17 Schematic mechanism of VSM Equipment
In other words, the thermal energy activates the Zeeman interaction. With further increase
in temperature, the n et m oment r eaches i ts p eak, where t he greatest popul ation of
moments a ligns w ith the e xternal f ield. This pe ak temperature is c alled the B locking
Temperature (TB). After this point, the thermal vibrations are strong enough to overcome
the Zeeman i nteraction energy and r andomize t he m oments. A fter r eaching t he r oom
temperature unde r e xternal f ield, t he s ample i s c ooled dow n t o r equired t emperature.
95 | P a g e
After t his s tage, w hile t he s ample i s he ated up, t he ne t m oment i s m easured. T his is
known as the Field Cooled (FC) method, and the magnetization will diverge from that of
ZFC ne ar T B. This be havior oc curs a s t he pa rticle’s s pins t ry t o a lign w ith e asy c rystal
axis in t he vi cinity of t he a pplied f ield di rection a nd f reeze i n t hat di rection as t he
temperature is reduced [16].
5.9.2 Measurement Process

At a pa rticular t emperature i n paramagnetic r ange, t he s ample w as cooled in applied
magnetic field H to as low as possible temperature T0. Then the temperature of the sample
is steadily increased and MFC (T) values were recorded in the heating process. To measure
MZFC (T), the s ystem w as c ooled without a pplied magnetic f ield from a te mperature in
paramagnetic range to the possible lowest temperature T0. At this temperature, a magnetic
field H was applied and MZFC (T) values were recorded in heating process.
5.10 SQUID Magnetometer

For t he m easurements of m agnetization a Superconducting Q uantum i nterface D evice
(SQUID) ma gnetometer MPMS- XL5, USA was us ed. The m easurements w ere done at
the D epartment of S olid State P hysics, Faculty of E ngineering S ciences, Angström
Laboratory, Uppsala University, Sweden. The magnetic properties measurements system
MPMS X L5 is a v ery s ensitive and s ophisticated analytical i nstrument conf igured
specially for t he s tudy of m agnetic pr operties o f s mall s amples ove r a broad r ange of
temperature f rom 4.2 K t o 400K a nd m agnetic f ields f rom -10T t o +10T. T his s tandard
system made by Quantum Design Inc. USA can measure the magnetic moment of solid,
powder a nd l iquid s amples with differential s ensitivity of 10 -9 emu and can handle a
maximum s ignal s ize of 0.5 e mu. A ge neral vi ew of t he M PMS- XL5 with its s ystem
components i s s hown i n f ig.5.18. Based on this s ensitive de vice t he s o-called SQUID
magnetometer ha s b een developed. SQUID magnetometer i s us ed to characterize
materials when the highest detection sensitivity over a broad temperature range and using
applied magnetic fields upto several tesla is needed. Nowadays this instrument is widely
used worldwide in research laboratories.
The m ajor c omponents of a S QUID m agnetometer a re: s uperconducting m agnet,

superconducting detection coil, a SQUID connected to the detection coil, superconducting
magnetic s hield. S uperconducting m agnets a re s olenoid m ade of s uperconducting w ire
96 | P a g e
which m ust be ke pt at l iquid he lium Dewar. T he uni form m agnetic field i s pr oduced
along t he a xial c ylindrical bor e of t he c oil. T he s uperconducting pi ck-up coil s ystem,
which is configured as a second order gradiometer is placed in the uniform magnetic field
region of t he s olenoidal s uperconducting m agnet. T he S QUID d evice i s us ually a t hin
film that functions as an extremely sensitive current to voltage converter. Measurements
are done in this equipment by moving the samples through the second order gradiometer.
Hence, the magnetic moment of the sample induces an electric current in the pick-up coil
system. S uperconductingmagnetic s hield i s us ed to s hield t he S QUID s ensor f rom t he
fluctuations of the ambient magnetic field of the place where the magnetometer is located
and from the large magnetic fields produced by the superconducting magnet.
Fig: 5.18 External View of MPMS- XL5 SQUID Magnetometer
Using this equipment one can measure the FC/ZFC, DC and AC magnetization, the real
and i maginary components of A C m agnetic s usceptibility a s a f unction of f requency,
temperature, AC ma gnetic f ield amplitude a nd DC ma gnetic f ield, and time . Using a
specially designed sample holder the magnetic moment as a function of angle can also be
measured. It is an important feature of the instrument that one can change the magnetic
fields either b y oscillation mode or no ove rshoot mode. The oscillation mode is used to
minimize the remanent field of the magnet, whenever an accurate value of magnetic field
is ne eded, e .g. i n c ase of z ero f ield c ooling. I n t he h ysteresis m easurement t he no
97 | P a g e
overshoot mode has been selected, in which the field is changed directly from one value
to another, and the magnet is returned to its persistent mode.
The MPMS- XL5 features the new reciprocating sample measurement system. Unlike DC
measurements where th e s ample is move d thr ough the c oil in discrete s teps the R SO
measurements are performed using a servomotor, which rapidly oscillates the sample and
it i s s hown i n fig: 5.19. A s haft e ncoder on t he s ervomotor r ecords t he pos ition of t he
sample synchronous with the SQUID signal. The data received is fitted to an ideal dipole
moment response. To ensure this assumption is applicable samples need to be small: the
calibration sample is a cylindrical of 3mm diameter and 3 mm height.
SQUID Voltage
(a)
Position
(b)
Straw
Sample
3cm
SQUID pick-up coils
Fig: 5.19 Illustration of RSO m easurements with s mall a mplitude, (a) the ide al S QUID
response f or a di pole a nd ( b) t he m ovement of the s ample w ithin the S QUID pi ck-up
coils.
Samples of thi s s ize or s maller ma tch a n ideal poi nt di pole to an accuracy of

approximately 0.1%. RSO m easurements can be m ade i n one of t wo c onfigurations:
Centre or m aximum s lope. C entre s cans us e l arge os cillations ( 2or 3 c m) a round t he
centre poi nt of t he pi ck-up c oils. These s cans t ake a l ong t ime but t he sample al ways
remains properly located and a large num ber of measurements ar e r ecorded. These give
the m ost accur ate readings. The m aximum s lope m ethod oscillates t he s ample ove r a
98 | P a g e
small r egion (02cm) at t he m ost l inear pa rt of t he S QUID response. The s maller
amplitude m akes m easurements qui cker and prevents t he s ample be ing s ubjected t o
significant ma gnetic f ield variation; how ever it a lso makes the me asurements le ss
accurate and susceptible to drift in the sample position.
5.11 Isothermal Magnetization Measurements

The isothermal of magnetization curves M (H), were carried out at a various temperatures
around a phase transition temperature, T C. These measurements allow us to calculate the
temperature dependence of magnetic entropy change by using equation
( M n − M n+1 ) H
=∆S ∑ Tn +1 − Tn
∆H n
In this thesis, FC, ZFC and the magnetization measurements were done in an MPMS-XL5
SQUID m agnetometer i n t he t emperature range f rom 10 K t o 350 K a nd dc m agnetic
∆S
fields w ith a r ange f rom 0 t o 5 T . T he m agnetic e ntropy c hanges M, were c alculated
from the magnetization data, which is based on Maxwell relation.
99 | P a g e
References
[5.1] U rushibara, A ., Y . M oritomo, T ., A samiysu, a nd Y . T okura., “ Insulator m etal
transition and giant m agnetoresistance i n La1-xSrxMnO3 Phys. R ev. B 51( 20) (1995)
14103-14109
[5.2] Mori, M., N.M. Sammens and G.A. Tompsett, “Fabrication processing condition for
dense sintered La0.6AE0.4MnO3 perovskites synthesized by the coprecipitation method
(AE = Ca and Sr)”, J. Power.Sources, 86, (2000) 395-400
[5.3] Philip, J. a nd T .R.N. K utty, “ Preparation of m anganite pe rovskites b y a w et
chemical method involving a redox reaction and their characterization”, Mater. Chem.
And Phys., 63 (2000) 218-225
[5.4] Goldschmidt, V. “Geochemistry”, Oxford University press (19958)
[5.5] Balcells, L., A .E. C arrillo, B ., m artynez, F., S andiumenge, a nd J. F ontcuberta,
“Room t emperature ma gnetoresistive s ensor based on thick films ma nganite
perovskite”, J. Magn and Magn Mater. 221, (2000) 224-230
[5.6] Prellier, W., P. Lecoeur, and B. Mercy, “Colossal-magnetoresistive manganite thin
films”, J. Phys. Condens. Matter, 13 (2001) R915-R944
[5.7] G upta, A ., G .Q.Gong, G .Xiao, P .R. D uncombe, P . Lecoeur, P . T rouilloud, Y .Y.
wang, V.P. Dravid, and J .Z. S un, “Grain-boundary e ffects on t he m agnetoresistance
properties o f pe rovskite m anganite films”, P hys.Rev. B 54 (22) (1996) R 15629-
R15632
[5.8] V alenzuela, R ., “ Relationship be tween s pin or der a nd t ransport a nd m agneto
transport pr operties i n La0.67Ca0.33Mn1-xAlxOy compound”, M agnetic C eramics
(London: Cambridge University Press), 1994,
[5.9] Jonker, G ., a nd V an S anten, J ., “ Spin – glass like b ehavior i n La0.3Ca0.7 Mn O 3”,
Physica, 16, (1950) 337,
[5.10] Schifeer, P., Ramrez, A. P., Bao, W., Cheong, S. W., “Low temperature magneto
resistance and the magnetic phase diagram of La1-xCax Mn O 3”, Phys. Rev. Lett. 75,
(1995) 3336,
[5.11] C hainani, A., M athew, M ., S arma, D . D., “ Giant ox ygen i sotope s hipt i n t he
magneto resistive perovskite LaCax Mn O3”, Phys. Rev. B. 17, (1993) 15397,
[5.12] H ervieu, M ., M ahesr, R ., R anoavihai, N ., Rao, C . N . R ., “ Evidence of m agnetic
polarons i n t he m agneto r esistive pe rovskites”, J . S olid-State. i norg. Chem., 32,
(1995)79,
100 | P a g e
[5.13] Ibarra, M ., A lgarabel, P ., M arquina, C ., Blasco, J ., G arcia, J ., “ Large m agneto
volume effect in Yttrium doped La-Ca-MnO perovskite”, Phys. Rev. Lett. 75, (1995)
3541,
[5.14] A rnold, Z ., K ameney, K ., Ibarra, M ., A lgarabel, P ., M arquina, C., B lasco, J .,
Garcia, J ., “ Spin – glass ins ulator s tate in (Tb-La)2/3 Ca1/3MnO3 perovskite”, P hys.
Rev. Lett. 67, (1995) 2875,
[5.15] D eleresa, J ., B lasco, J ., Ibarra, M ., G arcia, J ., M arquina, C ., A lgarabel, P ., Del
Moral, A ., “ Spontaneous be havior a nd m agnetic f ield a nd pr essure e ffects on
La2/3 Ca1/3MnO3”, Solid-St. Commum, 96, (1995) 627,
[5.16] Denardin, J.C., Brandl, A.L., Knobel, M., Panssod, P., Pakhhomov, A.B., Liu, H.,
Zhang, X .X., “ Thermoremanence and zero-field-cooled/field-cooled magnetization
study of Cox(SiO2)1-x granular films”, Physical Review B, 65, (2002) 064422
101 | P a g e
Chapter Six Study of La0.7(Ca1-xPbx)o.3MnO3 Perovskite
6.1 Introduction
A list of the studied samples in this chapter is given below:
(i) La0.7(Ca1-xPbx) 0.3MnO3 (ii) La0.7(Ca0.95Pb0.05) 0.3MnO3
(iii) La0.7(Ca0.90Pb0.10) 0.3MnO3 (iv) La0.7(Ca0.85Pb0.15) 0.3MnO3
(v) La0.7(Ca0.80Pb0.20) 0.3MnO3 (vi) La0.7(Ca0.75Pb0.25) 0.3MnO3
This chapter presents the results on t he scanning electron microscopy, energy dispersion
spectrum, differential s canning calorimetry, t hermo gravimetric a nalysis,
crystallographic, magnetic and magnetocaloric properties of the La0.7 (Ca1-x Pbx)0.3MnO3
series. The c rystallographic pr operties w ere i nvestigated b y x -ray d iffraction, a nd
Rietveld refinement and it was us ed t o e xtract de tailed i nformation on t he s tructural
changes a ssociated w ith t he va riation of t he C a/Pb r atio. C ombined w ith m agnetization
data, a s trong r elationship between structure and magnetic pr operties in t he
La0.7 (Ca1-x Pbx)0.3MnO3 series is documented. The value of ionic radius <rA> in A-site
(A=La, Ca and Pb) has a strong influence on m agnetic and magneto-caloric properties in
particular of perovskite – type manganites. With the substitution of different elements in
A – site, one c an achieve t he l arge m agnetic entropy changes i n a l arge t emperature
range, from 180 K t o over r oom temperature. Recently, the s tructure and magnetic
properties of pe rovskites m anganites ha ve be en s tudied b y t he m any ph ysicists a nd
researchers. Troyan Chuk et.al. [1] have observed that the La 1-xPb x MnO 3 manganites
systems (x = 0.4 t o 0.6) have a rhombohedral (slightly distorted) cubic structure. Hwang
et. al. [2] ha ve s tudied the crystal s tructure and m agnetic s caling b ehavior of
La 1-x Pb x Mn O 3 perovskites (x= 0.0 to 0.5) and indicated that all samples crystallized in
the rhombohedral s tructure. In our c ase, t he s ubstitution of Pb2+ ions on C a2+ with La3+
sites induces a m ixed valence s tate of M n3+/Mn4+ and enhances t he m agnetic t ransition
temperature in this series. The r esults are shown in figures. It i s ob served t hat t he
symmetry d ecreases f rom t he cubi c t o orthorhombic. M ore ov er t he C urie t emperature
increases from 252 K for x= 0.00 to 291 K for x= 0.25. Based on those interesting results,
the composition of La0.7(Ca1-x Pbx)o.3MnO3 were chosen for our work. In this chapter, the
detailed results about the structure, magnetic, and magneto-caloric properties of the above
samples are presented and possible explanations for this relationship are discussed.
102 | P a g e
6.2 Scanning Electron Microscope (SEM) Analysis
The microstructure of the La0.7(Ca1-xPbx)0.3MnO3 samples were investigated by Scanning
Electron Microscopy ( SEM), ut ilizing a J EOL-5410 m icroscope operated a t a n
acceleration vol tage of 12 kV . The (SEM) ana lysis shown in f ig 6.1 indicates tha t th e
crystallites of t he s amples a re qui te hom ogeneous a nd the s ize of th e c rystallites va ries
from 0. 5 µ m ( x= 0.00) t o a round 1 µ m ( x= 0.15) with i ncreasing P b c ontents. By
substitution of P b f or C a, a s econdary pha se m ay b e f ormed, with dr astic c hanges i n
microstructure. There is a possibility to explore the liquid phase and hence the crystalline
particles develop easily due to this existence of liquid phases [3-7].
La0.7Ca0.3 Mn O3(13000 C) La0.7Ca0.285Pb0.015 Mn O3(13000 C)
La0.7Ca0.27Pb0.03MnO3 (13000 C) La0.7Ca0.255Pb0.045MnO3 (13000 C)

Fig: 6.1 Surface electron micrographs of selected La0.7 (Ca1-x Pb x) 0.3 Mn O3 samples. The
scale bars correspond to 5 µm (the images are scaled equally).
103 | P a g e
La0.7Ca0.24Pb0.06MnO3 (13000C) La0.7Ca0.225Pb0.075MnO3 (13000 C)
Fig: 6.1 Surface electron micrographs of selected La0.7 (Ca1-x Pb x) 0.3 Mn O3 samples. The
scale bars correspond to 5 µm (the images are scaled equally).
6.2.1 Grain Size and Morphology

The grain s ize a nd s urface m orphology of t he La0.7(Ca1-xPbx)0.3MnO3 series w ere
investigated by s canning electron microscopy (SEM). Figure 6.1 s hows surface electron
micrographs o f La0.7(Ca1-xPbx)0.3MnO3 samples.The va riation i n c omposition c auses
significant changes in morphology. The La0.7(Ca1-xPbx)0.3MnO3 sample consists of highly
aggregated grains and appears to have almost a few porosities. The closely packed grains
occur i n di fferent pol ygonal for ms. When t he Pb content i s i ncreased at t he ex pense of
Ca, the grain size increases. In such a case the morphology of the grain interfaces become
neck-like. Apparently, the samples become more porous.
6.3 Energy Dispersion Spectrum (EDS) Analysis

6.3.1 Elemental Analysis
The elemental composition and homogeneity of the La0.7(Ca1-xPbx)0.3MnO3 samples were
investigated by means of quantitative energy dispersive x-ray spectroscopy (EDS) using a

JEOL-5410 s canning e lectron m icroscope e quipped. F or c omposition de tection t he
microscope w as ope rated at 1 2 kV. Figure 6.2 shows a t ypical E DS s pectrum of t he
104 | P a g e
La0.7Ca0.3MnO3, a nd L a0.7Ca0.225Pb0.075MnO3 samples. T he s pectrum c ontains
characteristic peaks of La, Ca, Mn, O, Pb which are target components in the compounds.
The c hemical c ompositions a re de termined b y t he E nergy D ispersion S pectrum ( EDS)
which i s s hown i n f ig: 6.2. The f igure s hows that t he s ample’s c ompositions are as
similar t o t he nor mal on es; i .e. t here ha s b een n o e vaporation of Pb by s intering. The
photograph of surface microstructure indicates whether a sample is well prepared or not.
(a)
(b)
Fig: 6.2 E DS of (a) LCMO and (b) LCPMO s eries. Characteristic pe aks ar e l abeled by
corresponding elements.
105 | P a g e
In general, t he m easured s ample c ompositions were i n qui te g ood a greement w ith t he
target c ompositions. The a nalysis s hows t hat C a a nd P b a re exchanged i n a n
approximately linear manner. In fact, the EDS technique is not very well suited for porous
specimens like the La0.7Ca0.225Pb0.075MnO3 samples. S ince t he oxygen s toichiometry has
not be en de termined p roperly i t w ould pe rhaps be m ore c orrect t o u se t he f ormula
La0.7Ca0.225Pb0.075MnO3±δ for t he m anganite compounds. However, bearing t his i n m ind,
the slightly simpler notating not involving ±δ will be used in the following.

Measurements
Figure 6.3, 6.4 and 6.5 show the results of thermal analysis scans for a s eries of samples
La0.7(Ca1-xPbx)0.3 Mn O 3 where x = 0.00, 0.05, 0. 1, 0.15, 0.2, 0.25 . It i s found t hat all
samples have shown the similar reaction. For all samples with different Pb concentration,
a continuous weight loss occurs until a rise in 8940 C accompanied by an exothermic heat
effect. After 9000 C only little weight loss is observed, and no thermal effect occurs. So it
is that the suitable calcinations temperature is at least over 900 0 C. The organic removal
process w as c ompleted at a bout 930 0 C, favoring the crystallization pr ocess. A ll D SC
curves show one broad endothermic peak around at 88 0-1200 C, the second endothermic
peak a t 409.81 0 C, t he t hird one a t 488 0 C a nd t he f ourth one a t 570 0 C a nd f ifth
exothermic peak happens at 830.19 0 C other sharp endothermic peaks around at different
temperatures which is shown in the above figures for sample with x= 0.25. It is suggested
that the first two endothermic peaks are due to the evaporation of water out of the samples
and t he s econd one c orresponds t o t he de composition of La2O3.nH2O in to intermediate
0
oxide pha ses. T he s harp e ndothermic pe ak a round 488 C is r elated to thermal
decomposition of l anthanum h ydroxide, La ( OH) 3 originating f rom La2O3 in the wet
milling process [ 21-24]. W hen keeping La2O3 at hi gh hum idity conditions, a part of La
(OH) 3 is oc curred. F rom c omparison w ith T GA a nalysis of t he r aw m aterials M nCO3
and P bCO3, t he e ndothermic pe aks a t 830.19 0 C a nd a t 894 0 C can be r elated to the
thermal de composition of P bMnO3. T he f uzzy exothermic pe ak a round 950 0 C can be
considered to correspond to the start of the reaction in which the perovskite structure is
formed [25-28].
106 | P a g e
0 300 600 900
20 1170 C
10 4850 C 8410 C
x=0.25 9170 C
0 4100 C
20 1150 C
10
Heat Flow /(µV)
4850 C
x=0.15 8410 C 9170 C
0
4100 C
20 870 C
10
4850 C 8410 C 9170 C
0 x=0.05
4100 C
-10 0
81 C
10
4850 C 0
x=0.00 8410 C 917 C
0
4100 C
0 300 600 900
0
Furnace temperature / C
Fig: 6.3 DSC pattern of La0.7(Ca1-xPbx)0.3MnO3 series
0 300 600 900

0 Mass variation=10%,
-10 2.25%, 4%, 5%, 5.21%
x=0.25
-20
0
Weight /(%)
-10
x=0.15
-20
0
-10
x=0.05
-20
0
-10 x=0.00
-20
0 300 600 900
Furnace Temperature / 0 C
Fig: 6.4 TGA pattern of La0.7(Ca1-xPbx)0.3MnO3 series
107 | P a g e
0 300 600 900
0.0
-1.5 5700 C 8410 C 0
x=0.25 917 C
-3.0 8410 C
0.0
dTG/%/min
-1.5 5700 C
x=0.15 8410 C 0
917 C
-3.0 8410 C
0.0
-1.5 5600 C
x=0.05 0
8410 C9170 C
-3.0 841 C
0.0
-1.5
x=0.00
5600 C 8410 C
0 9170 C
-3.0 840 C
0 300 600 0 900
Furnace Temperature / C
Fig: 6.5 dTG pattern of La0.7(Ca1-xPbx)0.3MnO3 series
In these e xperiments it is c learly s een that w ith increasing P b substitution, all the rmal
transitions a re shifted t o l ower t emperatures. T GA c urves s how t he w eight l osses a t
different temperatures. The total weight loss in sample la0.7Ca0.225Pb0.075MnO3 is 22.58%.
6.5 X- Ray Diffraction Analysis

Fig: 6.6 pr esents t he X-Ray D iffraction Patterns w ith index num ber hkl of t he
investigated examined samples and the enl arged vi ew of 2 θ = 32 0 to 33.5 0 has be en
shown i n f ig: 6.7 . When t he X -ray be am w ith g iven t he e nergy and t he w avelength
irradiates into the sample, it will be reflected on various crystal planes and interferes with
another. T he di ffraction intensity o f X -ray d epends on the ang le be tween t he be am and
crystal pl ane. B ased on t he i ntensity a nd t he position of s pectrum l ine, t he l attice
parameters, the symmetry as well as the crystal phases can be obtained. The structure of
the studied samples was examined in a BruKer D5005 X-ray diffractometer, in a Bruker
D8 X-ray Diffractometer which uses t he C u - K α radiation with λ = 1.540 56 Å and
1.56056 Å . It is clear from t he fi gure that all s amples a re o f s ingle pha se w ith
orthorhombic structure. La1-xPbxMnO3 compounds have been investigated in Ref [1, 2]
108 | P a g e
with he xagonal c ells of s pace gr oup R 3c [ 8-14] f or a ll x= 0.00 to 0. 5. T he l attice
parameters derived from data of fig: 6.6 are shown in table-6.1 and table-6.4. Significant
increases o f pa rameters a nd unit c ell vol ume is r elated with increasing of Pb2+ ions
leading to increase average ion radius of A – sites, <rA>. Typical ionic radii were directly
quoted from “Electronic Table of Shanon Ionic Radii, J. David Van Horn, 2001”.
6.5.1 Structural Characterization

After each s intering, t he s amples w ere e xamined f or ph ase pu rity by X RD. Figure 6.6
shows x -ray di ffraction patterns of t he La0.7(Ca1-xPbx)0.3MnO3 samples. All
diffractograms were obtained at room temperature. At first, the diffraction patterns appear
at around 2θ =22o. However, from the enlarged view of the 2θ = 32°–33.5° region, shown
in F igure 6.7. It i s c lear t hat t he c ompositional va riation causes s ignificant s tructural
changes.
La0.7(Ca1-xPbx)0.3MnO3
(200)
Intensity (a.u.)
(004)
(312)
(202)
(002)
(224)
(116)
(131)
(404)
(532)
x=0.25
x=0.20
x=0.15
x=0.10
x=0.05
x=0.00
30 45 60 0 75 90
2 Theta (θ )
Fig: 6.6. X-ray diffraction patterns of La0.7(Ca1-xPbx)0.3MnO3 samples with index number
h, k, l
As x is i ncreased, t he i ntense di ffraction pe ak observed f or t he LCPMO s eries with

sample ( x = 0 , 0.05, 0. 1, 0. 15, 0. 20, 0. 25) g radually c hanges. Corresponding g radual
109 | P a g e
changes of the XRD lines can be observed at other reflection angles. By XRD indexation
the samples were shown to be well-crystallized perovskite oxides containing no i mpurity
phases. The fitted line positions of the samples with low values of x, i.e. with no splitting
of the main reflection, suggested an orthorhombic perovskite unit cell. This structure has
an intense 200 reflection at about 2θ = 32.8 0. The superposition of the diffraction peaks
appears as a s ingle l ine i n t he obs erved x -ray pa ttern. Thus, this pr eliminary a nalysis
indicated that the gradual change of the XRD patterns, induced by increasing the amount
of Pb at the expense of Ca, was associated with a cubic to orthorhombic phase transition.
This conclusion is, of course, only valid for room temperature. The x-ray analysis did not
provide a ny i nformation on a pos sible t emperature de pendence on t he s tructural
properties of the samples. By matching the XRD patterns to the International Centre for
Diffraction Data ( ICDD) da tabase, it w as f ound that t he at oms w ere cr ystallized in a n
orthorhombic structure, and their forms in terms of the hkl indices were obtained for the
parent m aterial. The l attice pa rameters a, b, c were calculated for t he or thorhombic
structure by using the following formula
1/d2= h2/a2+k2/b2+l2/c2 6.1
00
0.05
0.10
Intensity (a.u.)
0.15
0.20
0.25
32.0 32.5 33.00 33.5

2 Theta (θ )
Fig: 6.7 Enlarged vi ew of t he 2 θ = 32.0 0-33.50 for X -ray di ffraction pa tterns of

La0.7(Ca1-xPbx)0.3MnO3 series
110 | P a g e
In this cal culation, the hi gher d egree r esults of t he X RD s can were u sed to test t he
accuracy of the measurements. The fig. 6.8, 6.11, 6.12 a nd Table 6.1, 6.4, 6.5 s how that
the l attice pa rameter as well as uni t cel l vol ume i ncrease w ith increasing l ead contents.
This i s a n i ndication t hat t he M nO6 octahedron i s e longated l ong t he c a xis b y dopi ng
with smaller amounts of Lead substituted for Calcium. The smaller size of the increase in
a, b, c is expected, due to the replacement of the smaller atomic size calcium ion (<rCa>
=1.0Å) by the larger atomic size of Lead (<rPb> =1.35Å). The structure will tilt to fit the
larger atom inside the cell.
6.5.2 Rietveld Analysis
To give a m ore detailed description of the structural changes caused by the exchange of
Ca and Pb a Rietveld refinement analysis [15, 16] was adopted. This method is far more
complex t han ba sic i ndexation. It pr ovides a c omplete s tructural m odel a nd a f it of t he
entire diffractogram, including line positions, line widths and relative line intensities. A
Rietveld model employs lattice parameters, atomic positions, occupation factors, thermal
parameters, etc. A thorough introduction to the Rietveld refinement method can be found
in Y oung [ 17]. The R ietveld a nalysis w as carried out us ing t he c omputer pr ogram
Fullprof - 2.
6.5.3 Structural Model

Establishing a R ietveld model from s cratch can be a t edious t ask. One must provide an
initial s et of structural pa rameters ( space group, lattice cons tants, atom t ypes, atomic
positions, etc.), which results in a calculated x-ray pattern in fairly good agreement with
the obs erved x -ray pa ttern. Otherwise the minimization algorithm will probably diverge
and the result will be of no physical relevance. To calculate the initial parameter values
for the perovskite La0.7 (Ca1-x Pbx)0.3MnO3 series we had taken an idea from the literature
[18] and are used with appropriate modifications. The previous investigations suggest to
use t he s pace group P bnm w ith Z = 4 for L a0.7Ca0.3MnO3 (Z is the num ber of f ormula
units per unit cell). This space groups represent orthorhombic symmetry. The space group
has a num ber of e quivalent c rystal pos itions t he s o-called W yckoff p ositions. When
setting up a Rietveld model, the available atoms or ions must be distributed among these
positions. The following Table-6.2 gives an ove rview of t he equivalent c rystallographic
111 | P a g e
positions a nd t he c orresponding r elative c rystal c oordinates of t he P bnm s pace groups.
The table also lists the atomic site occupation corresponding to the nominal compositions
of the La0.7 (Ca1-x Pbx)0.3MnO3 compounds. For the Pbnm space group, one third of the
oxygen i ons w ere pl aced a t 4 c sites a nd t he r emaining ox ygen i ons a t 8d sites. In t he
a p
following, t he not ation O and O are us ed t o d istinguish t hese i ons. All X RD pa tterns
indicate t hat a ll s pecimens ha ve s ingle pha se, orthorhombic s tructure and i ndexed i n
Pbnm space group. Refined lattice parameters and cell volume, ionic radius, bond a ngle,
bond l ength of t his s eries a re given i n t able 6.1, 6.4, 6.5, 6.6 a nd di splayed i n f ig: 6. 8,
6.11, 6.12, 6.13, 6.14, 6.15, 6.16 and 6.17.
5.480
a
7.7450 c
5.475 b
Lattice parameter a, b, (Å)
Lattice parameter c (Å)
7.7425
5.470 (Q)
(P)
7.7400
5.465
7.7375
5.460
7.7350
La0.7(Ca1-xPbx)0.3MnO3 x=0.00,0.05,0.10,0.15,0.20,0.25
5.455
x=0.00,0.05,0.10,0.15,0.20,0.25
7.7325
5.450
0.000 0.025 0.050 0.075 0.000 0.025 0.050 0.075
Pb content Pb content
Fig: 6.8 Lattice parameters as a function of Pb Content
Table-6.1: Lattice Parameters (From Single Phase)

Samples (x) Lattice P arameter Lattice P arameter Lattice P arameter
a (Å) b (Å) c (Å)
0.00 5.4540 5.4626 7.7325
0.05 5.4571 5.4646 7.7343
0.10 5.4607 5.4672 7.7376
0.15 5.4652 5.4706 7.7402
0.20 5.4686 5.4725 7.7426
0.25 5.4724 5.4797 7.7456
112 | P a g e
Fig: 6.9 Reitveld refinement analysis of La0.7(Ca1-xPbx)0.3MnO3 samples (12500) from X-
ray diffraction patterns with considering single phase.
113 | P a g e
ray diffraction patterns with considering single phase.
114 | P a g e
ray diffraction patterns with considering double phase.
115 | P a g e
ray diffraction patterns with considering double phase.
116 | P a g e
Table-6.2. A n ove rview of e quivalent c rystallographic pos itions ( given i n W yckoff
notation) of t he s pace g roups P bnm w ith corresponding c oordinates a nd t he a tomic
occupation factors used for refinement of the La0.7 (Ca1-x Pbx)0.3MnO3 series.
Space group Z Position Coordinates Atomic occupation
Pbnm (no.62, 3) 4 4a (0, 0, 0) 0.7Mn3+ and 0.3Mn4+
4c (x, y, 0.25) 0.7La3+,0.3(1-x)Ca2+

0.3(x)Pb2+ and 4O2a
8d (x, y, z) 8O2P
The f ig: 6.9 and 6.10 s how t he R eitveld r efinement di agram f rom XRD s pectra w ith
considering single phase and double phase (Mn3O4). In these figures, the symbols indicate
the experimental results, the black solid line shows the fit, the vertical green lines show
the Bragg positons of the standard, and the blue line at the bottom shows the difference
between the experimental results and the fit. In order to track the crystallographic changes
caused by the Ca/Pb exchange, selected parameters, such as lattice constants and atomic
positions, w ere a llowed to va ry dur ing r efinement. T o e ase t he i nterpretation a s m any
parameters as pos sible were k ept f ixed. Table-6.3 lists the mos t impo rtant R ietveld
parameters and gives an idea of the degree of freedom associated with the refinements.
The fig.6.14 indicates bond angle increases with increasing lead contents and the fig 6.16,
6.17 indicate bond l ength de creases w ith i ncreasing l ead c ontents. T he MnO6 octahedra
are t ilted and rotated and t he deviations f rom t he i deal 180° M n–O–Mn bond angles of
the pa rent cubi c pe rovskite s tructure ar e evi dent. The l argest t ilt ang les ( and therefore
smallest Mn–O–Mn bond angles) are seen for the Pbnm compounds.
With respect t o t he c rystallographic pr operties, t he pr incipal di fference a mong t he

members of the La0.7(Ca1-xPbx)0.3MnO3 series is the mean ionic radius <rA> of the A-site
cations (La, Ca, and Pb). The mean ionic radius increases systematically with increasing x
2+ 2+
due to the difference in ionic radii of Ca and Pb (cf. Table 6.5 a nd Figure 6.13). This
suggests that <rA> is the essential structural parameter responsible for the change of the
117 | P a g e
Mn–O–Mn bond a ngle. This a ssertion i s s upported b y pr evious i nvestigations on the
relationship be tween c omposition a nd s tructure i n pe rovskite m anganites [ 19]. T hese
authors a lso c onsidered manganite s eries w ith ~ 33 % di valent A -site s ubstitution and
studied t he e ffect of va rying t he m ean r adius of t he A -site ions . However, rather t han
changing t he s ize of t he di valent cation, t heir approach w as t o va ry t he s ize of t he
trivalent A-site member, i.e. they considered the series (R1-yR’y)0.67A0.33MnO3, where (R,
R’ = La, Y, Nd, etc., and A = Ca, Sr, Ba, etc).
Table-6.3 An overview of the most important parameters of the Rietveld model and an indication
whether they w ere f ixed or allowed t o v ary dur ing r efinement. S ymbols a re explained in
Appendix A.
Parameter group Parameter Fixed or Free
Structural Space group Fixed
Z Fixed
α, β, γ Fixed
a, b, c Fixed
Atomic Atom types Fixed
Atomic positions Both Fixed and free
Site occupation Fixed
Temperature factor Fixed
Experimental Wavelength Fixed
Zero point Fixed
Peak shape U, V, W Free
γ 1, γ 2 ,γ 3 Free
Other Background level Free
118 | P a g e
The m ean Mn–O–Mn bond angle i ncreased systematically with increasing A -site ioni c
radius (6.15). T ogether t hese r esults s tress t hat < rA> i s a f undamental s tructural
parameter, not onl y for La0.7 (Ca1-x Pbx)0.3MnO3 series but f or t he m anganite family
R1-xAxMnO3 in general.
5.51 7.7325
(P) c
5.50 7.7310 (Q)
Lattice parameter a, b(Å)

5.49 a 7.7295
b
5.48 7.7280
5.47
7.7265 La0.7(Ca1-xPbx)0.3MnO3
5.46
7.7250 x=0.00,0.05,0.10,0.15,0.20,0.25
x=0.00,0.05,0.10,0.15,0.20,0.25
5.45
0.000 0.025 0.050 0.075 0.000 0.025 0.050 0.075
Pb content Pb content
Fig: 6.11 Lattice parameters as a function of Pb Content from double phase
Table-6.4 Lattice Parameters (From double Phases)

Pb Content (x) Lattice P arameter Lattice P arameter Lattice P arameter
a(Å) b(Å) c(Å)
0.00 5.4843 5.4653 7.7246
0.05 5.4864 5.4662 7.7250
0.10 5.4932 5.4670 7.7272
0.15 5.4996 5.4677 7.7281
0.20 5.5054 5.4682 7.7292
0.25 5.5086 5.4692 7.7312
119 | P a g e
233.0
232.5
232.0
Volume V (Å)3
231.5
231.0
230.5 Volume with single Phase

Volume with doule Phase
230.0
0.000 0.025 0.050 0.075
Pb content
Fig: 6.12 Unit cell Volume as a function Pb Content with single and Double Phase
1.1775
Ionic Radius of A - site (Å)
1.1700
1.1625
1.1550
1.1475
0.000 0.025 0.050 0.075
Pb content
Fig: 6.13 Ionic radius of A-site as a function Pb Content
Table-6.5 Unit cell Volume

Volume f rom single Volume f rom D ouble Ionic r adius of
3
Pb Content (x) Phase (Å) Phase (Å)3 A - site (Å)
0 230.37 231.53 1.1512
0.05 230.64 231.76 1.1565
0.10 230.96 232.06 1.1617
0.15 231.44 232.39 1.1670
0.20 231.75 232.68 1.1722
0.25 232.14 232.92 1.1775
120 | P a g e
170
Bond angle (deg,)

160
150
0.000 0.025 0.050 0.075

Pb Content
Fig: 6.14 Bond angle as a function of Pb content
170
165
Bond angle (deg.)
160
155
150
145
1.1550 1.1625 1.1700 1.1775
Ionic radius of A-site (Å)
Fig: 6.15 Bond angle as a function of Ionic radius of A-site
1.980
Bond length Mn-OP (Α°)
1.975
1.970
1.965
0.000 0.025 0.050 0.075

Pb content
Fig: 6.16 Bond Length (Mn-OP) as a function of Pb content
121 | P a g e
1.945
1.944
Bond length Mn-Oa (Α°)
1.943
1.942
1.941
1.940
1.939
0.000 0.025 0.050 0.075

Pb content
Fig: 6.17 Bond Length (Mn-Oa) as a function of Pb content
This c an be unde rstood b y i nvoking t he G oldsmith’s t olerance f actor, t , w hich w as

introduced i n c hapter t wo. t values of t he La0.7 (Ca1-x Pbx)0.3MnO3 series ar e l isted in
Table 6. 7 and i s pl otted against x in Figure 6.18. The t olerance factor i s 0.8702 for t he
x = 0 and it increases linearly to 0.8778 f or x = 0.25, in accordance with the increasing
mean ionic r adius. The tolerance factor c an be regarded as m easurements of t he s ize
mismatch between the radius of the A -site i ons and the s pace b etween the M nO6
octahedra, where they reside [20] (Hwang et al., 1995). t=1 corresponds to a perfect size
match and the Mn–O–Mn bond a ngle would be 180°. When t< 1, the A-site ions are too
small to fill the space between the MnO6 octahedra. This forces the octahedra to tilt and
rotate in an attempt to reduce the excess space around the A-site. The results in a decrease
of the Mn–O–Mn bond angle. There exist a cor relation between the mean A-site radious
<rA> (which is di rectly proportional t o x ) and t he M n-O-Mn bond angle. This could be
understood from the distortion of the network of MnO6 octrahedra arising from the size
mistch between <rA> and the space left between octrahedra. These data indicate that, as
the com positional pa rameters x i ncreases t he l attice pa rameters i ncrease as a g eneral
trend. This could be attributed to the ionic radii of Pb2+ which is larger than that of Ca2+.
Also this increase in the cell parameters may be attributed to the reduction of Mn4+ into
Mn3+. The f ig: 6.1 8 and 6.1 9 show the va riation of t olerance f actor a nd transition
temperature as a function of lead contents and tolerance factor and Curie temperature are
increased with increasing lead contents. It follows the general trend with Pb contents. The
results a re s ummarized in table 6. 7. Fig 6.20 shows t he t ransition t emperature a s a
function of tolerance factor and 6.21 shows t he c ombined effect of t olerance factor and
Curie temperature with Pb contents together.
122 | P a g e
0.8775
Tolerence Factor
0.8750
0.8725
La0.7(Ca1-xPbx)0.3MnO3 ,
x=0.00, 0.05, 0.10, 0.15,
0.20, 0.25
0.8700
0.000 0.025 0.050 0.075

Pb content
Fig: 6.18 Tolerance factor as a function of Pb content
290 La0.7(Ca1-xPbx)0.3MnO3 ,
Transition Temperature (K)
x=0.00, 0.05, 0.10, 0.15,

0.20, 0.25
280
270
260
250
0.000 0.025 0.050 0.075

Pb content
Fig: 6.19 Transition temperatures as a function of Pb content
300
Transition Temperature (K)
x=0.00, 0.05, 0.10, 0.15,
0.20, 0.25
285
270
255
0.8700 0.8725 0.8750 0.8775

Tolerence factor
Fig: 6.20 Transition temperatures as a function of Tolerance factor
123 | P a g e
290 x=0.00, 0.05, 0.10, 0.15,
0.20, 0.25
ture (K)
280
Transition Tempera
270
0.879 0.000
260 0.876 0.025
0.050
0.873
0.075
0.870
250 0.879
0.000
0.876
0.025 r
Pb 0.873 acto
Con 0.050 F
ten nce
e
t 0.075 0.870
oler
T
Fig: 6.21 Transition temperature as a function Tolerance factor and Pb content
Table-6.6 Bond angle and Bond length

Pb c ontent Bond a ngle Bond length(Mn-OP) (Å) Bond length(Mn-Oa) (Å)
(x) (deg.)
0.00 145.97 1.9768 1.9448
0.05 151.52 1.9748 1.9435
0.10 155.45 1.9723 1.9419
0.15 158.78 1.9706 1.9410
0.20 164.88 1.9617 1.9398
0.25 168.44 1.9549 1.9386
Table-6.7 Tolerance factor and transition temperature

Pb Contents (x) Tolerance Factor Transition Temperature (K)
0.00 0.8702 252
0.05 0.8716 255
0.10 0.8731 264
0.15 0.8747 268
0.20 0.8762 282
0.25 0.8778 291
124 | P a g e
6. 6 Magnetic Properties
6.6.1 The Thermo-Magnetic Zero Field Cooled (ZFC) and Field Cooled (FC)
Measurements
After c onfirmation of t he purity of t he s amples, t he t emperature de pendence
magnetization was ex amined by t he m easurement of z ero field cooled and field cooled
thermo-magnetic curves to determine the magnetic states and behaviors of the samples in
terms of pa ramagnetism, ferromagnetism or antiferromagnetism. The s amples with
doping levels x=0.00, 0.05, 0.1, 0.15, 0.20, 0.25 of the series LCPMO were studied. The
field c ooled ( FC) a nd t he z ero f ield c ooled ( ZFC) magnetization measurements w ere
performed under DC magnetic fields of 20 Oe and 50 Oe for a temperature range 30 K -
320 K and t he r esults were di splayed i n f ig. 6.22. It is c lear f rom the fig.6.22 that a
mixture of magnetic behaviors were observed in different parts of the temperature range.
The t ransition temperature w as determined from F C/ZFC curves b y the m aximum
inflection point a nd the transition temperature f or dopi ng l evel x = 0.2 5 was ve rified by
dM/dT (Fig: 6.23) curves. From these thermo-magnetic curves, the ferromagnetic [29-33]
to paramagnetic tr ansition temperature, TC can be de termined. The C urie t emperature
increases with increasing the Pb contents in the samples from 252 K (x= 0.00) to 291 K
(x=0.25). This tendency almost agrees with dependence of Tc (x) in the system La 1-xPb x
MnO3 [5]. It is clear that the substitution of Pb2+ for Ca2+ induces a mixed valence state
of M n3+/Mn4+ and e nhances t he f erromagnetic t ransition t emperature due t o doubl e
exchange interaction.
Table-6.8 Transition Temperature by different process

Pb content (x) Transition Transition Transition Transition
temperature temperature (K) temperature (K) temperature
(K) from from A rrot pl ot from A rrot pl ot (K) from
FC/ZFC (5T) (2T) dM/dT
0.00 251 251
0.05 255 255
0.10 264 263
0.15 268 264 264 267
0.20 282 277 276 281
0.25 291 284 283 290
125 | P a g e
x=0.00
3.75 x=0.05
x=0.10
x=0.15
Magnetization (emu/g)
3.00 x=0.20
x=0.25
2.25
1.50
H=50 Oe
0.75
0.00
150 200 250 300
Temperature (K)
Fig: 6.22 The thermo-magnetic zero – field – cooled (ZFC) and field cooled (FC) curves
as a function of temperature of the LCPMO series.
3.0
2.5 FC
2.0
ZFC H=50 Oe
1.5
La0.7Ca0.225Pb0.075MnO3
1.0
dM/dT
0.5
0.0
50 100 150 200 250 300
Temperature (K)
Fig: 6.23 dM/dT vs T graph of the LCPMO series
Because of l arge P b2+ ions i n the s amples, the increase of P b2+ content s ubstituted f or
Ca2+ ion l eads t o a n i ncreasing i n t he average r adius of t he A - sites c ation <rA>
126 | P a g e
(table-6.5). Increasing t he r adius <rA> of A -site causes an increase i n the i nternal
pressure, which decreases the buckling of the MnO6 octahedral and then the T c enhances
[34-38]. Fig: 6.19 and fig 6.24 shows the variation of Curie temperature (TC) as a function
of the fractional composition (x) of lead contents and volume. From the TC (x) and TC(V)
curve, w e c an de duce t hat t he i ntroduction of lead i n t his series causes a s ignificant
increase of the ferromagnetic ordering temperature.
290
Transition temperature (K)
280
270
260
250
230.0 230.5 231.0 231.5 232.0 232.5
Volume (Α°)3
Fig: 6.24 Transition temperatures as a function volume
The de creasing of m agnetization on ZFC cur ve i n low t emperature r ange i ndicated that
there i s s hort – range or der [39-43] in t he s tudied s amples. T he m aximum w ill be t he
result of t he c ompetition be tween t he ( local) a nisotropy ( decreasing with i ncreasing
temperature, s o allowing an i ncreasing m agnetization) and the de crease of t he m agnetic
order w hen C urie t emperature i s a pproached. In a ddition, t he r ole of g rains a nd g rain
boundaries could be another reason of such phenomena. At grain boundary, the exchange
interaction (SE and DE) are weak compared to those inside the grain [44-46]. This leads
to t he i nhomogeneity o f m agnitude of e xchange i nteraction. From t he FC a nd ZFC
measurements we can correlate T r, T f and T C and we can explain the similar composition
dependence t o t hat of C urie t emperature T C for t he s tudied s amples. A t hi gher
temperatures, the FM is broadened leading to increasing of magnetization in ZFC curve.
This phase separation phenomenon is the intrinsic feature of perovskite – type manganites
[47-49] a nd w as e xperimentally obs erved in various m anganites as w ell as af firmed by
the theoretical studies.
127 | P a g e
6.6.2 Transition temperature from the Arrot plot using M-H curves
The Curie temperature had been estimated from the inflection point in the magnetization
curve vs temperature (FC/ZFC vs T) measured at an applied magnetic field of 20, 50 O e
respectively, Tc ~252, 255, 264, 268, 282 a nd 2 91 for doping l evel x=0.00, 0.05, 0. 1,
0.15, 0.20, and 0.25 respectively.
5000
La0.7Ca0.255Pb0.045MnO3
Magnetization2 (emu/g)2
4000
T=264
3000
2000
600 800 1000
H/M (Oe-g/emu)
Fig: 6.25 Arrot Plot: Square Magnetization as a function of H/M for x=0.15 sample.
5000
La0.7Ca0.24Pb0.06MnO3
Magnetization2(emu/g)2
4000
3000 T=277
600 800 1000

H/M(Oe-gm/emu)
128 | P a g e
4000
La0.7Ca0.225Pb0.075MnO3
Magnetization2 (emu/g)2
3000
T=290
2000
800 1000 1200

H/M (Oe-g/emu)
In order to get deeper insight knowledge into the magnetic transition, the magnetization
isotherms were applied to construct the so called Arrot plots of M 2 vs H/M. The sets of
magnetization isotherms w ere me asured in the tr ansition region with the temperature
separation of Δ T = 5 k, 3 k and 1 k respectively. We observed a positive slope of the M 2
vs H/M plot and analyzed the data assuming the PM-FM transition to be of second order
in this s ample. According t o the m ean-field theory ne ar T C, M2 vs H /M a t va rious
temperatures should show a series of parallel lines. The line at T=TC should pass through
the origin. The figure 6.25, 6.26 and 6.27 show the isotherms are almost parallel straight
lines at TC=268 K, 277 K and 286 K for x=0.15, 0.20 and 0.25 respectively.
6.7 Relationship between Structure and Magnetism
In Figure 6. 28, the transition temperatures ob tained for t he La0.7(Ca1-xPbx)0.3MnO3

compounds, have be en p lotted against ionic r adius of A-site. T he f igure 6.28 illustrates
that the Curie temperature depends more specifically on the mean ionic radius, <rA>, of
the A -site i ons t han o n t he c omposition pa rameter x. E ven m ore s pecifically, the
relationship between TC and <rA> is due to the linkage between <rA> and the Mn–O–Mn
bond angle. This can be understood from the following: The concept of double-exchange
and magnetic int eraction in mixed-valence m anganites were di scussed pr eviously. To
129 | P a g e
recapitulate, the f erromagnetic properties of m anganite s ystems a re a scribed t o t he
4+
hopping of mobile eg (S = 1/2) electrons between localized Mn core spins (S = 3/2) with
strong on -site Hund’s coupling. The hoppi ng t akes pl ace vi a t he i nterstitial ox ygen i on.
The s trength of t he f erromagnetic c oupling is r elated to the h ybridization strength
between eg(Mn)–2pσ (O)–eg(Mn) orbitals [28] (Coey et al., 1999). The orbital overlap, and
thereby t he h ybridization s trength, de pend s trongly on bot h t he M n–O d istance and t he

Mn–O–Mn bond a ngle. Intuitively, it seems that the hybridization is weakened when the
bond a ngle d ecreases ( Figure 6.29). T hus, a s maller M n–O–Mn bond a ngle gives a
weaker ferromagnetic coupling and thereby a l ower Curie temperature (TC represents the
temperature, where the ferromagnetic exchange energy can no longer compensate for the
thermally i nduced s pin fluctuations). Figure 6.2 9 shows t he C urie t emperatures of t he
La0.7(Ca1-xPbx)0.3MnO3 series as a function of the mean Mn–O–Mn bond angle obtained
from t he R ietveld a nalysis. In a ccordance w ith the a bove c onsiderations, TC increases
with increasing bond angle. A similar result were obtained by [19], whom considered the
relationship be tween t he M n–O–Mn bond a ngle a nd f or va riously A -site s ubstituted
R1-yAyMnO3 compounds with y ≈ 0.67. Even though the Mn–O–Mn bond angle and <rA>
play decisive roles for the magnetic coupling strength in mixed-valence manganites, these
are not t he onl y factors influencing TC. F or i nstance, t here i s a t endency for t he C urie
temperature to decrease w ith increasing electropositivity of the di valent A -site c ation,

because a mor e electropositive c ation will te nd to strengthen the tg(Mn)–2pσ (O)–tg(Mn)
hybridization, w hich causes a nti-ferro-magnetic c oupling be tween M n neighbors [ 19].

This i s m entioned t o e mphasize t hat t he r elationship be tween TC and < rA>, w hich i s
evident f or t he La0.7(Ca1-x Pbx)0.3MnO3 series a nd f or ot her m ixed-valence m anganite

systems, c annot be generalized t o put f orward a n uni versal TC versus < rA> l aw. By
comparing r esults f or a wide r ange of c ompositions [ 50] T homas et al. ( 1997) s howed
that there is no clear trend associating the Curie temperature of mixed-valence manganites
with the size, atomic weight, or electropositivity of the divalent A-site cation.
130 | P a g e
290

280
270
260
250
1.026 1.035 1.044
Ionic Radious in A-site (Α°)
Fig: 6.28 Transition temperatures as a function of mean ionic radius <rA>
290
280
270
260
250
150 160 170
Bond angle (deg.)
Fig: 6.29 Transition temperatures as a function of bond angle
290
280
270
260
250
1.965 1.970 1.975
Bond length Mn-Op (Å)
Fig: 6.30 Transition temperatures as a function of bond length
131 | P a g e
6.8 The Hysteresis Loop Measurements of LCPMO series
The h ysteresis l oss i s t he a rea enclosed b y t he h ysteresis l oop on t he M, H pl ane. It
represents the energy expended per unit volume during one cycle of the hysteresis loop.
The h ysteresis l oss i ncreases as t he m aximum m agnetic f ield r eached during the cycle
increases. This loss is closely related to the coercivity so that processing of materials to
reduce t he coe rcivity also reduces t he h ysteresis loss. Generally l ow h ysteresis l oss i s a
desirable ch aracteristic o f s oft m agnetic m aterials. Figure 6.3 1 and 6.3 2 show a t ypical
magnetic hysteresis loop for the sample x=0.00 and x=0.05 and 6.33, 6.34 and 6.35 show
the h ysteresis l oop f or t he s eries of La0.7(Ca1-xPbx)0.3MnO3 for di fferent applied
magnetic f ield at a t emperature of 10 K. From t he f igure i t w as s een that t he very l ow
coercivity are present at very low field.
48
36
24 x=0.00
12
-12
-24 T=10 K
-36
-48
-800 -400 0 400 800
Magnetic Field (Oe)
Fig: 6.31 Hysteresis loop of La0.7Ca0.3MnO3 sample.
48
36
24 x=0.05
12
-12
-24
T=10K
-36
-48
-800 -400 0 400 800
Magnetic Field (Oe)
Fig: 6.32 Hysteresis loop of La0.7Ca0.285Pb0.015MnO3 sample.

132 | P a g e
60
x=0.00
45 x=0.05
x=0.10
30 x=0.15
x=0.20
15 x=0.25
-15
-30
T=10 K
-45
-60
-800 -400 0 400 800
Magnetic Field (Oe)
Fig: 6.33 Hysteresis loop of La0.7(Ca1-xPbx)0.3MnO3 Series at 1000 Oe
x=0.00
75
x=0.05
x=0.10
50
x=0.15
25 x=0.20
x=0.25
0
-25
T=10 K
-50
-75
-6000 -3000 0 3000 6000

Magnetic Field (Oe)
Fig: 6.34 Hysteresis loop of La0.7(Ca1-xPbx)0.3MnO3 Series at 7000 Oe
100
x=0.00,
75 x=0.05,
x=0.10,
50 x=0.15,
x=0.20,
x=0.25,
25
-25
T=10 K
-50
-75
-100
-24000 -12000 0 12000 24000
Magnetic Field (Oe)
Fig: 6.35 Hysteresis loop of La0.7(Ca1-xPbx)0.3MnO3 Series at 3.2 T
133 | P a g e
From these the hysteresis loop measurements of the samples La0.7(Ca1-xPbx)0.3MnO3, the
saturation magnetization, Bohr m agneton coercovity and remanance w ere cal culated at
the applied m agnetic field of 2.61*10 4 Oe and 1 000 Oe. The r esults were s hown i n t he
table 6.9.
Table-6.9 Saturation Magnetization, Bohr Magneton (µB) Coercivity, and Remanance

Pb Saturation Bohr Applied Coercivity (Oe) Remanance
Content Magnetization Magneton Magnetic at 1000 Oe (emu/g) at
(x) (emu/g) (µB /f.u.) Field (Oe) 1000 Oe
0.00 89.7 3.42 2.61*104 26.96 0.68
0.05 91.2 3.5 2.61*104 22.67 1.88
0.10 93.2 3.62 2.61*104 22.70 1.05
0.15 84.6 3.32 2.61*104 31.91 1.51
0.20 90.5 3.60 2.61*104 11.20 0.65
0.25 85.7 3.44 2.61*104 14.51 1.02
The hysteresis is indicating that the ferromagnetic state exists in the samples at 10 K and
the magnetic moment starts to saturate at 7000 Oe. This implies that an antiferromagnetic
or ferromagnetic state is present at the very low temperature.
6.9 Magneto-caloric Properties of the La0.7(Ca1-xPbx)0.3MnO3 Series

6.9.1 Introduction
This section explains the results of an investigation of the magneto-caloric properties of
the samples in the La0.7(Ca1-xPbx)0.3MnO3 series. As described in the following Section
the ma gneto-caloric ef fect i n a m aterial c an be expressed in two terms: t he i sothermal
magnetic entropy change Δ SM, and the adiabatic temperature change Δ Tad upon a change
of the applied magnetic field, respectively. Both quantities are temperature and magnetic
field de pendent and a re of ten w ritten Δ SM (T) ΔH
and Δ Tad (T) , r espectively. In t he
ΔH
present s tudy ma gneto-caloric qua ntities w ere m easured f rom i sothermal m agnetization
curves. T he c onsistency of t he m easurements c an be e valuated b y us ing results of he at
capacity measurements.
134 | P a g e
6.9.2 The Magneto-Caloric Effect
When a dc ma gnetic f ield is a pplied to a s olid, which is the rmally is olated from its
surroundings, a c hange of t he t emperature of t he s olid m ay be o bserved. T his
phenomenon i s know n as m agneto-caloric ef fect or , m ore p recisely, the adi abatic
temperature cha nge due to a cha nge of t he applied magnetic f ield. The magneto-caloric
effect was first discovered by Warburg (1881) [51] in pure iron and explained physically
by Debye (1926) [52] and Giauque (1927) [53].
The magneto-caloric effect is the result of entropy changes arising from the coupling of
the magnetic spin system of the solid with the applied magnetic field. The total entropy of
a magnetic solid is the sum of the lattice, electronic, and magnetic entropies (SL, SE, and
SM, respectively). In most cas es t he l attice an d electronic ent ropies ar e es sentially
independent of the magnetic field H, whereas the magnetic entropy depends strongly on
H. A n a pplied f ield w ill us ually t end t o align the m agnetic s pins and thus de crease t he
entropy of the spin system (Figure 6.36 below). Hence, if the applied field is changed by
Δ H at a constant temperature T, the magnetic entropy is changes Δ SM(T)Δ H, while SL and
SE remain c onstant. T he qua ntity Δ SM(T)Δ H is th e is othermal ma gnetic e ntropy change.
Figure 6.36 shows the simplified illustration of the effect of an applied external magnetic
field H to a ferromagnetic spin system. The field increases the order in the spin system by
forcing the spins to align in its direction.
Fig: 6.36 Simplified illustration of the e ffect of a n applied magnetic f ield H to a

ferromagnetic spin system.
Increasing or der corresponds t o de creasing e ntropy. If t he change of t he magnetic f ield

takes place adiabatically, the total entropy is conserved. In this case, the combined lattice
and electronic entropies must change by Δ (SL + SE) = -Δ SM in order to fulfill the condition
135 | P a g e
Δ S= 0. The cha nge of lattice and electronic e ntropies m ay caus e a cha nge of t he
temperature of t he m agnetic s olid, e .g. b y i ntensified or reduced l attice vi brations,
depending on t he s ign of Δ H. This t emperature cha nge i s t he adi abatic t emperature
change, Δ Tad(T)Δ H, i ntroduced a bove. Due t o t he l inkage be tween the i sothermal
magnetic entropy change and the adiabatic temperature change the magneto-caloric effect
may be expressed in both terms.
6.10 Indirect Measurements of the Magneto-Caloric Effect
The i sothermal m agnetic ent ropy ch ange, Δ SM(T)Δ H, c an be de termined f rom
measurements of ma gnetization as a f unction of the a pplied magnetic f ield and

temperature. For a small temperature change Δ T, the magnetocaloric effect can be written
to give the approximation
1
∫ (M (H , T ) − M (H , T + ∆T ))
Hf
∆S M (Tavg ) ∆H ≅ − µ 0 dH 6.2
∆T
H
Hi
where Tavg denotes the average temperature of T and T+Δ T, i.e. T+Δ T/2.
The i ntegral i n E quation ( 6.2) c orresponds t o t he a rea e nclosed be tween the t wo

isothermal ma gnetization curves M(H) a nd M(H,T+Δ T). H aving obt ained e xperimental
magnetization curves with discrete external fields separated by Δ H, the calculation of this
area is straightforward using numerical integration. Thus, a complete Δ SM(T)Δ H curve can
be de rived f rom a s eries of i sothermal m agnetization c urves obt ained a t di screte

temperatures with an appropriate, i.e. fairly small, temperature interval.
Isothermal magnetization curves were obtained using the vibrating-sample magnetometer

and us ing t he MPMS XL-5 SQUID magnetometer. For e ach member of t he
La0.7(Ca1-xPbx)0.3MnO3 series, the f ield dependence of t he s pecific m agnetization was
recorded at fixed temperatures i n an appropriate t emperature r ange around the C urie
temperature. T he i nterval be tween t he i sotherms w as 5, 3, 2 a nd 1 K , a nd a c omplete
series t ypically consisted of a bout 18 -24 m agnetization c urves. T he a pplied f ield w as
varied between the remnant field Hr of the electro-magnet (Hr ≈ 00 Oe) and the maximum
field Hmax provided b y t he m agnet ( Hmax = 50 k Oe). T his c orresponds t o a f lux de nsity
variation of B = µ0H. In the following, field changes will usually be given in tesla, i.e. in
terms of µ 0H. Since Hmax >> Hr, the remnant field was neglected and field changes were
136 | P a g e
calculated as Δ H = Hmax, i .e. HI and HF in E quation ( 6.2) w ere s et t o 0 and Hmax,
respectively. T he f ield direction w as not a ltered be tween m easurements, s o pos sible

effects of coercivity were ignored (the coercivity of the samples was on the same order of
magnitude as the mini mum a pplied field (Hr), a nd t hus ne gligible compared t o Δ H).
Because the calculation of the isothermal magnetic entropy change is based on numerical
integration, where t he exact di fferentials dM, dT, a nd dH have be en s ubstituted,
respectively, by t he m easured quantities Δ M, Δ T and Δ H, the er ror as sociated with
Δ SM(T)Δ H values calculated from magnetization data may sum up to be as high as 20–30
% ( Gschneidner, J r. a nd P echarsky, 2000) [54]. T he s amples us ed for ma gnetization

measurements were s mall pi eces of t he La0.7(Ca1-xPbx)0.3MnO3 compounds. The pi eces
were irregularly shaped, making it very difficult to determine the demagnetization factors.
The lack of demagnetization correction may also contribute to the total error. Figure 6.41
and 6.42 show the result of the indirect magneto-caloric measurement carried out for the
end member L a0.7Ca0.225Pb0.075MnO3. The c omplete s eries of is othermal ma gnetization
curves a re s hown along with t he c orresponding calculated magnetic ent ropy ch ange f or
two selected values of the m agnetic f ield change, 5 T, 4T , 3 T, 2T , 1 .35T and 1 T,
respectively. The C urie t emperature of t his s ample x = 0.25 i s 291 K. The ar ea en closed
between neighboring i sotherms i s cl early i ncreasing as t he t emperature a pproaches TC
from bot h e nds of t he t emperature r ange. Q ualitatively t his i s i n ve ry good a greement

with t hermodynamic c onsiderations e xplained i n a bove. T he m agnetic entropy change
increases c orrespondingly and di stinct pe aks oc cur c lose t o t he C urie po int. F or a f ield
-1 -1
change of 5 T, a maximum magnetic entropy change of 5.96 Jkg K is obtained at higher
temperature of 291 K. The width of the peak at half maximum is about 23 K. Figure 6.37,
6.38, 6.39, 6.40, 6.4 1, 6.4 2, summarize the r esults of the ind irect me asurements of the
La0.7(Ca1-xPbx)0.3MnO3 series, s howing bot h i sothermal m agnetization c urves a nd
corresponding c alculated Δ SM(T)Δ H profiles for fi eld changes of 5 T, 4T, 3T, 2T, 1.35T
and 1 T , respectively. For t he three s amples i n the s eries, the m agnetic entropy change
exhibits a peak in the vicinity of the Curie temperature. However, the increase of the area
between ne ighboring i sotherms ne ar TC becomes le ss di stinct w ith increasing x and t he
maximum magnetic entropy change decreases correspondingly to a more or less constant

-1 -1
level of about 2.8 Jkg K (considering data for µ0Δ H = 1.5 T ). The exchange of Ca and
137 | P a g e
Pb also causes an asymmetric br oadening of t he Δ SM(T)Δ H profiles. T his br oadening
could be an i ndication o f t he presence of a di stribution of C urie t emperatures, probably

associated with the surface near regions of the grains.
6.11 Magnetic Isotherm of LCPMO series and Magnetic Entropy Measurements

The M(H) isotherms have been measured for the samples of La0.7 ( Ca1-x Pbx )o.3 Mn O 3
(x= 0.15, 0.20, 0.25) s ystems a nd i nvestigated a t va rious t emperatures i n a na rrow
temperature interval around the respective Curie temperatures, in magnetic field up to 50
kOe. T he f ig: 6.36, 6.38, 6.40 s how t he s et of i sothermal M (H) c urves of pe rovskite
La0.7 ( Ca1-x Pbx )o.3 Mn O3 at different applied magnetic field. From these M (H) curves,
around T C, t he |Δ Sm|(T) de pendence ha s be en determined a ccording t o t he f ollowing
equation [55-57]
( M n − M n+1 ) H
=∆S ∑ Tn +1 − Tn
∆H n
6.3
and pr esented i n f ig: 6.3 8, 6. 40 and 6.4 2. F or m agneto-caloric m aterials, the r elative
cooling power (RCP) represents a good way for comparing them and it is defined as
RCP = |Δ Sm|max. δ Tfwhm 6.4
where δ Tfwhm means the full-width at the half maximum of the magnetic entropy change
vs temperature, as indicated in fig: 6.38, 6.40 and 6.42. In fig: 6.38, 6.40 and 6.42, the
|Δ Sm|(T) f or t he s tudied s amples a re pl otted a s a f unction of t emperature f or di fferent
applied magnetic field. The maximum magnetic entropy changes [58-61] |Δ Sm|max, as well
as the relative cool ing power (RCP) values for all samples are listed in table -6.10. The
magnetic ent ropy change, |Δ Sm|max has r eached hi gher v alue o f 6.94 J/Kg K fo r t he
composition x= 0.15, 6.47 J/Kg K for the composition x= 0.20 and 5.96 J/Kg K f or
the composition x= 0.25, a t an applied field of 5 T and also |Δ Sm|max has reached higher
value of 3.79 J/Kg K for t he composition x = 0.15, 3.89 J/Kg K for t he c omposition x=
0.20 and 3.47 J/Kg K for the composition x= 0.25 at an applied field of 2 T. It can be seen
from the table -6.10 that our studied samples have quite large |Δ Sm|max as materials with
giant ma gneto-caloric e ffect (GMCE) [ 62-66]. A pr omising ma terial for a pplication
should ha ve hi gh relative cool ing po wer ( RCP) and t he v alue o f T C close t o room
temperature.
138 | P a g e
75
T=230 K
Magnetization (emu/g) 60
45
30
T=282 K
15
La0.7Ca0.255Pb0.045MnO3
0
0 12000 24000 36000 48000
Magnetic Field (Oe)
Fig: 6.37 Magnetic Isotherm of LCPMO series (x=0.15) at 5 T.
1T
6.0 1.35T
Magnetic Entropy (J/kgK)
2T
3T
4T
4.5 5T
3.0 x=0.15
1.5
0.0
225 240 255 270 285
Temperature (K)
Fig: 6.38 Magnetic entropy as a function of temperature at different magnetic fields.
139 | P a g e
T=250 K
60
45
30
T=304 K
15
La0.7Ca0.24Pb 0.06MnO3
0
0 10000 20000 30000 40000 50000
Magnetic field (Oe)
Fig: 6.39 Magnetic Isotherm of LCPMO series (x=0.20) at 5 T
1T
1.35T
6.0 2T
3T
4T
x=0.20 H=5T
4.5
3.0
1.5
0.0
255 270 285 300
Temperature (K)
Fig: 6.40 Magnetic entropy as a function of temperature at different magnetic fields
140 | P a g e
T=265 K
45
30
T=302 K
15
La0.7Ca0.225Pb0.075MnO3
0
0 12000 24000 36000 48000
Magnetic Field (Oe)
Fig: 6.41 Magnetic Isotherm of LCPMO series (x=0.25) at 5 T
6.0 1T
1.35T
2T
3T x=0.25
4T
4.5 5T
3.0
1.5
0.0
270 280 290 300
Temperature (K)
Fig: 6.42 Magnetic entropy as a function of temperature at different magnetic fields
141 | P a g e
The magnetic e ntropy change, |Δ Sm|max and the relative cool ine pow er, RCP va lues ar e
large for t he s tudied s amples, t he T C for t he s amples x = 0.25 are near t o the room
temperature. T he dopi ng e ffect m ight s olve t his di sadvantage. The f ig: 6.43 and 6. 44
show the comparison of magnetic entropy at different applied magnetic field as a function
of Pb c ontents and temperature for t he co mposition x = 0.15, 0.20 and 0.2 5. In t hese
figures the maximum entropy exists around Curie temperature which is desirable.
6.25
5.00
x = 0.15, 0.20, 0.25
2T
5T
3.75
0.045 0.060 0.075

Pb Content
Fig: 6.43 Comparison of magnetic entropy as a function of Pb content at different applied
magnetic field.
6.25
2T
5T
5.00
3.75
260 265 270 275 280 285

Fig: 6.44 Comparison of m agnetic e ntropy as a function transition temperature at
different applied magnetic fields.
142 | P a g e
The fig: 6.45 and 6.46 display the variation of magnetic entropy as function of fractional
composition of l ead c ontents and as a f unction of t emperatures at di fferent appl ied
magnetic field together.
H=5T La0.7(Ca1-xPbx)0.3MnO3 ,
7.0
x= 0.15, 0.20, 0.25
)
tropy (J/kgK
6.5
Magnetic En
6.0
285 0.045
280
275 0.060
5.5 270
265 0.075
260
285
0.045 280
275 )
Pb 0.060 K
Co 270 e(
nte tur
nt 265 ra
0.075 pe
m
260 Te
Fig: 6.45 Magnetic entropy as a function of Pb content and temperature at 5T
4.00
H=2T
x= 0.15, 0.20, 0.25
)
tropy (J/kgK
3.75
Magnetic En
3.50
285 0.045
3.25 280
275 0.060
270 0.075
265
260
3.00 285
0.045 280
275
Pb 0.060 K)
Co
nte 270 re(
nt atu
0.075
265
per
m
260 Te
Fig: 6.46 Magnetic entropy as a function of Pb content and temperature at 2 T
143 | P a g e
150
135
120
RCP (J/kg)
RCP (2T)
RCP(5T)
105
La0.7(Ca1-xPbx)0.3MnO3 , x=0.15, 0.20, 0.25

90
75
0.045 0.060 0.075
Pb Contents
`
Fig: 6.47 Comparison of Relative cooling power as a function of Pb content at different
applied fields.
150
Relative Cooling Power (J/kg)
135 La0.7(Ca1-xPbx)0.3MnO3 ,
x=0.15, 0.20, 0.25
120
RCP (2T)
105 RCP(5T)
90
75
260 265 270 275 280 285
Fig: 6.48 Comparison of Relative cooling power as a function of Transition temperature
at different applied fields.
The fig: 6.47 and 6.48 display the variation of relative cooling power as a function of lead
contents and temperature at different applied magnetic field.
144 | P a g e
Table–6.10 T ransition temperatures, Magnetic Entropy and R elative Cooling Power at
different magnetic field
Pb content(x) TC from TC from dM /dT Δ Smax in RCPmax in J/Kg
FC/ZFC cur ves in K J/kgK
in K
0.00 251 251
0.05 255 255
0.10 264 264
0.15 268 266 6.94(5T), 138.80(5T),
3.79(2T) 72.01(2T)
0.20 282 282 6.47(5T) 145.58(5T),
3.89(2T) 83.64(2T)
0.25 291 290 5.96(5T), 143.04(5T),
3.47(2T), 81.37(2T),
2.82(1.5T) 42.3(1.5T)
6.12 Summary
A detailed study of the magneto-caloric effect in the La0.7 (Ca1-x Pbx)0.3 Mn O 3 (x=0.00,
0.05, 0.1, 0.15, 0.2, 0.25) compounds has been analyzed. The magneto-caloric properties
of t he s amples i n t he La0.7(Ca1-xPbx)0.3MnO3 series w ere i nvestigated b y means of
indirect measurements, providing the temperature dependence of the isothermal magnetic
entropy change Δ SM(T)Δ H, . It has been found the large magnetic entropy changes as we
knew, i.e. the large magneto-caloric effect, in these samples. Among them, the magnetic
entropy ch ange r eaches a m aximum value of 5.98 J/kg K at the applied field of 50 kO e
for the La0.7 Ca0.225 Pb0.075 Mn O 3 sample, and 3.47 J/kgK at 20 kO e associated with the
ferromagnetic to paramagnetic tr ansition at 29 1 k. Δ SM(T)Δ H showed di stinct pe aks
around the Curie temperature. The observed maximum |Δ SM(T)Δ H| values obtained with a
field change o f 5 T were compared quantitatively using an approximate thermodynamic

relation. The results were found to be in good accordance. The magnetic entropy changes
of t he s amples are very good prototypical ma terial f or r oom te mperature ma gnetic
refrigeration. A compound of the La0.7(Ca1-xPbx)0.3MnO3 series with x ≈ 0.2 5 would be
expected to exhibit t he high ferromagnetic tr ansition temperature a s gadolinium and t o
145 | P a g e
show a lmost c ompetitive ma gneto-caloric pr operties. It gives us a s uggestion t hat t his
material w ould be a suitable pr e-eminent c andidate f or t he adv anced magnetic
refrigeration technology; namely; a larger value of entropy change is expected compared
to the pol ycrystalline s amples; a nd ∆the
s m distribution i s qui te uni form, w hich i s
desirable for an Ericson – cycle magnetic refrigerator.
6.25
Pb Series
Magnetic entropy (J/kgK)
5.00
0.075, 2.65
3.75
2.50
0.000 0.075 0.150 0.225 0.300

Pb content
Fig: 6.4 9 Comparative s tudies on M agnetic e ntropy as a f unction of P b c ontent (The
arrow sign shows the highest magnetic entropy for low substitution Pb=0.075 at1.35T)
6.25
Magnetic entropy(J/kgK)
Pb Series
5.00
291, 2.65
3.75
2.50
250 275 300 325 350

Temperature (K)
Fig: 6.50 Comparative studies on Magnetic entropy as a f unction of C urie t emperature
(The arrow sign shows the highest magnetic entropy at 291K for applied magnetic field
1.35T)
146 | P a g e
Table-6.11 Comparative studies on Magneto-Caloric Effect for Lead (Pb) series
Composition Curie T emp. T C Applied Δ SM Reference
(K) Field H (T) (J/kgK)
La0.70Ca0.30MnO3 256 1 1.38 67
La0.70Ca0.30MnO3 227 1 1.95 68
La0.70Ca0.30MnO3 202(TS=12800C) 1 4.07 Present work
La0.70Ca0.30MnO3 258(TS=12000C) 1.35 6.5 Present work
La0.70Pb0.30MnO3 358 1.35 1.53 69
La0.70Ca0.20Pb0.1MnO3 295 1.35 2.53 70
La0.70Ca0.10Pb0.20MnO3 337 1.35 3.72 70
La2/3(Ca,Pb)1/3MnO3 290 7 7.5 71
La0.70Ca0.255Pb0.045MnO3 268 5 6.94 Present work
La0.70Ca0.255Pb0.045MnO3 268 1.35 2.80 Present work
147 | P a g e
The large magnetic entropy change produced by the abrupt reduction of magnetization is
attributed t o t he s trong c oupling be tween s pin a nd l attice i n t he m agnetic o rdering
process. So this compound could be considered a suitable candidate as working material
in magnetic r efrigeration near r oom t emperature. T able- 6.11 a nd t he f igure 6.48, 6.49,
6.50 shows the comparative studies on magnetocaloric effect for lead series.
J/kgK)
6
∆H=1.35T
Magnetic entropy(
5
0.075, 291,2.65
4
2
0.000 350
0.075 325 e (K)
Pb
0.150 300 atur
Con 0.225 275 per
ten 0.300 250 m
t Te
Fig: 6.51 Comparative studies on Magnetic entropy as a function of Pb content and Curie
temperature (The a rrow s ign s hows t he hi ghest m agnetic e ntropy f or l ow s ubstitution
Pb=0.075 and at the Curie temperature for the applied magnetic field 1.35T)
148 | P a g e
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153 | P a g e
Chapter Seven Study of La0.7(Ca1-xSrx)o.3MnO3 Perovskite
7.1 Introduction
(i) La0.7(Ca1-xSrx) 0.3MnO3 (ii) La0.7(Ca0.95 Sr0.05)0.3 Mn O3
(iii) La0.7(Ca0.90 Sr0.10)0.3 Mn O3 (iv) La0.7(Ca0.85 Sr0.15)0.3 Mn O3
(v) La0.7(Ca0.80 Sr0.20)0.3 Mn O3 (vi) La0.7(Ca0.75 Sr0.25)0.3 Mn O3
Referring t o the fo regoing c hapters, t he s tructure a nd t he m agnetic pr operties of

manganese – based perovskite manganites samples depend on s everal important factors:
(i) The value of <rA> has a strong influence on magnetic and magneto-caloric properties
in particular of perovskite – type manganites. With the substitution of different elements
in A – site, one can achieve t he l arge magnetic entropy changes i n a l arge t emperature
range, from 1 80 K t o ove r r oom temperature; (ii) W hether t he s pin s tates of M n3+, a nd
Mn4+ take hi gh, i ntermediate or l ow s pin; (iii) The e xchange i nteraction [1,2]. T he
manganese ions interact through an intermediate oxygen, where the Mn3+ -O2- - Mn4+ and
Mn3+ -O2- - Mn3+ or Mn4+ -O2- - Mn4+ systems have ferromagnetic and antiferromagnetic
states respectively [3-7]. The results presented in the last chapter for La0.7 (Ca1-x Pbx )o.3
MnO3 system ar e ve ry i nteresting , especially i n m agnetocaloric ef fect. The m aximum
values of magnetocaloric effect are occured at 291 K but the values are not quite high at
low f ield. In or der t o get m ore hi gher va lues of m agnetocaloric ef fect near r oom
temperature, the amount of Pb2+ ions in La0.7 (Ca1-x Pbx )o.3Mn O 3 series was substituted
by S r2+ in t he a bove series. In t his c hapter, t he de tailed r esults a bout t he s tructure,
magnetic, and magneto-caloric properties of the above samples are presented and possible
explanations are discussed.

The Electric and magnetic pr operties of p erovskite m aterials ar e s trongly de pendent on
microstructure o f the s amples. Mainly the grain s izes of the s amples pl ay an important
role fo r affecting the m agnetic properties of the samples. The grain growth is related to
the grain boundary. Recrystallization and grain growth may create the movement of grain
boundary. The micrographs of the studied samples are seen to be more dense. The figure
7.1 s hows t he S EM o f La0.7(Ca1-xSrx)o.3MnO3 series at di fferent t emperature. The
microsturture of the samples are dependent on the amount of SrCO3 and MnCO3 present
154 | P a g e
in the samples. These two components may influence the microstructure of the perovskite
samples by the formation of liquid phase during sintering period. This facilitates the grain
growth by increasing the rate of cation interdiffusion as a result of its segregation to the
grain boundaries [8]. The behavior of grain growth reflects the competition between the
driving force for the grain boundary movement and retarding force exerted by pores [9].
During t he s intering pr ocess, the t hermal ene rgy creates a force t hat dr ives t he g rain
boundaries t o g row ove r t he por es, s o de creasing t he vol ume of por e a nd m aking t he
material more dense.
La0.7Ca0.3Mn O3(12000 C) La0.7 (Ca0.95Sr0.05)0.3MnO3(12000C)
La0.7 (Ca0.90Sr0.10)0.3MnO3(12000C) La0.7 (Ca0.85Sr0.15)0.3MnO3(12000C)
Fig: 7.1 The SEM pictures of the La0.7(Ca1-xSrx)0.3MnO3 perovskites
155 | P a g e
La0.7 (Ca0.80Sr0.20)0.3MnO3(12000C) La0.7 (Ca0.75Sr0.25)0.3MnO3(12000C)
Fig: 7.1 The SEM pictures of the La0.7(Ca1-xSrx)0.3MnO3 perovskites
The pr esintering and s intering p rocesses w ere s etup a t not t oo hi gh t emperatures. T he

Scanning E lectron M icroscope ( SEM) a nalysis s hown i n f ig 7.1 i ndicates t hat t he
crystallites of t he s amples a re qui te hom ogeneous a nd i ncreases f rom a round 1 µm
(x=0.00) to around 4 µm (x=0.15). In the studied samples the crystalline particles develop
easily du e t o t he e xistence of l iquid pha ses [ 10-16]. D uring t he l iquid pha se f ormation,
grain growth oc curs vi a a di ssolving/ s olution–precipitation pr ocess. E nergetically, in
general s mall grains ar e l ess s table t han large gr ains due t o bigger s urface a reas. As a
consequence, s mall grains w ould be di ssolved i n t he l iquid pha se s tates. It i s obs erved
that an increase in the amount of Sr content results in an increase in the coverage of the
grains by the liquid phase, and this is very useful to grain growth. As a result, the average
grain size increases with increasing concentration of Sr contents.

The che mical com positions of La0.7(Ca1-xSrx)0.3MnO3 perovskites are de termined by t he
Energy Dispersion Spectrum (EDS) which is shown in fig: 7.2. The figure shows that the
sample’s c ompositions are as s imilar t o t he normal one s; i .e. t here ha s be en no
evaporation of Sr by sintering. In this measurement, the electron beam with diameter of
100 Å i s accelerated at 12 kV toward the s urface of s ample, interact w ith surface at om
and emit secondary electron. A detector collected the secondary electron and then we can
156 | P a g e
see t he s urface m icrostructure o f s ample. The energy di spersion spectra m easurement
provides t he i nformation a bout t he pr esence a nd c ontent of t he e lements i n t he s tudied
samples. S imilar t o t he principle of t he S EM, the e nergy of s econdary e lectrons w as
collected and it de pends on t he ki nd of e lement i n m aterials. The s pectrum c ontains
characteristic peaks of La, Ca, Mn, O, Sr, which are target components in the compounds
which are target components in these samples.
(a)
(b)
Fig: 7.2 EDS of LCMO and LCSMO series
157 | P a g e
Measurements
The figure 7.3 and the 7.4 show the results of thermal analysis scans for x=0.25 and for
the series of s amples La0.7(Ca1-xSrx)0.3MnO3 where x = 0.00, 0.05, 0.1, 0 .15, 0.2, 0.25
respectively. It is found that all samples have shown the similar reaction. For all samples
with di fferent S r c oncentration, a continuous w eight l oss o ccurs unt il a r ise i n 1030 0 C
accompanied by an exothermic he at effect. After 1030 0 C onl y little w eight los s is
observed, and no thermal effect occurs. So it is that the suitable calcinations temperature
is at l east ove r 1050 0 C. The or ganic r emoval pr ocess was completed at about 1030 0 C,
favoring the c rystallization process. A ll D SC c urves s how one br oad e ndothermic pe ak
around at 81.820 0-86.180 C, the second endothermic peak at 188.33 0 C, t he third one at
388.780 C the fourth one at 736.62 0 C, the fifth one at 811.60 0 C, the sixth one 907.18 0 C
and the seventh exothermic peak happens at 1022.680 C and the other sharp endothermic
peaks around at different temperatures which is shown in the figures for sample with x=
0.25. It i s s uggested t hat t he f irst t wo e ndothermic pe aks a re du e t o t he evaporation of
water out of t he s amples a nd t he t hird one c orresponds t o t he de composition of
La2O3.nH2O into intermediate oxide phases.
0.00
166.330C
86.350C
-0.75
Heat Flow/(µV)
811.500C
-1.50
389.790C
735.520C
x=0.25 907.180C 1022.680C
-2.25
0 300 600 900 1200
Fig: 7.3 DSC pattern of La0.7(Ca1-xSrx)0.3MnO3 (x=0.25) sample.
158 | P a g e
0
-1 x=0.25
0
-2 388.78 C
0
-1 x=0.20
-2
Heat Flow /(µV)
0
-1 x=0.15
-2
0
-1 x=0.10
-2
0
-1 x=0.05
-2
0
x=0.00
-1
-2 387.930C
0 400 800 1200
Furnace Temperature /0C
Fig: 7.4 DSC pattern of La0.7(Ca1-xSrx)0.3MnO3 series
100
M.V.=2.580%,M=0.545mg
M.V.=9.226%,M=1.950mg
90
Weight/(%)
x=0.25 M.V.=9.664%,M=2.042mg
80
T.M.=21.133mg
Residue=75.17%,
M =15.88mg
M.V.=3.365%,M=0.711mg
0 300 600 900 1200

0
Furnace Temperature/ C
Fig: 7.5 TGA pattern of La0.7(Ca1-xSrx)0.3MnO3 (x=0.25) sample.
159 | P a g e
100
x=0.25
80
100
x=0.20
80
100
Weight / (%)
80 x=0.15
100
80 x=0.10
100
x=0.05
80
100
x=0.00
80
0 300 600 9000 1200
Furnace Temperature / C
Fig: 7.6 TGA pattern of La0.7(Ca1-xSrx)0.3MnO3 series
The s harp endothermic pe ak around 388 0 C is r elated to thermal de composition of

lanthanum h ydroxide, La (OH)3 originating from La2O3 in the wet milling process [ 17-
20]. W hen keeping La2O3 at hi gh hum idity c onditions, a pa rt of La ( OH)3 is occurred.
From c omparison with TGA a nalysis of th e r aw ma terials M nCO3 and SrCO3, t he
endothermic pe aks at 736.19 0 C, 811.19 0 C a nd a t 907 0 C can be r elated t o the t hermal
decomposition of SrMnO3. The fuzzy exothermic peak around 10220 C can be considered
to correspond to the start of the reaction in which the perovskite structure is formed [21-
24]. In these experiments it is clearly seen that with increasing Sr substitution, all thermal
transitions are shifted to lower temperatures. The figures 7.5 and 7.6 show TGA curves of
the w eight l osses a t di fferent t emperatures f or x= 0.25 a nd f or La0.7(Ca1-xSrx)0.3MnO3
series. The total weight loss in sample la0.7(Ca0.75Sr0.25)0.3MnO3 is 24.83%.
160 | P a g e
Since the ionic radious of Sr2+ ions (<rSr> = 1.31Å i s less than the ionic radious of Ba2+
ions ( <rBa> = 1.47Å a nd t he i onic r adious of P b2+ ions (<rPb>= 1.35Å) , t he l attice
parameters and unit cell volume are expected to decrease due to the substitution of Sr2+
ions w hich will a ffect t he m agnetic and magnetocaloric p roperties. The pha se
identification and lattice c onstants determination w ere pe rformed b y u sing t he X RD
pattern. W hen the X-ray beam with given the energy and the wavelength irradiates into
the sample, it will be reflected on va rious crystal planes and interferes with another. The
diffraction intensity of X-ray depends on the an gle between the beam and cr ystal plane.
Based on t he i ntensity and t he pos ition of s pectrum l ine, t he l attice pa rameters, t he
symmetry a s w ell as t he c rystal pha ses c an b e obt ained. T he s tructure of t he s tudied
samples w as e xamined i n a B ruKer D 5005 X -ray diffractometer, i n a Bruker D 8 X-ray
Diffractometer, which uses the Cu - K α radiation with λ = 1.54056 Å and 1.56056 Å.
Fig: 7.7 presents the X-Ray Diffraction Patterns of the investigated examined samples.
(112)
Intensity (a.u.)
(132)
(220)
(224)
(202)
(002)
(116)
(136)
(532)
x=0.25
x=0.20
x=0.05
x=0.00
30 60 90 120
2 Theta (deg.)
Fig: 7.7 X-ray diffraction patterns of La0.7(Ca1-xSrx)0.3MnO3 samples (12800 C) with index
number, h, k, l
161 | P a g e
Intensity (a.u.)
x=0.25
x=0.20
x=0.05
x=0.00
32.25 32.50 32.75 33.00 33.25
2 Theta (deg.)
Fig: 7 .8 The Enlarged view of t he 2 θ = 32.0 0-33.50 for X -ray di ffraction pa tterns of
La0.7(Ca1-xSrx)0.3MnO3 series.
It i s c lear t hat a ll s amples a re of s ingle pha se with or thorhombic s tructure. La 1-xPb x
MnO3 compounds ha ve been i nvestigated i n R ef [ 25-28] w ith hexagonal c ells of s pace

group R3c [29-35] for all x=0.00 to 0.5. The lattice parameters derived from XRD data of
fig: 7.7 are shown in table-7.1. Significant increases of parameters and unit cell volume is
related with increasing o f Sr2+ ions l eading t o i ncrease a verage i on r adius of A – sites,
<rA> (Table 7.1 be low).Typical ionic radii were directly quoted from “Electronic Table
of Shanon Ionic Radii, J. David Van Horn, 2001”.
7.5.1 Structure Characterization

The X RD pa tterns f or La0.7(Ca1-xSrx)0.3MnO3 series a re s hown i n f ig 7.7 (Sintered at
12800 C) and in f ig:7.9 (Sintered a t 1200 0 C). In fig 7.8 , the e nlarged view of 2 θ i s
displayed. From the f igures it is c learly s een that a ll the s amples a re c rystallized in the
orthorhombic structure with Pbnm symmetry. The lattice parameters and volume of unit
cell calculated from XRD were plotted in fig 7.10 and 7.11 The lattice parameters a, b, c
and uni t c ell vol ume a re g radually i ncreased w ith i ncreasing S r c ontents.The R ietveld
refinement technique (Fig: 7.12, F ig: 7.13) for La0.7(Ca1-xSrx)0.3MnO3 series was used to
analyze t he X RD pa tterns and to determine t he l attice pa rameters and the at omic
162 | P a g e
positions of La0.7(Ca1-xSrx)0.3MnO3 elements in the crystal. The results are shown in table
7.1
Fig: 7.9 X-ray diffraction patterns of La0.7(Ca1-xSrx)0.3MnO3 samples (12000)
5.510 7.7475
5.505
a
5.500 7.7450 c
Lattice parameter a, b, (Å)
b
Lattice parameter c, (Å)
5.495
7.7425
5.490
5.485
7.7400
5.480
5.475 La0.7(Ca1-xSrx)0.3MnO3 7.7375 La0.7(Ca1-xSrx)0.3MnO3
5.470 x=0.00, 0.05,0.10,0.15,0.20,0.25 x=0.00,0.05,0.10,0.15,0.20,0.25
7.7350
5.465 (Q)
(P)
5.460
0.000 0.025 0.050 0.075 0.000 0.025 0.050 0.075
Sr content Sr content
Fig: 7.10 Lattice parameters as a function of Sr Content
163 | P a g e
Table-7.1 Lattice Parameters (From Single Phase)
Sr Content(x) Lattice Parameter a(Å) Lattice Parameter b(Å) Lattice Parameter c(Å)
0.00 5.4853 5.4772 7.7339
0.05 5.4875 5.4788 7.7356
0.10 5.4935 5.4806 7.7382
0.15 5.4968 5.4822 7.7408
0.20 5.5010 5.48338 7.7436
0.25 5.5035 5.4852 7.7466
234.00
233.75
Volume of unit cell (a°)3
233.50
233.25
233.00
232.75
232.50
0.025 0.050 0.075

Sr content
Fig: 7.11 Volume of unit cell as a function Sr content.
Table-7.2 Unit cell Volume, Bond angle and Bond length

Sr c ontent Bond a ngle Bond length Bond l ength Volume (Å)3 from
(x) (deg.) (Mn-OP) Å (Mn-Oa) Å single Phase
0.05 150.52 1.9988 1.9686
232.5702
0.10 154.45 1.9958 1.9680
232.9792
0.15 157.78 1.9706 1.9676
233.2656
0.20 163.88 1.9492 1.9672
233.5964
0.25 167.44 1.9449 1.9666
233.8528
164 | P a g e
Fig: 7. 12 Reitveld analysis of La0.7(Ca1-xSrx)0.3MnO3 samples ( 12800) from X -ray
diffraction patterns with considering single phase.
165 | P a g e
Fig: 7.13 Reitveld analysis of La0.7(Ca1-xSrx)0.3MnO3 samples ( 12800C) from X -ray
diffraction patterns with considering double phase.
166 | P a g e
The fig: 7.14 s hows that the bond a ngle increases as Sr contnents increases and the fig:
7.15, 7.16 s how that the bond l ength decreases with increasing doping contents. The fig:
7.17 and the fig: 7.18 show that Curie temperature and and tolerance factor increase with
the increasing Sr contents.
168
165
Bond angle(deg.)
162
159
156
153
150
0.025 0.050 0.075
Sr content
Fig: 7.14 Bond angle as a function of Sr content.
1.995
Bond length (Mn-OP)Å
1.980
1.965
1.950
0.025 0.050 0.075

Sr content
Fig: 7.15 Bond length (Mn-OP) as a function of Sr content
167 | P a g e
1.9690
1.9685
Bond length (Mn-Oa)Å
1.9680
1.9675
1.9670
1.9665
0.025 0.050 0.075

Sr content
Fig: 7.16 Bond length (Mn-Oa) as a function of Sr content.
Table-7.3 Tolerance factor and Curie temperature

Sr Contents(x) Tolerance Curie Temperature Curie Temperature Radius of
Factor (K) (Ts=12000C) (K) (Ts=12800C) A-site (Å)
0.00 0.8702 252 202 1.1512
0.05 0.8711 263 175 1.1559
0.10 0.8721 268 255 1.1605
0.15 0.8731 275 214 1.1652
0.20 0.8740 282 231 1.1698
0.25 0.8750 293 221 1.1745
0.30 255 1.1791
0.50 303 1.1977
290
Curie Temperature (K)
280
270
260
0.000 0.025 0.050 0.075

Sr Content
Fig: 7.17 Curie temperature as a function Sr content
168 | P a g e
0.875
0.874
Tolerance factor
0.873
0.872
0.871
0.870
0.000 0.025 0.050 0.075

Sr content
Fig: 7.18 Tolerance factor as a function Sr content
7.6 Magnetic Properties

7.6.1 The Thermo-Magnetic Zero–Field–Cooled (ZFC), Field-Cooled (FC)
Measurements
For t he s amples (x= 0.00, 0.05, 0.10, 0.15, 0.20, 0.25, 0 .30 a nd 0.50) of t he s eries
LCSMO, t he t hermo-magnetic m agnetization measurements w ere pe rformed in a
magnetic f ield o f 20 O e a nd 50 Oe r espectively and t he results w ere d isplayed i n f ig:
7.19 and 7.20.
3.00
Ts=12000C
2.25 H=20 Oe
1.50
x=0.00
x=0.05
x=0.10
x=0.15
0.75 x=0.20
x=0.25
0.00
150 200 250 300 350 400
Temperature (K)
Fig: 7.19 The t hermomagnetic F ield - Cooled ( FC) a nd Zero – Field – Cooled (ZFC)
curves of the LCSMO series
169 | P a g e
x=0.00
Ts=12800C x=0.05
x=0.10
9
x=0.15
Magnetization (emu/g) x=0.20
x=0.25
x=0.30
x=0.50
6
3 H=20 Oe
0
150 200 250 300 350
Temperature (k)
Fig: 7.20 The thermomagnetic zero – field – cooled (ZFC) curves of the LCSMO series
From these thermo-magnetic curves, the ferromagnetic [36-39] to paramagnetic transition

temperature, TC can be determined. The Curie temperature increases with increasing the
Sr contents in the samples from 258 K to 293 K when the samples were sintered at 1200 0
C a nd 185 K ( x= 0.00) to 30 5 K ( x= 0.50) when the s amples w ere s intered at 1280 0 C.
This t endency a lmost a grees w ith de pendence of T c (x) in the s ystem La 1-xSr x MnO3
2+ 2+
[12]. I t i s clear t hat t he s ubstitution of S r for C a induces a m ixed valence s tate o f
Mn3+/Mn4+ and e nhances t he f erromagnetic t ransition t emperature d ue t o doubl e
exchange i nteraction. Because of l arge S r2+ ions i n the s amples, the i ncrease of S r2+
content substituted for Ca2+ ion leads to an increasing in the average radius of the A- sites
cation <rA> (Table-7.3) which is shown in fig: 7.21. Increasing the radius <rA> causes an
increase i n t he i nternal pr essure, w hich d ecreases t he buc kling of t he M nO6 octahedral
and t hen t he T c enhances [ 40-43]. F rom t he f ig: 7.22 a nd 7.23 i t is s een t hat t he C urie
temperature i ncreases with the i ncreasing o f bond angle and t olerance factor. The
decreasing of magnetization on ZFC curve in low temperature range indicated that there
is short – range order [44-47] in the studied samples. The maximum will be the result of
the c ompetition be tween the ( local) ani sotropy ( decreasing w ith increasing t emperature,
so allowing an i ncreasing m agnetization) and the de crease of t he m agnetic or der w hen
Curie t emperature i s ap proached. In a ddition, t he r ole of grains a nd grain bounda ries
could be another reason of such phenomena. At grain boundary, the exchange interaction
(SE a nd D E) a re w eak compared t o t hose i nside t he grain [ 48-50]. T his l eads t o t he
inhomogeneity of magnitude of exchange interaction.
170 | P a g e
295
290
Curie temperature (K) 285
280
275
270
265
260
1.155 1.160 1.165 1.170 1.175
Ionic Radius of A-site (Å)
Fig: 7.21 Curie temperature as a function of ionic radius of A-site
290 Sr series
280
270
260
150 155 160 165
Bond Angle (θ0)
Fig: 7.22 Curie temperature as a function of Bond angle
290
Sr series
Curie temperature (K)
280
270
260
250
0.8700 0.8725 0.8750
Tolerance factor
Fig: 7.23 Curie temperature as a function of tolerance factor
171 | P a g e
From the FC and ZFC curve we can correlate Tr, Tf and TC and we can explain the similar
composition de pendence t o t hat of C urie t emperature T C for t he s tudied s amples. At
higher temperatures, the FM is broadened leading to increasing of magnetization in ZFC
curve. T his pha se s eparation phe nomenon i s t he i ntrinsic f eature of pe rovskite – type
manganites [ 51-53] a nd w as e xperimentally obs erved i n va rious m anganites a s w ell a s
affirmed by the theoretical studies.
7.6.2 The Hysteresis Loops of LCSMO series

The magnetic hysteresis loops were measured at the temperature of 100 K in fields from
-1.35T to +1.35T, and the results are plotted in fig 7. 24 . From the figure 7.25, it is seen
that the sample x=0.1, x=0.3 starts to saturate from 7000 Oe where as x=0.5 does not start
to s aturate even from 1. 35T. From t hese f igures i t ha s be en said that t he coe rcivity and
remanence magnetization are very low.
40
30
x=0.10
20
10
-10
T=10 K
-20
-30
-40
-900 -600 -300 0 300 600 900
Magnetic field H(Oe)
Fig: 7.24 Hysteresis loop of La0.7Ca0.27Sr0.03MnO3 sample.
172 | P a g e
50
25 T=10 K
-25
x=0.10
x=0.30
x=0.50
-50
-10000 -5000 0 5000 10000

Fig: 7.25 Hysteresis loop of LCSMO series
Table-7.4 Saturation Magnetization, Coercivity, and Remanence

Sr C ontents Saturation Applied Coercivity Remanance
(x) Magnetization Magnetic Field (Oe) (emu/g)
(emu/g) (T)
0.10 54.83 1.35 20.57 1.17
0.30 52.27 1.35
0.50 1.35
7.7 Magnetic Isotherm of LCSMO series and Magnetic Entropy Measurements

The M(H) isotherms have been measured for the samples (x=0.00, 0.05, 0.1, 0.3, 0.5) of
La0.7 ( C a1-x Srx )o.3 Mn O 3 series i nvestigated a t va rious t emperatures i n a na rrow
temperature i nterval ar ound the r espective C urie t emperatures, in m agnetic f ield up t o
13.5 k O e . T he fig: 7.26 ( TS=12000 C), a nd t he f ig: 7.28, 7.30, 7.32, 7.34, 7.36
(TS=12800 C) s how the set of isothermal M(H) curves of perovskite La0.7 ( Ca1-x Srx )o.3
Mn O3 (x= 0.00, 0.05, 0.1, 0.3, 0.5). From these M (H) curves measured around TC, the
|Δ Sm|(T) dependence has been determined according to the following equation [54-55]
( M n − M n+1 ) H
=∆S ∑ Tn +1 − Tn
∆H n
7.1
173 | P a g e
and presented in fig: 7.27, 7.29, 7.31, 7.33, 7.35 and 7.37. For magneto-caloric materials,
the r elative cool ing pow er ( RCP) r epresents a good w ay f or c omparing them a nd i t i s
defined as
where δ Tfwhm means the full-width at the half maximum of the magnetic entropy and the
results were shown in table-7.5. In fig: 7.27, 7.29, 7.31, 7.33, 7.35 a nd 7.37, the |Δ Sm|(T)
for t he s tudied s amples a re pl otted a s a f unction of t emperature f or di fferent s intering
samples. The maximum magnetic entropy ch anges [ 56-60] |Δ Sm|max, as w ell as the RCP
values f or all s amples a re lis ted in table-7.5. | Δ Sm|max has r eached hi gher value of
5.00 J/KgK for the composition x= 0.25 whose sintering temperature was 12000 C and the
magnetocaloric effect was calculated at 1.35T. It can be seen from the table – 7.5 that our
studied samples have quite large |Δ Sm|max as materials with giant magnetocaloric effect
(GMCE) [ 61-65]. A pr omising m aterial f or a pplication s hould ha ve hi gh R CP a nd t he
value of TC close to room temperature. In our case, the |Δ Sm|max and RCP values are large,
the T C for the samples x=0.25 are near room temperature. The doping effect might solve
this disadvantage.
Table -7.5 Magnetic entropy and RCP of the LCSMO series

Sample TC from Δ Smax TC from Δ Smax RCPmax RCPmax
(x) ZFC curves (J/kGK) ZFC cur ves (J/kGK) (J/kg) (J/kg)
0 0 0
(K) (Ts=1200 (K) (Ts=1280 (Ts=1280 (Ts=12000
(Ts=12000 C) at 1.35T (Ts=12800 C) at C) at C) at
C) C) 1.35T 1.35T 1.35T
0.00 258 6.5 202 4.75 47.50 87.23
0.05 263 0.62 175 2.48 47.045
0.10 268 3.62 255 2.28 31.92 30.34
0.15 275 1.65 215
0.20 282 1.81 230
0.25 293 5.00 220 58.60
0.30 256 2.81 54.28
0.50 303 2.72 27.2
174 | P a g e
75
240
245
Magnetization (emu/g) 60 250
255
260
265
x=0.25 270
45
275
280
285
290
30 295
300
305
310
15 315
Ts=12000C
0
0 3000 6000 9000 12000 15000
Fig: 7.26 Magnetization of LCSMO (x=0.25) series as a f unction Magnetic field sintered
at 12000C
x=0.00
6.0 x=0.10
Magnetic entropy, ∆S (J/kgK)
x=0.25
4.5
3.0
1.5
0.0
225 250 275 300 325
Temperature (K)
Fig: 7.27 Magnetic entropy of LCSMO series (x=0.00, 0.10 and 0.25) sintered at 1200 0C
as function of temperature
175 | P a g e
75
Magnetization, ( emu/g)
179.45
60
45
30
x=0.00
15
224.75K
∆T=5K
0
0 3000 6000 9000 12000
Magnetic Field, H (Oe)
at 12800C
5.00
Magnetic entropy, ∆S(J/kgK)
x=0.00
1.35T
3.75 1.0T
2.50
1.25
0.00
180 195 210 225
Temperature (K)
Fig: 7.29 Magnetic entropy as function of temperature at 1.35 T and 1 T (x=0.00) sintered
at 12800C
176 | P a g e
60 La0.7Ca0.285Sr0.015MnO3 164K
45
30
199K
15
∆T=5K
0
0 4000 8000 12000
Magnetic field (Oe)
Fig: 7.30 Magnetization of LCSMO (x=0.05) seris as a function Magnetic field sintered at
12800C
2.5
2.0
x=0.05
1.5
1.0
1.0T
0.5 1.35T
170 180 190 200

Temperature (K)
Fig: 7.31 Magnetic entropy as function of temperature at 1.35 T and 1 T (x=0.05)
177 | P a g e
75
∆T=5K 195K
60
45
30
15 240K
La0.7Ca0.27Sr0.03MnO3
0
0 4000 8000 12000
Magnetic Field (Oe)
at 12800C
2.5
x=0.10
Magnetic Entropy, ∆S (J/kgK)
2.0
1.5
1.0
1.35
0.5
1T
0.0
200 210 220 230 240
Temperature (K)
178 | P a g e
225K
45
∆T=5K
30
15
270K
0
0 4000 8000 12000
Magnetic Field (Oe)
at 12800C
3.0
2.5 x=0.30
2.0 1.35T
1T
1.5
1.0
0.5
0.0
230 240 250 260 270
Temperature (K)
179 | P a g e
60
264.95
269.85
274.75
45 280.15
285.25
290.45
296.05
300.55
30 305.45
310.45
315.55
320.55
325.55
15
0
0 4000 8000 12000 16000
Magnetic Field (Oe)
Fig: 7.36 Magnetization of LCSMO (x=0.50) series as a function Magnetic field sintered
at 12800C
3.0
2.5
Magnetic entropy, ∆S (J/kgK)
x=0.50
2.0
1.5
1.0
0.5 1.35T
1.0T
0.0
270 280 290 300 310 320
Temperature (K)
180 | P a g e
7.8 Summary
A de tailed study o f the ma gneto-caloric e ffect in the La0.7 (Ca1-x Srx)0.3 Mn O 3
(x= 0.00, 0.05, 0.1, 0.15 , 0.2, 0.25 , 0.30, 0. 50) c ompounds ha s be en i nvestigated f or
different sintering temperature. We have found the large magnetic entropy changes as we
knew, i.e. the large magneto-caloric effect, in these samples. Among them, the magnetic
entropy change reaches a maximum value of 5.00 J/kg K at the applied field of 13.5 kOe
for t he La0.7 (Ca0.75 Sr0.25)0.3Mn O 3 sample w hose s intering t emperature w as 1200 0 C,
associated with the first order ferromagnetic to paramagnetic transition at 293 k. It gives
us a s uggestion t hat t his m aterial w ould be a suitable pr e-eminent c andidate f or t he
advanced magnetic refrigeration technology; namely; a l arger value of entropy change is
expected compared to the pol ycrystalline s amples; an d t he∆ s m distribution i s qui te
uniform, w hich i s de sirable f or an E ricson – cycle m agnetic r efrigerator. The l arge
magnetic entropy change produced by the abrupt reduction of magnetization is attributed
to the strong coupling between spin and lattice in the magnetic ordering process. Table-
7.6 and the figure 7.17, 7.18 show the comperative studies on magnetocaloric effect for
strontium series.
10 1.35(T)
5(T)
6
(0.075, 5.00)
2
0.00 0.05 0.10 0.15 0.20 0.25
Sr Content
Fig: 7.38 Comperative studies on Magnetic entropy as a function of Sr content
(The arrow sign shows the highest magnetic entropy at 1.35 T for Sr =0.0.75)
181 | P a g e
Table-7.6 Comparative studies on Magneto-Caloric Effect for Strontium (Sr) series
Composition Curie Temperature. Applied Δ SM Reference
TC (K) Field H (T) (J/kgK)
La2/3Sr1/3MnO3 370 1 1.5 66
La0.67Sr0.33MnO3 348 5 1.69 67
La0.70Ca0.25Sr0.05MnO3 275 5 10.5 68
La0.70Ca0.20Sr0.1MnO3 308 5 7.45 68
La0.70Ca0.1Sr0.2MnO3 340 5 6.97 68
La0.70Ca0.05Sr0.25MnO3 341 5 6.86 68
0
La0.70Ca0.27Sr0.03MnO3 268(TS=1200 C) 1.35 3.62 Present work
La0.70Ca0.225Sr0.075MnO3 293(TS=12000C) 1.35 5.00 Present work
La0.70Ca0.285Sr0.015MnO3 175 (TS=12800C) 1.35 2.5 Present work
La0.70Ca0.285Sr0.015MnO3 175 (TS=12800C) 1 1.84 Present work
10 1.35(T)
5(T)
6
(293, 5.00)
2
260 280 300 320 340
Fig: 7.39 Comperative studies on Magnetic entropy as a function Curie temperature
(The arrow sign shows the highest magnetic entropy at 1.35 T for Tc= 293 K).
182 | P a g e
References
[7.1] Zener, “Interaction between the shells in the transition metals”, Phys.Rev. 82 (1951)
403
[7.2] P.W. Anderson, H.Hasegawa, “Considerations on double exchange,” Phys. Rev. 100
(1955) 675
[7.3] P .M. R accah a nd J .B. G oodenough, “ A l ocalized-Electron to collective-Electron
Transition in the system (La,Sr)CoO3”, J. Appl. Phys. 39 (1968) 1209
[7.4] V .G. B hide, D .S. R ajoria, C .N.R. R ao, G .Rama R ao a nd V .G. J adhao, “ Itinernt-
electron ferromagnetism in La1-xSrxCoO3: A M össbauer study”, P hys.Rev. B 12
(1979) 2832
[7.5] J.B. Goodenough, “An interpretation of the magnetic properties of perovskite-type
mixed crystal La1-xSrxCoO3-• ”, J.Phys. Chem. Solids 6 (1958) 287
[7.6] T hornton, B .C. Tofeild a nd D .E. W illiams, “ Spin s tate e quilibria a nd t he
semiconductor t o m etal t ransition of LaCoO3”, Solid S tate C omm. 44 ( 1982) 1213 -
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187 | P a g e
Chapter Eight Study of La0.7(Ca1-xBax)o.3MnO3 Perovskite
8.1 Introduction

(i) La0.7(Ca1-xBax) 0.3MnO3 (ii) La0.7 (Ca0.95 Ba0.05)0.3 MnO3
(iii) La0.7 (Ca0.90 Ba0.10)0.3 MnO3 (iv) La0.7 (Ca0.85 Ba0.15)0.3 MnO3
(v) La0.7 (Ca0.80 Ba0.20)0.3 MnO3 (vi) La0.7 (Ca0.75 Ba0.25)0.3 MnO3
The l ast t wo s ystems have revealed many i nteresting ma gnetic pr operties inc luding
magnetocaloric effect i n l arge t emperature r ange, f rom 245K t o 310K . M oreover, t he
obtained values of magnetocaloric effect have reached the maximum value of 3.94 J/kgK
for t he s ample P b = 0 .075 a t 29 1 K a nd 5 .00 J /kgK for t he s ample S r= 0.075 at
temperature 293 K. To find the more magnetocaloric effect around room temperature the
above series are also chosen to study in this thesis. Materials having coupled electric and
magnetic pa rameters tha t r esults in simultaneous electric s tructure and magnetic
properties ha ve at tracted a cons iderable r evival of i nterest i n recent years [ 1-2]. From a
technical poi nt of vi ew, the mut ual c ontrol of e lectric a nd magnetic p roperties is a n
attractive possibility, for it adds one more degree of freedom to manipulate the properties
of bot h magnetic and el ectric m aterials. La0.7 (Ca1-x Bax)o.3 Mn O 3 is one of t he t ypical
manganite perovskite materials whose magnetic and electric properties are very sensitive.
It crystallizes in an orthorhombic s tructure with P bnm s ymmetry. A s s hown i n t he
previous chapters, the value of <rA> has a same or more strong influence on magnetic and
magneto-caloric properties in particular of perovskite – type manganites due to the larger
ionic r adious of dopi ng content B arium. T his c hapter c ontains t he s tudies of t he r esults
about the structure, magnetic, and magneto-caloric properties of the above series:

The pr e-sintering a nd s intering pr ocesses w ere s etup a t not t oo high t emperatures. T he
figure 8.1 displays the SEM micrographs of LCBMO series which are sintered at different
temperature. It can be explained from the micrographs that the dense microstructures are
obtained f or a ll s amples. T he a verage g rain sizes of t he s amples ar e increased with
increasing Ba doping contents. The Scanning Electron Microscope (SEM) analysis in fig
8.1 indicates t hat t he crystallites of t he s amples ar e qui te hom ogeneous and increases
188 | P a g e
from a round 0.5 µ m ( x= 0.00) t o a round 3 µ m ( x= 0.15). This a lso indicates tha t B a
substitution within small range promotes the grain growth, while MnCO3 or BaCO3 may
be formed as secondary liquid phase at grain boundaries and hinders the grain growth. In
the studied samples the crystalline particles develop easily due to the existence of liquid
phases [3-5].
La0.70 Ca0.30 Mn O3 (12800 C) La0.7(Ca0.95Ba0.05)0.3MnO3 (12800C)
La0.70 (Ca0.90Ba0.10)0.3 Mn O3 (12800 C) La0.7 (Ca0.85Ba0.15)0.3Mn O3 (12800 C)
Fig: 8.1 The SEM pictures of the La0.7(Ca1-xBax)0.3MnO3 perovskites
189 | P a g e
La0.7(Ca0.80Ba0.20)0.3MnO3 (12800 C) La0.7(Ca0.75Ba0.25)0.3MnO3(12800 C)
Fig: 8.1 The SEM pictures of the La0.7(Ca1-xBax)0.3MnO3 perovskites

The elemental an alysis of La0.7(Ca1-xBax)0.3MnO3 perovskites are de termined by t he
Energy Dispersion Spectrum (EDS) which is shown in fig: 8.2 (a, b,). The micrographs of
the s amples show t hat t he s ample’s compositions are as similar to the n ormal ones; i.e.
there h as b een no e vaporation of B a b y sintering p rocess. T he phot ograph of s urface
microstructure indicates the samples are well prepared.
(a)
Fig: 8.2 EDS of LCMO and LCBMO series
190 | P a g e
(b)
Fig: 8.2 EDS of LCMO and LCBMO series
In this me asurement, the same p rocess i s us ed t o see t he s urface m icrostructure o f

samples. The s pectrum contains cha racteristic p eaks of La, Ca, Mn, O, B a, which are
target components in the compounds. The energy dispersion spectra measurement ensures
the information about the presence and content of the elements in the studied samples.
8.4 Differential Scanning calorimetry (DSC) and Thermal Gravimetric Analysis

(TGA) Measurements
The f igure 8.3 , 8.4 a nd 8.5 show t he r esults of t hermal analysis s cans for a s eries of
samples La0.7(Ca1-xBax)0.3 Mn O3 where x=0.00, 0.05, 0.1, 0.15, 0.2, with DSC and TGA
and dTG curves for the starting material La2O3. It is found that all samples have shown
the similar reaction. For all samples with different Ba concentration, a continuous weight
loss occurs until a rise in 9200 C accompanied by an exothermic heat effect. After 900 0 C
only little weight loss is observed, and no t hermal effect occurs. So it is that the suitable
calcinations te mperature is a t le ast ov er 900 0 C. T he or ganic r emoval pr ocess w as
completed at about 9300 C, favoring the crystallization process. All DSC curves show one
broad endothermic peak around at 82-1150 C, the second endothermic peak at 409.99 0 C,
the third one at 4920 C and the fourth one at 851 0 C and fifth exothermic peak happens at
920.640 other sharp endothermic peaks around at different temperatures which is shown in
the figures for sample with x= 0.05. It is suggested that the first endothermic peak is due
to t he e vaporation of w ater from the s amples a nd t he s econd one c orresponds t o t he
decomposition of La2O3.nH2O into intermediate oxide phases.
191 | P a g e
0 300 600 900
20
10 980C 8470C9210C
0 x=0.20
-10 4100C
Heat Flow /(µV) 20
10
1060C 8470C9210C
0 x=0.15
-10 4100C
10
1160C
8470C 0
0 x=0.10 921 C
-10 4100C
10
1160C 8470C 0
0 921 C
x=0.05
4100C
-10
0 300 600 900
Furnace Temperature (/0C)
Fig: 8.3 DSC pattern of La0.7(Ca1-xBax)0.3MnO3 series
0 300 600 900

0
-10
-20 x=0.20
-30
0
-10
Weight/( %)
-20 x=0.15
-30
0
-10
-20 x=0.10
-30
0
-10
x=0.05
-20
-30
0 300 600 900
Furnace Temperature (/0C)
Fig: 8.4 TGA pattern of La0.7(Ca1-xBax)0.3MnO3 series
192 | P a g e
0 300 600 900
0
-1
5650C 8560C
-2 x=0.20 9210C
-3 0
410 C
0
-1
5650C
-2 8560C 0
dTG/%/min
x=0.15
-3 921 C
4100C
0
-1
-2 5650C
x=0.10 8560C 9210C
-3 4100C
0
-1
-2 5650C
x=0.05 8560C 9210C
-3 410 C 0
0 300 600 0 900

Furnace Temperature/ C
Fig: 8.5 dTG pattern of La0.7(Ca1-xBax)0.3MnO3 series
The s harp endothermic pe ak a round 492 0 C is r elated to thermal de composition of

lanthanum hydroxide La(OH) 3 originating from La2O3 in the wet milling process [6-9].
When keeping La2O3 at high humidity conditions, a part of La (OH) 3 is occurred. From
comparison with TGA analysis of the raw materials MnCO3 and BaCO3, the endothermic
peaks a t 851.28 0 C a nd a t 920.64 0 C c an be r elated t o t he t hermal de composition of
BaMnO3 respectively. The f uzzy e xothermic p eak a round 950 0 C c an be c onsidered t o
correspond to the start of the reaction in which the perovskite structure is formed [10-13].
In these e xperiments it i s c learly s een that w ith increasing B a s ubstitution, all the rmal
transitions a re s hifted t o l ower t emperatures. T GA c urves s how t he w eight l osses a t
different te mperatures. The tot al w eight los s in sample la 0.7(Ca0.95Ba0.05)0.3MnO3 is
24.79%.

Since the ionic radious of Ba2+ ions (<rBa> = 1.47Å is larger than the ionic radious of Pb2+
ions (<rPb>= 1.35Å) and t he i onic r adious of Sr2+ ions ( <rSr> = 1.31 Å , the l attice
parameter a nd uni t c ell volume a re e xpected t o increase due t o t he s ubstitution of B a2+
ions which will effect the magnetocaloric effects. When the X-ray beam with given the
energy and the w avelength irradiates int o the s ample, it w ill be r eflected on various
193 | P a g e
crystal planes and interferes with another. The diffraction intensity of X-ray depends on
the angle between the beam and crystal plane. Based on t he intensity and the position of
spectrum l ine, the l attice pa rameters, the s ymmetry as w ell as t he crystal phases can be
obtained. The structure of the studied samples was examined in a BruKer D5005 X-ray
diffractometer, in a Philips D5000 X-ray diffractrometer and in a Bruker D8 X-ray
(200)
La0.7(Ca1-xBax)0.3MnO3
(312)
Intensity (a.u.)
(220)
(202)
(424)
(400)
(002)
(420)
(352)
(444)
(516)
x=0.25
x=0.20
x=0.10
x=0.05
x=0.00
30 60 90 120 150
2 Theta (θ0)
Fig: 8.6 X-ray di ffraction pa tterns of La0.7(Ca1-xBax)0.3MnO3 samples ( 12800 C) with
index number h, k, l.
Intensity (a.u.)
x=0.25
x=0.20
x=0.10
x=0.05
x=0.00
32.25 32.50 32.75 33.00

2 Theta (θ0)
Fig: 8.7 The e nlarged vi ew of 2 θ = 320 to 3 3.50 for X-ray di ffraction pa tterns of
La0.7(Ca1-xBax)0.3MnO3 samples (12800 C)
194 | P a g e
Diffractometer, which uses the Cu - K α radiation with λ = 1.54056 Å and λ = 1.56056
Å. The f ig: 8.6 presents t he X -Ray D iffraction Patterns of t he i nvestigated examined
samples. It is c lear tha t a ll s amples a re o f s ingle ph ase with orthorhombic s tructure.
La 1-x Pb x Mn O 3 compounds ha ve be en i nvestigated i n R ef [ 14-15] w ith he xagonal
cells of s pace group R3c [ 16-24] f or a ll x= 0.00 t o 0.5. T he l attice p arameters de rived
from XRD data of fig: 8.6 are shown in table-8.1. Significant increases of parameters and
unit c ell vol ume is r elated with increasing of B a2+ ions l eading t o i ncrease a verage i on
radius of A – sites, <rA> (table 8.1 below). Typical ionic radii were directly quoted from
“Electronic Table of Shanon Ionic Radii, J. David Van Horn, 2001”.
Fig: 8.8 O bserved ( star) a nd c alculated ( solid l ine) X -ray di ffraction pattern for
La0.7(Ca1-xBax)0.3MnO3 series
195 | P a g e
Fig: 8.8 Observed ( star) a nd c alculated ( solid l ine) X -ray di ffraction pa ttern f or
La0.7(Ca1-xBax)0.3MnO3 series
196 | P a g e
The s tructure r efinement of La0.7(Ca0.90Ba0.10)0.3MnO3 samples w as pe rformed in the
orthorhombic s etting of the P bnm s pace group and the s tructural pa rameters f or s ample
x=0.05 was calculated by Reitveld refinement technique.
8.5.1 Structure Characterization

The XRD patterns for La0.7(Ca1-xBax)0.3MnO3 systems are shown in fig 8.6 and in fig 8.7
the e nlarged view o f 2 θ is di splayed. From th e f igures it is c learly s een that a ll the
samples are crystallized in the orthorhombic structure with Pbnm s ymmetry. The lattice
parameters and volume of unit cell calculated from XRD pattern were plotted in fig 8. 9
and 8.11. The lattice parameters a, b, c and unit cell volume are gradually increased with
increasing Ba contents. T he R ietveld refinement t echnique f or La0.7(Ca1-xBax)0.3MnO3
systems was used to analyze the XRD patterns and to determine the lattice parameters and
the a tomic pos itions of La0.7(Ca1-xBax)0.3MnO3 elements i n the cr ystal. The r esults ar e
shown in table 8.1
5.52
(P) 7.760 c
5.51
Lattice parameter a, b (Å)
5.50
7.755
(Q)
5.49
5.48 7.750
x=0.00,0.05,0.10,0.15,0.20,0.25
5.47 a
7.745
b La0.7(Ca1-xBax)0.3MnO3
5.46
x=0.00,0.05,0.10,0.15,0.20,0.25
5.45 7.740
0.000 0.025 0.050 0.075 0.000 0.025 0.050 0.075
Ba content Ba content
Fig: 8.9 Lattice parameters as a function of Ba content
Refined l attice pa rameters a nd c ell vol ume, bond a ngle, bond l ength of t his s eries a re
given in table 8.1, 8.2, 8.3 and displayed in fig: 8.9, 8.11, 8.12, 8.13 and 8.14. T he fig:
8.8 and 8.10 show the Reitveld refinement diagram from XRD spectra with considering
single pha se and doubl e pha se ( Mn3O4). In t hese f igures, t he s ymbols i ndicate t he
experimental results, the black solid line shows the fit, the vertical green lines show the
Bragg pos itons of t he s tandard, and t he bl ue l ine a t t he bot tom s hows t he di fference
197 | P a g e
between the experimental results and the fit. In order to track the crystallographic changes
caused by the Ca/Ba exchange, selected parameters, such as lattice constants and atomic
positions, w ere a llowed t o va ry dur ing r efinement. The f ig.8.12 indicates bond a ngle
increases w ith increasing Barium con tents a nd t he f ig 8.13, 8.14 indicate bond l ength
decreases w ith increasing l ead contents. The M nO6 octahedra ar e t ilted and rotated and
the deviations from the ideal 180° Mn–O–Mn bond angles of the parent cubic perovskite
structure ar e evi dent. The l argest t ilt ang les ( and therefore s mallest M n–O–Mn bond
angles) are seen for the Pbnm compounds. With respect to the crystallographic properties,
Fig: 8.10 O bserved (star) and calculated (solid line) X -ray di ffraction pattern for
La0.7(Ca1-xBax)0.3MnO3 (with considering double phase Mn3O4) series.
198 | P a g e
Fig: 8.10 Observed (star) and calculated (solid line) X -ray di ffraction pattern for
La0.7(Ca1-xBax)0.3MnO3 (with considering double phase Mn3O4) series
199 | P a g e
234.8
234.4
Unit cell Volume (Å)3

234.0
233.6
233.2
232.8
0.000 0.025 0.050 0.075
Ba content
Fig: 8.11 Unit cell Volume as a function of Ba content
170
165
Bond angle(deg.)
160
155
150
145
0.000 0.025 0.050 0.075
Ba content
Fig: 8.12 Bond angle as a function of Ba content
1.977
1.974
Bond length(Mn-OP) (Å)
1.971
1.968
1.965
1.962
1.959
0.000 0.025 0.050 0.075
Ba content
Fig: 8.13 Bond length (Mn-OP) as a function of Ba content
200 | P a g e
1.9900
1.9875
Bond length(Mn-Oa) (Å)
1.9850
1.9825
1.9800
0.000 0.025 0.050 0.075

Ba content
Fig: 8.14 Bond length (Mn-Oa) as a function of Ba content
the principal difference among the members of the La0.7 (Ca1-x Bax)0.3MnO3 series is the
mean i onic r adius <rA> of t he A -site c ations ( La, C a, a nd B a). T he m ean i onic r adius
2+
increases systematically with increasing x due to the difference in ionic radii of Ca and
2+
Ba (cf. T able 2.1) . This s uggests t hat <rA> is the e ssential s tructural pa rameter
responsible for the change of the Mn–O–Mn bond angle. The figure 8.11 and 8.15 s how
that the volume and tolerance factor are increased with increasing Ba content.
Table-8.1 Lattice Parameters (From Single Phase)

Ba Content (x) Lattice P arameter Lattice P arameter Lattice P arameter
a(Å) b(Å) c(Å)
0.00 5.4934 5.4786 7.7425
0.05 5.5047 5.4802 7.7458
0.10 5.5055 5.4838 7.7506
0.15 5.5062 5.4857 7.7553
0.20 5.5069 5.4874 7.7584
0.25 5.5078 5.4883 7.7607
201 | P a g e
0.879
Tolerance factor Ba seriesl
0.876
0.873
0.870
0.000 0.025 0.050 0.075
Ba content
Fig: 8.15 Tolerance factor as a function of Ba content
Table-8.2 Unit cell Volume, Transition temperature, Tolerance factor

Transition Tolerance Factor Ionic Radius
Ba content (x) Volume temperature (K) of A-site (Å)
(Å)3
0.00 233.019 252 0.8702 1.1512
0.05 233.645 205 0.8719 1.1583
0.10 233.999 157 0.8738 1.1653
0.15 234.282 160 0.8757 1.1724
0.20 234.448 162 0.8775 1.1794
0.25 234.594 164 0.8794 1.1865
Table- 8.3 Bond angle and Bond length

Ba content (x) Bond angle (deg.) Bond length (Mn-OP) (Å) Bond length (Mn-Oa) (Å)
0.00 147.97 1.9768 1.9448
0.05 153.52 1.9753 1.9884
0.10 157.45 1.9723 1.9868
0.15 160.78 1.9686 1.9845
0.20 165.58 1.9642 1.9826
0.25 169.44 1.9598 1.9805
202 | P a g e
1.1850
Ba series
Ionic radius of A-site (Å)
1.1775
1.1700
1.1625
1.1550
0.000 0.025 0.050 0.075
Ba content
Fig: 8.16 Ionic radius as a function of Ba content
210
200
Ba series
190
180
170
160
0.8975 0.9000 0.9025 0.9050 0.9075

Tolerance factor
Fig: 8.17 Transition temperatures as a function of Tolerance factor
8.6 Magnetic Measurements

8.6.1 The Hysteresis Loop of LCBMO series
The f ig. 8.1 8 and 8.1 9, 8.20, 8.21 present t he t ypical f ield dependencies of t he
magnetization of LCBMO series and for x=0.1, 0.2, and 0.25 respectively. It appears that
a s pontaneous m agnetization pr evails a t 10 K. T he s pontaneous m agnetization M0
obtained by a l inear ex trapolation of t he 1.81 T f ield a nd t he f igure di splays ve ry l ow
coercivity and remanence. The r esults f or t he s amples of t he s eries LCBMO, were
203 | P a g e
displayed in table 8.4. It is clear that ferromagnetism and anti ferromagnetism coexist at
very low temperature.
90 x=0.10
x=0.20
Magnetization (emu/g) 60 x=0.25
30
-30
T=10 K
-60
-90
-16000 -8000 0 8000 16000
Magnetic Field (Oe)
Fig: 8.18 Hysteresis loop of LCBMO series
x=0.10
50
25
-25 T=10 K
-50
-900 -600 -300 0 300 600 900

Magnetic Field (Oe)
Fig: 8.19 Hysteresis loop of La0.7Ca0.27Ba0.03MnO3 sample
60
40
X=0.15
20
-20
T=10 K
-40
-60
-900 -600 -300 0 300 600 900
Magnetic Field (Oe)

204 | P a g e
40
x=0.25
20
-20
T=10 K
-40
-900 -600 -300 0 300 600 900
Magnetic Field (Oe)
Table-8.4 Saturation Magnetization, Bohr Magneton (µB) Coercivity, and Remanence

Ba Saturation Bohr Magneton Applied Coercivity Remanence
Contents Magnetization (µB /f.u.) Magnetic (Oe) at (emu/g)
(x) (emu/g) Field (Oe) 1000 Oe at 1000 Oe
0.00 77 2.92 1.81*104 26.96 0.68
0.05 80 3.1 1.81*104 22.67 1.88
0.10 88 1.81*104 22.70 1.05
0.15 84.6 1.81*104 31.91 1.51
0.20 86.5 1.81*104 11.20 0.65
0.25 85.2 3.2 1.81*104 14.51 1.02
8.6.2 The Thermo-Magnetic FC and ZFC curves of the LCBMO series

For the some samples (x= 0.05, 0.15, 0.25) ZFC curve and for all samples (x=0.00, 0.05,
0.1, 0.15, 0.20, 0.25) of the series LCBMO, FC/ZFC magnetization measurements were
performed in a magnetic field of 50 Oe and the results were displayed in fig: 8.22 and fig:
8.23. F rom t hese t hermo-magnetic cur ves, the f erromagnetic [ 25-29] t o pa ramagnetic
transition temperature, TC can be de termined. T he C urie t emperature cha nges w ith
increasing the Ba contents in the samples from 252 K (x= 0.00) to 205 K (x=0.05). This
tendency does not support the universality of the notion that substitution of Ba content in
205 | P a g e
LCMO s ystem will a lways enhance the C urie te mperature T c (x). It c an intend t hat t he
substitution of Ba2+ for C a2+ induces a m ixed valence s tate of M n3+/Mn4+ and enhances
the ferromagnetic transition temperature due to double exchange interaction. Because of
large Ba2+ ions in the samples, the increase of Ba2+ content substituted for Ca2+ ion leads
to an increasing in the average radius of the A- sites cation <rA> (Fig.8.25). The fig: 8.24
and t he f ig: 8.2 6 show t he va riation of C urie t emperarture w ith B a contents and bond
angle. Increasing t he r adius <r A> causes an increase i n the i nternal p ressure, which
decreases t he buc kling of t he M nO6 octahedral a nd t hen t he T c enhances [ 30-33].The
decreasing of magnetization on Z FC curve in low temperature range indicated that there
is short – range magnetic order [34-38] in the studied samples. The maximum will be the
result of t he c ompetition be tween t he ( local) a nisotropy ( decreasing with i ncreasing
temperature, s o allowing an i ncreasing m agnetization) and t he decrease of t he m agnetic
order w hen C urie t emperature i s a pproached. In a ddition, t he r ole of g rains a nd g rain
boundaries could be another reason of such phenomena. At grain boundary, the exchange
interaction (SE and DE) are weak compared to those inside the grain [39-41]. This leads
to t he i nhomogeneity of m agnitude of e xchange i nteraction. From t hese F C a nd ZFC
curve w e can correlate T r, T f and T C and w e c an e xplain t he s imilar c omposition
dependence to that of Curie temperature TC for the studied samples.
3.0
2.5 H=20 Oe
2.0
1.5
1.0
x=0.05
x=0.15
0.5 x=0.25
0.0
75 150 225
Temperature (K)
Fig: 8.22 The thermo-magnetic zero field cooled curves of the LCBMO series
206 | P a g e
4.50 x=0.00
x=0.05
x=0.10
3.75 x=0.15
x=0.20
x=0.25
3.00
2.25
1.50
0.75
H=50 Oe
0.00
75 150 225 300
Temperature (K)
Fig: 8.23 The thermo-magnetic field cooled (FC) and zero – field – cooled (ZFC) curves
of the LCBMO series
210
200
190
180
170
160
150
0.025 0.050 0.075
Ba content
Fig: 8.24 Curie temperatures as a function of Ba content
At hi gher t emperatures, t he F M i s br oadened l eading t o i ncreasing of m agnetization i n

ZFC curve. This phase separation phenomenon is the intrinsic feature of perovskite – type
manganites [ 42-44] a nd w as e xperimentally obs erved i n va rious m anganites a s w ell a s
affirmed by the theoretical studies.
207 | P a g e
210

200
190
180
170
160
150
1.160 1.165 1.170 1.175 1.180 1.185
Ionic Radius of A-site (Å)
Fig: 8.25 Curie temperatures as a function of Ionic Radius of A-site
210
Ba series
200
190
180
170
160
155 160 165 170

Bond Angle(θ°)
Fig: 8.26 Curie temperatures as a function of Bond Angle
8.6.3 Arrot Plot from M-H Curves

5500
La0.7Ca0.285Ba0.015MnO3
4950
M2(emu/g)2
4400
T=207K
3850
450 525 600 675 750 825

H/M (Oe-g)/emu
Fig: 8.27 Arrot-plot from (M-H) curve for the sample x=0.05
208 | P a g e
From the Arrot plot the transition temperatures have also been calculated and it has been
found that the Curie temperature from both measurements is nearly same.
4500
La0.7Ca0.255Ba0.045MnO3
3750
3000
M2(emu/g)2
T=158K
2250
1500
750
600 900 1200 1500

H/M (Oe-g)/emu
La0.7Ca0.225Ba0.075MnO3
6000
5000
M2(emu/g)2
T=1620K
4000
3000
375 500 625 750 875

H/M (Oe-g)/emu
209 | P a g e
Table-8.5 Transition Temperature by different processes
Ba content (x) TC (K) from TC (K) from A rrot TC (K) from Arrot
FC/ZFC graph plot (H=5T) plot (H=2T)
0.00 252
0.05 207 207 205
0.10 168
0.15 160 158 158
0.20 162
0.25 164 162 161
8.7 AC Susceptibility of LCBMO series

Spin-glass be havior i s usually ch aracterized by AC s usceptibility. In a s pin glass,
magnetic spins experience random interactions with other magnetic spins, resulting a state
that is highly irreversible. The spin glass state is realized below the freezing temperature.
Study of the magnetic moment in an alternating magnetic field (AC) and measuring the
susceptibility of the samples will provide the information on t he atomic moments of the
compounds i n t he s amples. T he m agnetic susceptibility o f La0.7(Ca1-xBax)o.3MnO3
(x= 0.05, 0.10, 0.15, 0.2 5) samples was measured for different frequencies of 17 H z, 51
Hz, 170Hz and 510 Hz at ac excitation field of 2 Oe and the results are shown in figures
8.30, 8.3 1, 8.3 2, 8.3 3, 8.3 4, 8.3 5, 8.3 6 a nd 8.37 for x = 0.05, 0.10 , 0.15 a nd 0.25
respectively. The f reezing t emperature i s de termined by m easuring χ` vs temperature, a
curve which reveals a cusp at the freezing temperature. These frequencies were kept fixed
for the other compositions as well as for comparison purposes. All the samples showed a
peak in the r eal p art of the ac s usceptibility, which indicates a tr ansition from a
paramagnetic s tate to a f erromagnetic, antiferromagnetic or s pin glass s tate. The
irreversibility in spin-glass leads to a non zero out of phase, below the spinglass freezing
temperature. There is a peak in the real part of the ac susceptibility and the peak position
shifts towards high temperature as a result of increased fequency, which indicates a spin
glass s tate at a t emperature a round 150 K. It can be s een al so that t he m áximum ac
susceptibility de creases w ith increasing frequency. C lose ex amination of t he above
figures reveals that the variation in the peak susceptibility values with frequency falls in
an exponential manner.
210 | P a g e
0.045
HAC=2 Oe
χ' (emu/g-oe)
0.030
B
51Hz
170Hz
510Hz
0.015
La0.7Ca0.285Ba0.015MnO3
0.000
50 100 150 200
Temperature (K)
Fig: 8.30 The temperature dependence AC susceptibility (real part) for x=0.05 measured
at different AC frequencies.
2.0x10-4
17 Hz
51 Hz HAC=2 Oe
170 Hz
1.5x10-4 510 Hz
χ"(emu/g-Oe)
La0.7Ca0.285Ba0.015MnO3
1.0x10-4
5.0x10-5
180 190 200 210 220

Temperature (K)
Fig: 8.31 The t emperature de pendence A C s usceptibility (imaginary part) f or x = 0.05
measured at different AC frequencies.
211 | P a g e
0.060
0.045
χ'(emu/g-Oe)
17Hz
51Hz
0.030 170Hz
510Hz
HAC=2 Oe
0.015
La0.7Ca0.27Ba0.03MnO3
0.000
50 75 100 125 150 175
Temperature (K)
1.2x10-3
La0.7Ca0.27Ba0.03MnO3
-3
1.0x10
HAC=2 Oe
-4 17Hz
8.0x10
51Hz
χ"(emu/g-Oe)
170Hz
510Hz
6.0x10-4
4.0x10-4
2.0x10-4
0.0
40 60 80 100 120 140 160
Temperature (k)
Fig: 8.33 The t emperature de pendence A C s usceptibility (imaginary part) for x = 0.10
212 | P a g e
0.0400
HAC=2 Oe
0.0375
17Hz
χ'(emu/g-Oe)
51Hz
170Hz
0.0350 510Hz
0.0325
La0.7Ca0.255Ba0.045MnO3
50 75 100 125 150

Temperature (K)
La0.7Ca0.255Ba0.045MnO3
4.0x10-4
HAC=2 Oe
3.0x10-4
χ"(emu/g-Oe)
17Hz
51Hz
2.0x10-4 170Hz
510Hz
1.0x10-4
0.0
50 75 100 125 150
Temperature (K)
213 | P a g e
0.045
χ' (emu/g-Oe)
0.030
La0.7Ca0.225Ba0.075MnO3
17Hz
0.015 51Hz
170Hz
510Hz HAC=2 Oe
0.000
50 75 100 125 150 175
Temperature (K)
Fig: 8.36 The t emperature de pendence A C s usceptibility (real p art) for x = 0.25
0.0010
La0.7Ca0.225Ba0.075MnO3
0.0008
HAC=2 Oe 17Hz
51Hz
170Hz
χ"(emu/g-Oe)
0.0006 510Hz
0.0004
0.0002
0.0000
50 75 100 125 150
Temperature (K)
214 | P a g e
8.8 Magnetic Isotherm of LCBMO series and Magnetic Entropy Measurements
The M(H) i sotherms h ave be en m easured f or t he s amples ( x= 0.05, 0.15,0.25) of
La0.7 ( C a1-x Bax )o.3 Mn O3 series i nvestigated at va rious t emperatures i n a na rrow
temperature interval around the respective Curie temperatures, in magnetic field up to 50
k Oe . The fig: 8.38, 8.40, and 8.42 show the set of isothermal M(H) curves of perovskite
La0.7 ( Ca1-x Bax )o.3 Mn O 3 (x= 0.05, 0.15, 0.25 ) . From these M (H) curves measured
around T c, t he |Δ Sm|(T) de pendence h as be en determined according t o t he f ollowing
equation [45-49]
( M n − M n+1 ) H
=∆S ∑ Tn +1 − Tn
∆H n
8.1
and pr esented i n f ig: 8. 39, 8. 41 and 8.4 3. For m agneto-caloric m aterials, the r elative
cooling power (RCP) represents a good way for comparing them and it is defined as
where δ Tfwhm means t he f ull-width at the ha lf ma ximum of the ma gnetic e ntropy
changeand the results were shown in table- 8.6. In fig: 8.39, 8.41 and 8.43 the |Δ Sm|(T)
for the studied samples are plotted as a function of temperature. The maximum magnetic
entropy changes [50-54] |Δ Sm|max, as well as the RCP values for all samples are listed in
table -8.6. |Δ Sm|max has reached higher value of 5.98J/kg K for the composition x= 0.05 it
can be s een from t he t able – 8.6 t hat our s tudied s amples have qui te l arge | Δ Sm|max as
materials w ith giant ma gneto-caloric ef fect ( GMCE) [ 55-59]. A pr omising m aterial f or
application s hould ha ve hi gh R CP a nd t he v alue of T c close t o room t emperature.
Unfortunately, a lthough t he | Δ Sm|max and RCP v alues a re l arge, t he T c for the s amples
x= 0.05 a re qui te l ower t han r oom t emperature. T he dopi ng e ffect m ight s olve t his
disadvantage.
215 | P a g e
75
T=185 K
60
45 T=222 K
30
15
La0.7Ca0.285Ba0.015MnO3
0
0 12000 24000 36000 48000
Magnetic field H (Oe)
Fig: 8.38 Magnetic isotherm of LCBMO series (x=0.05) at 5T
1T
6.0 1.35T
2T
3T
4T
4.5 5T
x=0.05
3.0
1.5
0.0
180 190 200 210 220
Temperature (K)
Fig: 8.39 Magnetic entropy change as a f unction of temperature for the samples x= 0.05
at different applied magnetic fields.
216 | P a g e
T=218 K
La0.7Ca0.255Ba0.045MnO3
60
45
30
T=140 K
15
0
0 12000 24000 36000 48000
Magnetic Field H(Oe)
Fig: 8.40 Magnetic isotherm of LCBMO series (x=0.15) at 5 T
1T
2.5 1.35T
2T
3T
4T
5T
2.0
1.5
1.0
0.5
x=0.15
0.0
140 160 180 200 220
Temperature (K)
Fig: 8.41 Magnetic entropy change as a f unction temperature for the samples x= 0.15 at
different fields
217 | P a g e
90
La0.7Ca0.225Ba0.075MnO3 T=182 K
60
45 T=140 K
30
15
0
0 12000 24000 36000 48000
Magnetic field H (Oe)
Fig: 8.42 Magnetic isotherm of LCBMO series (x=0.25) at 5 T
1T
1.35T
3.75 2T
3T
4T
5T
3.00
2.25
1.50
0.75
150 165 180

Temperature (K)
Fig: 8.43 Magnetic entropy change as a f unction of temperature for the samples x= 0.25
at different applied magnetic fields.
218 | P a g e
Table-8.6 Transition temperature, Magnetic Entropy and RCP of LCBMO series
Sample (x) TC (K) from ZFC curves Δ Smax (J/kgK) RCPmax (J/kg)
0.00 252
0.05 207 5.99(5T)3.92(2T) 58.8(2T)
0.15 159 2.64(5T)1.30(2T) 23.4
0.25 162 5.96(5T)3.43(2T) 28.13(2T)
8.9 Summary
A de tailed study o f th e s tructural, magnetic and the ma gneto-caloric ef fect i n the
La0.7 (Ca1-x Bax)0.3 Mn O3 (x=0.00, 0.05, 0.1, 0.15, 0.2, 0.25) compounds has been studied
extensively. It has be en found t he l arge m agnetic e ntropy c hanges i n t hese s amples.
Among them, the magnetic entropy ch ange r eaches a m aximum value of 5.99 J/kg K at
the applied field of 50 kOe and 3.92 J/kgK at the applied field of 20 kOe respectively for
the La 0.7 Ca0.285 Ba0.015 Mn O 3 sample, associated with the f irst or der ferromagnetic to
paramagnetic transition at 207 K. Though the Curie temperature of this sample is low but
it gives us a suggestion that this material would be a suitable pre-eminent candi date for
the adva nced m agnetic refrigeration technology at l ow t emperature; na mely; a l arger
value of entropy change is expected compared to the polycrystalline samples; and the ∆ s m
distribution i s qui te un iform, w hich i s de sirable f or a n E ricson – cycle ma gnetic
refrigerator. T he l arge magnetic e ntropy change pr oduced b y t he abrupt r eduction of
magnetization is attributed to the strong coupling between spin and lattice in the magnetic
ordering process. Table- 8.7 and the figure 8.44, 8.45, 8.46 show the comperative studies
on magnetocaloric effect for Barium series.
219 | P a g e
4.50
Ba series
3.75

∆H=1T
3.00
(0.015, 2.48)
2.25
1.50
0.75
0.000 0.075 0.150 0.225 0.300

Ba content
Fig: 8.44 Comparative studies on Magnetic entropy as a function of Ba content
4.50
3.75
Ba series
3.00 ∆H=1T
(207, 2.48)
2.25
1.50
0.75
150 200 250 300 350

Temperature (K)
Fig: 8.45 Comparative studies on Magnetic entropy as a function of temperature
220 | P a g e
Table-8.7 Comparative studies on Magneto-Caloric Effect for Barium (Ba) series
Composition Curie Temperature Applied Δ SM Reference
TC (K) Field H (T) (J/kgK)
La2/3Ba1/3MnO3 337 1 2.70 60
La2/3Ba1/3MnO2.98 312 1 2.60 60
La0.67Ba0.33MnO3 292 5 1.48 61
La0.70Ba 0.30MnO3 336 1 1.60 61
La0.70Ca0.18Ba0.12MnO3 298 1 1.85 61
La0.70Ca0.06Ba0.24MnO3 320 1 1.72 61
0
La0.70Ca0.285Ba0.015MnO3 207(TS=1280 C) 5 6.00 Present work
La0.70Ca0.285Ba0.015MnO3 207(TS=12800C) 4 5.31 Present work
La0.70Ca0.285Ba0.015MnO3 207 (TS=12800C) 3 4.77 Present work
La0.70Ca0.285Ba0.015MnO3 207(TS=12800C) 1.35 3.21 Present work
0
La0.70Ca0.255Ba0.045MnO3 162(TS=1280 C) 1.35 0.96 Present work
La0.70Ca0.225Ba0.075MnO3 164(TS=12800C) 1.35 1.33 Present work
221 | P a g e
/kgK)
4 ∆H=1T
Magnetic entropy (J
(0.015, 207,2.48)
3
1
350
0.000 300 (K)
0.075 250 ure
Ba0.1500.225 200 erat
con p
ten 0.300 150 Tem
t
Fig: 8.46 Comparative studies on Magnetic entropy as a function of Ba content and Curie
temperature
222 | P a g e
References
[8.1] N icola, A ., S paldin a nd M anfred Fiebig, “ The R enaissance of Magnetoeletric
Multiferroics” Science, 309 (2005) 392
[8.2] M . F iebig, “ Magneto-electric di agnostic o f pr essure relaxations i n s tructure of
temperature –influenced Yttrium iron garnets J. Phys. D: Appl. Phys. 38 (2005) R123-
R152
[8.3] Z ener, C ., “Study on t he m agnetic s tructure i n l ightly dope d manganese ox ides”,
Phys. Rev., 81, (1951) 440,
[8.4] Zener, C ., “Giant magnetoresistance of m anganese ox ides w ith layered perovskite
structure”, Phys. Rev., 82, (1951) 403,
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226 | P a g e
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[8.60]. M.H. Phan, S.C. Yu, Y.M.Moon, N.H. Hur, “Dependence of the magneto caloric
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monovalent doping La0.7Ba0.2M0.1MnO3 (M=Na, Ag, k) manganites”, J. Magn.Magn.
Mater. 256 (2003) 306
227 | P a g e
Chapter Nine Conclusions
9.1 Conclusions
Through s tructural a nd thermomagnetic s tudies, La0.7(Ca1-xMx)0.3MnO3 (M=Pb, Sr,
Ba) samples have been identified as potential candidates for magnetic refrigeration. The
lanthanide gadolinium ( Gd) i s c onsidered as the pr ototype material f or ma gnetic
refrigeration at ambient conditions because it exhibited substantial magneto-caloric effect
near room temperature.
Considering t he m aximum m agnetic e ntropy change, t he v alues obt ained f or t he

L0.7(Ca1-xSrx)0.3MnO3 samples w ith x = 0.25 are i ndeed competitive w ith t hat of
gadolinium based materials. For the x = 0 sample, the maximum magnetic entropy change
has exceeded the ma ximum |Δ SM(T)Δ H| value of gadolinium. H owever, t he Curie
temperature is not hi gh enough t o b e c onsidered a s a pr omising m aterial f or m agneto-

caloric use. The samples with x = 0.25 has shown a maximum magnetic entropy change
and Curie temperature (Benford and Brown, 1981) [9.1] which are close to the values for
gadolinium based materials. Apart f rom t he m aximum m agnetic ent ropy change t he
width of the Δ SM(T)Δ H peak has also increased, which is considered to be a very important
parameter for magnetic refrigeration (Brown, 1976) [9.2], (Pecharsky and Gschneidner,
Jr., 1999) [ 9.3], ( Bohigas a nd co-workers, 2000) [ 9.4] as r egards t o relative cool ing
power. Like all conventional cooling devices, the purpose of a magnetic refrigerator is to
transfer he at from a cold reservoir (the heat load) to a hot reservoir (the heat sink). The
cooling power of a magnetic refrigerant can be defined as the amount of heat, which the
material is capable of absorbing from the heat load and subsequently rejecting to the heat
sink in a single thermodynamic cooling cycle.
According to the e mpirical r elation between the c omposition parameter x , and the
corresponding Curie t emperature TC derived i n t he pr evious c hapters, the c ompounds
with c omposition L a0.7Ca0.225Sr0.075MnO3 and L a0.7Ca0.225Pb0.075MnO3 have the Curie
temperature of 293 K and 291 K respectively which is comparable to that of gadolinium
(Tegus et al., 2002) [9.5]. According to figures 7.27 and 6.41 our studied materials exhibit
a maximum magnetic entropy change of 5 J /kg.K and 3.47 J /kg.K at 1.35 T esla and at 2
Tesla respectively which is almost equivalent to the maximum magnetic entropy change
of gadolinium and other materials (Hu et al., 2001) [9.6]. Therefore it might be claimed to
228 | P a g e
have found a suitable m aterial for magnetic r efrigeration which could be less ex pensive
and be available for commercial use. The FWHM of the magneto-caloric peak have been
approximated to be 28 K and 23 K respectively. So these compounds could be considered
as the possible candidates in future for magnetic refrigeration technology.
Results on s tructural, magnetic, and m agnetocaloric properties of three series of C a and
Pb, C a and S r, C a and Ba doped l anthanum m anganites, La0.7(Ca1-xMx)0.3MnO3 (M=Pb,
Sr, Ba x=0.00, 0.05, 0.10, 0.15, 0.20, 0.25) have been presented and discussed. Elemental
analysis s howed a r easonable agreement b etween nom inal and actual s ample
compositions, although t he ox ygen s toichiometry m ight not be i deal. The grain s izes of
the al l t he s tudied samples ha ve changed and the s amples became m ore por ous w ith
increasing Pb, Sr and Ba content.
The s amples w ere observed t o b e single ph ase pe rovskites as revealed through the
structural analysis. The variation of the Ca/Pb, Ca/Sr and Ca/Ba ratios caused significant
structural changes. A transition from Cubic to orthorhombic (Pbnm) symmetry occurred
for all compositions. The Mn–O bond distance was found to be decreased with increasing
doping content whereas the mean Mn–O–Mn bond angle increased systematically with x.
2+
This was ascribed to the size mismatch between the divalent A-site ions (Ca and Pb2+,
Ca2+ and S r2+, C a2+ and B a2+) and t he s pace between t he ox ygen octahedra, where t hey
reside. The s ize m ismatch decreased with increasing P b, Sr and B a co ntent and the
Mn–O–Mn bond angle approached the ideal 180°.
The s amples i n P b a nd S r s eries s howed di stinct m agneto-caloric pe aks a round t heir

respective Curie temperature 291K and 293K respectively and the samples with Ba doped
manganite showed a high value of magnetic entropy at very low temperature. Maximum
|• SM(T)• H | values w ere not c ompared us ing r esults of magnetic heat cap acity
measurements. There is a es tablished model f or t he m agneto-caloric ef fect w hich

provided r easonable predictions f or t he magneto-caloric pr operties of the
La0.7Ca0.225Pb0.075MnO3 and La0.7Ca0.225Sr0.075MnO3 samples. The respective compounds
showed a m agneto-caloric e ffect c omparable t o t hat of g adolinium, w hich i s us ually,
suggested as w orking m aterial f or m agnetic r efrigeration near room t emperature. The
magnetic ent ropy change obs erved for t he t wo s amples ex ceeded the v alue of m agnetic
entropy c hange found in g adolinium. L a0.7Ca0.225Pb0.075MnO3 and
La0.7Ca0.225Sr0.075MnO3 samples (with a fairly low Pb and Sr content) thus seem to be a
229 | P a g e
suitable candi date as working substance in future magnetic cooling technology operable
near room t emperature. The s amples w ith low substitutions of Pb a nd S r c ontents have
shown distinct metal-insulator transitions below the Curie point, which could be ascribed
to the increasing local spin disorder associated with the cross-over from the ferromagnetic
to the paramagnetic state.
The va riation of di fferent pa rameters, namely t he C a/Pb, Ca/Sr and Ca/Ba r atios of t he
mixed-valence l anthanum m anganite s eries ha ve revealed a w ide r ange of i nteresting
physical phenomena. It has also demonstrated a strategy for tailoring working substances
for s pecific t echnological applications. Hopefully future work will be carried out t o test
the performance of the fascinating materials in real devices.
230 | P a g e
References
[9.1] B enford, S .M. a nd G .V. B rown, “ T-S d iagram of gadolinium ne ar t he C urie
temperature”, J.Appl. Phys. 52(3) (1981), 2110-2112
[9.2] Brown, G.V., “Magnetic heat pumping near room temperature”, J. Appl.Phys. 47(8),
(1976), 3676-3680
[9.3] P echarsky, V .K. a nd K .A. G schneidner, J r., “ Magnetocaloric e ffect a nd m agnetic
refrigeration”, J. Magn. Magn. Mater., 200, (19990, 44-56
[9.4] B ohigas, X ., E . M olins, A .Roig., J. T ejada a nd X .X. Z hang, “ Room t emperature
magnetic refrigerator us ing p ermanent m agnets”, IEEE T rans. M ag. 36( 3), ( 2000),
538-544
[9.5] Tegus, O., E. Bruck, K.H.J. Buschow and F.R. De Boer, “Transitional metal-based
magnetic refrigerants for room-temperature applications”, Nature, 415, ( 2002), 150-
152
[9.6] H u, F ., B . S hen, J . S un a nd Z. C heng, “ Large m agnetic entropy change i n
La(Fe,Co)11.83Al1.17”, Phys. Rev. B, 64, (2001), 012409-1-012409-3
231 | P a g e
Appendix A: The basics of the Rietveld Refinement Technique
The starting point for Rietveld was two observations. The first, which he did during his
work with neutron data at Patten was, that a Bragg reflection was a Gaussian or what we
call a normal distribution curve and could easily be described with the formula
1 1 x -µ 2
e
− ( )
f(x) = 2 σ
σ 2π
A.1
where µ is the mean value and σ is the standard deviation .
The s econd obs ervation w as m ade l ong b efore b y an Italian s cientist G . Cagliotti w ho
found t hat t he width of a Bragg r eflection va ried w ith t he θ-angle but al so was v ery
much de pendent on t he i nstrument a nd t he b eam de sign. H owever t he ha lf w idth c ould
satisfactorily be described with the formula
H2 = U tan2 θ + V tan θ +W A.2
Where H is the full width at half height, θ is the Bragg angle and U, V, W are constants
which depend on the instrument design.
Fig: A.1 Rietveld’s fit of a Gaussian with FWHM and Cagliottis fit of the halfwidth at
different 2θ angles.
This appendix gives a brief introduction to the Rietveld technique [1,2]. The basis of the
Rietveld method is the equation
y ic = y ib + ∑ Gik I k A.3
k
where yic is the calculated intensity at the i’th point of the pattern, yib is the background
intensity, Gik is a normalized peak profile function, and Ik is the intensity of the k’th Bragg
232 | P a g e
reflection. The sum runs over all reflections contributing intensity to point i. The intensity
Ik is given by the expression
2
I k = SM k Lk Fk Pk Ak E k A.4
where S is the scale factor, Mk is the multiplicity, Lk is the Lorentz-polarization factor,
Fk is the structure factor, Pk is a f actor describing the effects of preferred orientation (for
powders unaffected by preferred orientation Pk = 1), Ak is the absorption correction and Ek
an extinction correction factor. The structure factor is given by

n
Fk = ∑ f j e
2πi ( hkt r j − hkt B j hk )
A.5
j =1
where fj the scattering factor of the j’th atom and hk, rj and Bj are matrices representing the
Miller i ndices, a tomic c oordinates and a nisotropic t hermal vi bration pa rameters,

respectively. The superscript t indicates matrix transposition and the sum runs over the n
atoms of a unit cell.
Various choices can be made for the peak profile function, Gik. In the present analysis the
Pseudo-Voight profile, which constitutes a simple convolution between a Gaussian and a

Lorentzian profile, was used. It is given by the expression
2 2 ln 2 −4 ln 2 X ikk
Gik = γ (1 + 4 X ik2 ) + (1 − γ ) e A.6
H kπ Hk π
-1
where Hk is the width (FWHM) of the k’th Bragg reflection, Xik = (2θ i-2θ k))Hk , and γ is
the “m ixing” pa rameter, w hich determines t he d egree o f “ Lorentzianess” of t he pr ofile.

The variation of the peak width is defined by the function
H k = U tan 2 θ + V tan θ + W A.7

where U, V, a nd W are refineable pa rameters, which in a non -trivial w ay d escribes the
line broadening due to s tress, strain, particle size, etc. The positions of the Bragg peaks
are de termined the s et of cel l di mensions, i n conjunction with a z ero parameter and t he
wavelength (diffractometer constants) p rovided. The goal of a R ietveld refinement is to
minimize the deviation between the calculated x-ray pattern and the observed pattern, i.e.
to minimize the quantity
R = ∑ wi ( y io − y ic ) 2 A.8
i
233 | P a g e
where yio is t he s et of obs erved di ffraction i ntensities, yic is the c alculated intensities
obtained from Equation (A.3), and wi is the weight assigned to the i’th observation (based
on the counting statistics). R can be minimized employing a conventional minimization

method, s uch a s t he Newton-Raphson a lgorithm [3]. The r eal di fficulty lie s in
establishing t he m odel f or t he c alculation a nd i n c hoosing w hich pa rameters s hould be
fixed a nd w hich s hould be a llowed t o va ry dur ing minimization. It is us ually e asy to
obtain a good fit by introducing many degrees of freedom, but far more difficult to extract
relevant physical information from the fit.
234 | P a g e
References
[A.1] R.A., “The Rietveld Method”, Oxford University Press, (1995)
[A.2] Rietveld, H.M., “Aprofile refinement method for nuclear and magnetic structures”,
J.Appl.Chys. 2(2), (1969) 65-71
[A.3] Press, W .H., S .A.Teukolsky, W .T. V etterling a nd B.P. F lannery, “ Numerical
Recipes in Fortran (2nd edition)”, New York: Cambridge University press, (1992)
235 | P a g e
Publications
i. Giant ma gneto-caloric e ffect around room t emperature at m oderate l ow f ield

variation i n La0.7(Ca1-xSrx)0.3MnO3 perovskite, M.S. Islam, D .T. H anh, F .A.
Khan, M.A. Hakim D.L. Minh, N.N.Hoang, N.H. Hai, N. Chau, Physica B, 404,
2495-2498 (2009)
ii. Resistivity A nomaly A ssociated with Magnetic P hase T ransition in
Co80-xFexB10Si10 and N i80-xFexB20, M.S. Islam, and M .A.Asgar, N uclear Science
and Applications, 16(2), 1-5 (2007)
iii. Large m agneto-caloric e ffect a round room t emperature i n La0.7Ca0.3-xPbxMnO3
perovskite, D .T. H anh, M.S. Islam, F.A. K han, D .L.Minh, N .Chau, J ournal of
Magnetism and Magnetic Materials. 310, 2, 2826-2828, (2006)
iv. Magnetic P hase T ransition in Ni-Mo A lloys, M.S. Islam, F.A. K han, N . C hau,
M.A. Asgar, Journal of Bangladesh Physical Society., 2(1), 91-97, (2006)
v. Temperature de pendence of s aturation m agnetostriction of a morphous ribbons
having c omposition C o80-xFexB10Si10 with x = 2, 4, 6, 8 , M.S. Islam and
M.A.Asgar, Journal of Bangladesh Academy Sciences, 30(1), 95-99, (2006)
vi. Determination of Critical Exponents of Amorphous Ribbons with Co80-xFexB10Si10
and N i80-xFexB20 from T emperature and M agnetic F ield Dependence of
Magnetization, M.S. Islam, S .S. S ikder, M .A.Asgar, N uclear S cience a nd
Applications, 15(1), 39-43 (2006)
vii. Magnetic P roperties a nd Magneto-caloric E ffect i n La0.7(Ca1-xBax)0.3MnO3
Perovskites, M.S. Islam, T .D. H iep, M A H akim, F A K han, D L M inh, N .
Chau, J.Magn.Magn. Mater. (Communicated)
viii. Structure, Magnetic and Magnetocaloric P roperties of
La0.7(Ca1-xBax)0.3MnO3 Perovskite m anganites, M.S. Islam, N.H. Hai,
M.A.Hakim, F.A.Khan, D.L.Minh, N.Chau, Physica B, (Communicated)
236 | P a g e
Conference Proceedings
1. Magnetic P hase T ransition in Ni-Mo A lloys. 9th International C onference of

Physics, M.S. Islam, F.A. K han, N . C hau, M .A. A sgar, N ational U niversity of
Science and Technology, Hanoi, Vietnam, 22-24th November, 2005.
2. Giant ma gneto-caloric e ffect around room t emperature at m oderate l ow f ield
variation i n La0.7(Ca1-xSrx)0.3MnO3 perovskite, M.S. Islam, D .T. H anh, F .A.
Khan, D .L. M inh, N .H. H ai, N . C hau, P roceedings of t he 1 st IWOSM – 3rd
IWONN Conference, Halong Bay, Vietnam, 6-9th December, 2006.
3. Magnetic Phase Transition and Magnetocaloric Effect around room temperature in
La0.7(Ca1-xSrx)0.3MnO3 perovskites, M.S. Islam, D.T. H anh, A .Z.Ahmed,
M.A.Hakim, F .A. K han, D .L. M inh, N .H.Hai, N .Chau, B ose C onference on
Contemporary Physics-08, Dhaka University, Dhaka, Bangladesh, 19-21st March,
2008
4. Magnetic P roperties a nd Magneto-caloric E ffect i n La0.7(Ca1-xBax)0.3MnO3
Perovskites, M S. Islam, M Hudl, M A Hakim, F A Khan, D L Minh, N Chau, P
Nordblad, 3rd International Conference on Structure, Processing and Properties of
Materials, SPPM-2010, Dhaka, Bangladesh, 24-26 February 2010.
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Perovskite m anganites, M.S. Islam, M atthias Hudl, R . M athieu, M .A.Hakim,
F.A.Khan, D .L.Minh, N.Chau, P er N ordblad, International C onference on
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3-7 March 2010.
237 | P a g e

Studies of Structural and The Giant Magneto-Caloric Effect of Some Manganites Perovskite

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Studies of Structural and The Giant Magneto-Caloric Effect of Some Manganites Perovskite

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STUDIES OF STRUCTURAL AND THE GIANT

MAGNETO-CALORIC EFFECT OF SOME MANGANITES

MUHAMMED SHAFIQUL ISLAM

Signature of the Candidate

MUHAMMED SHAFIQUL ISLAM

Chapter One Motivation and Structure of this thesis

Chapter Two General Introduction

Chapter Three Literature Review

3.4.2.2.1 (La 1-x Ca x )MnO 3 42

Chapter Four Theoretical Aspects of the Magneto-Caloric Effect

Chapter Five Preparation of Manganites Perovskite and Experimental

Chapter Six Study of La 0.7 (Ca 1-x Pb x ) 0.3 MnO 3 perovskite

6.1 Introduction 101

6.7 Relationship between Structure and Magnetism 128

Chapter Seven Study of La 0.7 (Ca 1-x Sr x ) 0.3 MnO 3 perovskite

Chapter Eight Study of La 0.7 (Ca 1-x Ba x ) 0.3 MnO 3 perovskite

Chapter Nine Conclusions

Appendix A: The basics of the Rietveld Refinement Technique 231

Conference Proceedings 236

I w ould l ike t o pa y my r egards t o Prof Nguyen Chau, E x-Director C MS, V ietnam f or hi s he lp a nd

I a m gr ateful t o t he c oncerned a uthority of E ducation Ministry, G ovt. of t he Peoples R epublic of

Muhammed Shafiqul Islam

MUHAMMED SHAFIQUL ISLAM

One of t he v ery i mportant pr omising a pproaches t o t he design of nove l ma terials tha t

1. A brief introduction on manganite perovskites is explained in chapter two.

2. Starting f rom a l iterature r eview of t he r elevant books , j ournals a nd c onference

3. The theoretical aspects of m agnetocaloric ef fect ar e br iefly described in cha pter

4. The method o f s ample’s pr eparation i s de scribed br iefly i n c hapter f ive. All

5. The r esults of the measurements, obs ervations a nd a nalysis on t he p repared

[1.2] P.W. A nderson, H. H asegawa, “ Considerations on doubl e e xchange”, P hys. R ev.

[1.3] P.M. R accah and J.B. G oodenough, “ A l ocalized-electron t o collective-electron

[1.5] John B . G oodenough, “ An i nterpretation of t he m agnetic pr operties of t he

Fig: 2.1 (a) R esistivity, ( b) M agneto resistance i n 0.3 T a nd ( c) M agnetization of a

Besides m anganese, many perovskites-structure o xides form with aluminum, gallium or

Fig: 2.4 low-temperature ma gnetic mode s (letters) a nd f erromagnetic moment f or the

They calculated the transfer integral t to be

These e igen s tates c orrespond t o t he s ymmetric and a ntisymmetric combinations of t he

2.2 Crystal and Electronic Structure

A-site(nm) B-Site(nm) O-site(nm)

Table-2.1 s hows i onic radii us ed f or c alculation of t olerance f actors of l anthanum

The m onovalent A c ations ha ve a na rrow range of s olid s olubility i n t he r are e arth

The sequence of phases, O` O R, C, found on increasing the Mn4+ content by A-site

For M n3+ in oc tahedral coordination t he g round s tate i s 5

In L aMnO 3 films, t wo a bsorption ba nds a ppear, namely a s trong ba nd at 1.8 e V a nd a

2.2.3 Electronic Structure

Transitions – metal ox ides ar e m aterials w hose electronic p roperties are de termined by

(La 1-x Ca x )MnO 3

MR ha s l ong be en e mployed t o c ooling be low 1K us ing pa ramagnetic s alts ( e.g.,

This review aims to provide a through understanding of the magneto-caloric nature of a

3.2 Fundamental Aspects

3.2.1. Relation between Magnetic Entropy and Adiabatic Temperature change

3.2.2 Relation between Magnetic Entropy and Resistivity

3.2.3 Magneto-caloric behavior and Magnetic Transition

3.2.4 Magnetic Cooling Efficiency

3.3 Magneto-caloric Measurements

3.4 Manganite Materials

In general, t he c onventional s olid-state r eaction m ethod ha s be en us ed t o s ynthesize

3.4.2. Magneto-Caloric Effect

3.4.2.1. (La1-xMx) MnO3 where M = Na, K and Ag

3.4.2.2. (La1-xMx) MnO3 where M = Ca, Sr, Ba, Cd and Pb

3.4.2.2.2. (La1-xSrx) MnO3

3.4.2.2.3. (La1-xBax) MnO3