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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
Professor, Department of Physics, BUET, Dhaka-1000
5.
DR. JIBAN PODDER Member
Professor, Department of Physics, BUET, Dhaka-1000
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.
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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
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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
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4.5 Magnetic Refrigeration 74
References 77
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6.5 X-Ray Diffraction Analysis 107
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
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7.8 Summary 180
References 182
Publications 235
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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-7.1 Lattice Parameters (From Single Phase) 163
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-8.1 Lattice Parameters (From Single Phase) 200
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: 6.26 Arrot Plot: Square Magnetization as a function of H/M for x=0.20 127
Fig: 6.27 Arrot Plot: Square Magnetization as a function of H/M for x=0.25 128
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
Fig: 7.28 Magnetization of LCSMO (x=0.00) series as a function Magnetic field 175
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
Fig: 7.30 Magnetization of LCSMO (x=0.05) series as a function Magnetic field 176
0
sintered at 1280 C
Fig: 7.31 Magnetic entropy as function of temperature at 1.35 T and 1 T (x=0.05) 176
sintered at 12800C
Fig: 7.32 Magnetization of LCSMO (x=0.10) series as a function Magnetic field 177
sintered at 12800C
Fig: 7.33 Magnetic entropy as function of temperature at 1.35 T and 1 T (x=0.10) 177
0
sintered at 1280 C
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Fig: 7.34 Magnetization of LCSMO (x=0.30) series as a function Magnetic field 178
sintered at 12800C
Fig: 7.35 Magnetic entropy as function of temperature at 1.35 T and 1 T (x=0.30) 178
0
sintered at 1280 C
Fig: 7.36 Magnetization of LCSMO (x=0.50) series as a function Magnetic field 179
sintered at 12800C
Fig: 7.37 Magnetic entropy as function of temperature at 1.35 T and 1 T (x=0.50) 179
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: 8.20 Hysteresis loop of La 0.7 Ca 0.255 Ba 0.045 MnO 3 sample 203
Fig: 8.21 Hysteresis loop of La 0.7 Ca 0.225 Ba 0.075 MnO 3 sample 204
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: 8.28 Arrot-plot from (M-H) curve for the sample x=0.15 208
Fig: 8.29 Arrot-plot from (M-H) curve for the sample x=0.25 208
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
measured at different AC frequencies
Fig: 8.33 The t emperature d ependence AC s usceptibility (imaginary part) for 211
x=0.10 measured at different AC frequencies
Fig: 8.34 The t emperature d ependence AC s usceptibility (real pa rt) for x = 0.15 212
measured at different AC frequencies
Fig: 8.35 The t emperature d ependence AC s usceptibility (imaginary part) for 212
x=0.15 measured at different AC frequencies
Fig: 8.36 The t emperature de pendence A C s usceptibility (real p art) for x = 0.25 213
measured at different AC frequencies
Fig: 8.37 The t emperature d ependence AC s usceptibility (imaginary part) for 213
x=0.25 measured at different AC frequencies
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: 8.40 Magnetic isotherm of LCBMO series (x=0.15) at 5T 216
Fig: 8.41 Magnetic entropy change as a f unction of temperature for the samples 216
x= 0.15 at different applied magnetic fields
Fig: 8.42 Magnetic isotherm of LCBMO series (x=0.25) at 5T 217
Fig: 8.43 Magnetic entropy change as a f unction of temperature for the samples 217
x= 0.25 at different applied magnetic fields
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 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 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.
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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.
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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:
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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)
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References
[1.1] C. Zener, “Interacraction between the shells in the transition metals”, Phys. Rev. 82
(1951) 403
[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
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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.
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.
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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.
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
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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).
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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.
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.
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
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.
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).
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.
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.
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]
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]
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.
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
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].
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.
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].
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.
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.
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].
3.4.1. 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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
53 | P a g e
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(x=0.05, 0.08, 0.10)”, J. Magn. Magn. Mater. 283 (2004), 375,
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300 K in La0.70Ca0.20Sr0.10MnO3”, Mater. Lett. 59 (2005), 2149,
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La0.7Ca0.2Sr0.1MnO3 single crystal”, J. Magn. Magn. Mater. 290–291, (2005), 665,
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site va cancies on the magnetic entropy change a nd t he C urie t emperature of
La0.67Ca0.33Mn1−xO3 perovskite”, J. Alloys Compd. 395 (2005), 23,
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[3.54] M .H. P han, T .L. P han, S .C. Y u, N .D. T ho, N . C hau, “ Large m agnetic ent ropy
change abov e 300 K i n a col ossal m aterial La0.7Sr0.3Mn0.98Ni0.02O3”, Phys. S tat. S ol.
(b) 241 (2004), 1744,
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resistance a round r oom t emperature i n La0.7Ca0.3MnO3, La0.7Sr0.3MnO3”, J. A ppl.
Phys. 90, (2001), 5689,
[3.56] H . G encer, S . A talay, H .I. A diguzel, V .S. K olat, “ Magnetocaloric ef fect and
magnetic properties of Tb0.9Sn0.1MnO3”, Physica B 357 (2005), 326,
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Gd, Dy, Tb, Ce)”, J. Magn. Magn. Mater. 257 (2003), 254,
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(La0.47Gd0.2)Sr0.33MnO3 polycrystalline na noparticles”, Mater. S ci. E ng. B 116
(2005), 183,
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entropy change i n a H eusler al loy Ni25.6Mn23.1Ga24.3 crystal”, A ppl. P hys. Lett. 73
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[3.60] J.A. B arclay, “ Pressure i nduced qu enching o f J ahn-teller di stortion and i nsulator
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electron doped manganites La0.7Ca0.3MnO3”, J. Magn. Magn. Mater. 232 (2001), 205,
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La0.7 Ca0.3 Mn O3 single crystal”, Physica B, 327 (2003), 214,
[3.63] M .H. P han, H .X. P eng, S .C. Y u, N . T ho, N . C hau, “Large ma gnetic e ntropy
change in Cu-doped manganites”, J. Magn. Magn. Mater. 285 (2005), 199.
[3.64] M .A. C houdhury, S . A khter, D .L. M inh, N .D. T ho, N . C hau, “Large m agnetic
entropy change abov e r oom t emperature i n t he col ossal m agnetoresistance
La0.7Sr0.3Mn1-xNixO3 materials”, J. Magn. Magn. Mater. 272–276 (2004), 1295,
[3.65] M.H. Phan, N.D. Tho, N. Chau, S.C. Yu, M. Kurisu, “Large magnetocaloric effect
in single crystal Pr0.63Sr0.37MnO3”, J. Appl. Phys. 97 (2005) 3215,
[3.66] Z.M. Wang, G. Ni, Q.Y. Xu, H. Sang, Y.W. Du, “Effect of average A-site cation
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,
“Large magnetic entropy change in Nd2/3 Sr1/3 Mn O3”, Appl. Phys. Lett. 79 (2001),
2040,
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magnetoresistance ef fect i n the l ayered perovskite La1.34Sr1.66Mn2O7”, J. P hys. 39
(2001) 357,
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like be havior, giant ma gnetocaloric a nd giant magnetoresistance e ffect in PrPb
manganites”, J. Magn. Magn. Mater. 272–276 (2004), 1292,
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Amaral, “Charge-ordering c ontribution t o t he m agnetic e ntropy change of
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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 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.
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
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
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
∂M
respect t o temperature, is ma ximum a t T c, a nd t herefore
∂T H
(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
∂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.
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
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
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).
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.
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.
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)
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.
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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81 | P a g e
Chapter Five Preparation of Manganites Perovskite and Experimental Techniques
5.1 Introduction
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.
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.
84 | P a g e
temperature-controlled programmer at the Center for Materials Science (CMS), Vietnam
National University, Hanoi, Vietnam.
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
2000C
85 | P a g e
12000, 12500, 12800, 13000 C
2.50C/min
2000C
2h 30h 1h t(h)
86 | P a g e
The overall experimental stages and procedures are shown in fig: 5.4.
Starting Materials
Pre-sintering, Sintering
Physical Properties
XRD
Magnetic Magneto-caloric
Phase
Purity? Structure
Yes
No
No Yes
SEM
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.
Powder weighing
……………………… Air flow protected
Electronic Balance
………………………….......... Pestle & Mortar
Powder mixing
….
Powder for DSC, TGA ….. .. STD 2960
Pre-sintering
……………………… Carbolated Muffle Furnace
in air flow
Crushing …………………………. Pestle & Mortar
XRD Phase
……………………… XRD Philips D5005, D-8
purity?
XRD
SEM ………………………
Phase purity? XRD Philips D5005, D-8
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.
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
90 | P a g e
15
0
565.420C 8.16% loss
-5
15
Weight/(%), dTg/%/min, Heat Flow/(µV)
-15 CaCO3
-30
DSC
TGA
dTG
-45
15
-15
MnCO3
TGA
-30 dTG
DSC
0 300 600 900
Furnace Temperature/0C
Fig: 5.10 DSC, TGA, dTG of MnCO3
91 | P a g e
Weight/(%), dTg/%/min, Heat Flow/(µV)
15
12
9
DSC
TGA
6
dTG
0
BaCO3
-3
0 300 600 900
Furnace Temperature/0C
12
TGA
6
dTG
DSC
3
-3 SrCO3
16
Weight/(%),dTG(/%/min), Heat flow/(µV)
12
8 DSC
TGA
dTG
4
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.
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.
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].
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.
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.
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].
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).
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.
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
-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%.
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”.
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
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
La0.7(Ca1-xPbx)0.3MnO3
00
0.05
0.10
Intensity (a.u.)
0.15
0.20
0.25
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.
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.
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)
7.7425
5.470 (Q)
(P)
7.7400
5.465
7.7375
5.460
La0.7(Ca1-xPbx)0.3MnO3
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
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
Fig: 6.9 Reitveld refinement analysis of La0.7(Ca1-xPbx)0.3MnO3 samples (12500) from X-
ray diffraction patterns with considering single phase.
114 | P a g e
Fig: 6.10 Reitveld refinement analysis of La0.7(Ca1-xPbx)0.3MnO3 samples (12500) from X-
ray diffraction patterns with considering double phase.
115 | P a g e
Fig: 6.10 Reitveld refinement analysis of La0.7(Ca1-xPbx)0.3MnO3 samples (12500) from X-
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.
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.
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,
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.
Z Fixed
α, β, γ Fixed
a, b, c Fixed
γ 1, γ 2 ,γ 3 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)
5.47
7.7265 La0.7(Ca1-xPbx)0.3MnO3
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
119 | P a g e
233.0
232.5
232.0
Volume V (Å)3
231.5
231.0
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
120 | P a g e
170
150
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
121 | P a g e
1.945
1.944
Bond length Mn-Oa (Α°)
1.943
1.942
1.941
1.940
1.939
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
290 La0.7(Ca1-xPbx)0.3MnO3 ,
Transition Temperature (K)
270
260
250
300
Transition Temperature (K)
La0.7(Ca1-xPbx)0.3MnO3 ,
x=0.00, 0.05, 0.10, 0.15,
0.20, 0.25
285
270
255
123 | P a g e
La0.7(Ca1-xPbx)0.3MnO3 ,
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
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.
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
La0.7(Ca1-xPbx)0.3MnO3
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
Magnetization (emu/g)
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
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
128 | P a g e
4000
La0.7Ca0.225Pb0.075MnO3
Magnetization2 (emu/g)2
3000
T=290
2000
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.
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
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
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
270
260
250
1.026 1.035 1.044
Ionic Radious in A-site (Α°)
290
Transition temperature (K)
280
270
260
250
150 160 170
Bond angle (deg.)
290
Transition temperature (K)
280
270
260
250
1.965 1.970 1.975
Bond length Mn-Op (Å)
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
Magnetization (emu/g)
12
-12
-24 T=10 K
-36
-48
-800 -400 0 400 800
Magnetic Field (Oe)
48
36
24 x=0.05
Magnetization (emu/g)
12
-12
-24
T=10K
-36
-48
-800 -400 0 400 800
Magnetic Field (Oe)
Magnetization (emu/g)
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
Magnetization (emu/g)
x=0.15
25 x=0.20
x=0.25
0
-25
T=10 K
-50
-75
100
x=0.00,
75 x=0.05,
x=0.10,
Magnetization (emu/g)
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)
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.
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.
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
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
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.
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.
where Tavg denotes the average temperature of T and T+Δ T, i.e. T+Δ T/2.
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,
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
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
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
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
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
Magnetization (emu/g)
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
Magnetic Entropy (J/kgK)
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
Magnetization (emu/g) 60
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
Magnetic Entropy (J/kgK)
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.
Magnetic Entropy (J/kgK)
6.25
La0.7(Ca1-xPbx)0.3MnO3 ,
5.00
x = 0.15, 0.20, 0.25
2T
5T
3.75
6.25
Magnetic Entropy (J/kgK)
2T
5T
5.00
3.75
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
4.00
La0.7(Ca1-xPbx)0.3MnO3 ,
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
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
Transition temperature (K)
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
6.25
Pb Series
Magnetic entropy (J/kgK)
5.00
0.075, 2.65
3.75
2.50
6.25
Magnetic entropy(J/kgK)
Pb Series
5.00
291, 2.65
3.75
2.50
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 4 6.07 Present work
La0.70Ca0.255Pb0.045MnO3 268 3 5.00 Present work
La0.70Ca0.255Pb0.045MnO3 268 2 3.79 Present work
La0.70Ca0.255Pb0.045MnO3 268 1.35 2.80 Present work
La0.70Ca0.255Pb0.045MnO3 268 1 2.11 Present work
La0.70Ca0.24Pb0.06MnO3 282 5 6.47 Present work
La0.70Ca0.24Pb0.06MnO3 282 4 5.73 Present work
La0.70Ca0.24Pb0.06MnO3 282 3 4.87 Present work
La0.70Ca0.24Pb0.06MnO3 282 2 3.89 Present work
La0.70Ca0.24Pb0.06MnO3 282 1.35 3.00 Present work
La0.70Ca0.24Pb0.06MnO3 282 1 2.4 Present work
La0.70Ca0.225Pb0.075MnO3 291 5 5.96 Present work
La0.70Ca0.225Pb0.075MnO3 291 4 5.20 Present work
La0.70Ca0.225Pb0.075MnO3 291 3 4.43 Present work
La0.70Ca0.225Pb0.075MnO3 291 2 3.47 Present work
La0.70Ca0.225Pb0.075MnO3 291 1.35 2.65 Present work
La0.70Ca0.225Pb0.075MnO3 291 1 2.00 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
A list of the studied samples in this chapter is given below:
(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
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.
155 | P a g e
La0.7 (Ca0.80Sr0.20)0.3MnO3(12000C) La0.7 (Ca0.75Sr0.25)0.3MnO3(12000C)
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
7.4 Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA)
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
Furnace Temperature/0C
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
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
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
160 | P a g e
7.5 X- Ray Diffraction Analysis
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.
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
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
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
167 | P a g e
1.9690
1.9685
Bond length (Mn-Oa)Å
1.9680
1.9675
1.9670
1.9665
290
Curie Temperature (K)
280
270
260
168 | P a g e
0.875
0.874
Tolerance factor
0.873
0.872
0.871
0.870
3.00
Ts=12000C
2.25 H=20 Oe
Magnetization (emu/g)
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
170 | P a g e
295
290
280
275
270
265
260
1.155 1.160 1.165 1.170 1.175
Ionic Radius of A-site (Å)
290 Sr series
Curie Temperature (K)
280
270
260
150 155 160 165
Bond Angle (θ0)
290
Sr series
Curie temperature (K)
280
270
260
250
0.8700 0.8725 0.8750
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.
40
30
x=0.10
20
Magnetization (emu/g)
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
Magnetization (emu/g)
25 T=10 K
-25
x=0.10
x=0.30
x=0.50
-50
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
RCP = |Δ Sm|max. δ Tfwhm 7.2
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.
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
Magnetic field H(Oe)
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)
Fig: 7.28 Magnetization of LCSMO (x=0.00) series as a f unction Magnetic field sintered
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
Magnetization (emu/g)
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
Magnetic entropy, ∆S(J/kgK)
2.0
x=0.05
1.5
1.0
1.0T
0.5 1.35T
177 | P a g e
75
∆T=5K 195K
60
Magnetization (emu/g)
45
30
15 240K
La0.7Ca0.27Sr0.03MnO3
0
0 4000 8000 12000
Magnetic Field (Oe)
Fig: 7.32 Magnetization of LCSMO (x=0.10) series as a f unction Magnetic field sintered
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
Magnetization (emu/g)
30
15
270K
La0.7Ca0.21Sr0.09MnO3
0
0 4000 8000 12000
Magnetic Field (Oe)
Fig: 7.34 Magnetization of LCSMO (x=0.30) series as a f unction Magnetic field sintered
at 12800C
3.0
Magnetic entropy, ∆S(J/kgK)
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)
Fig: 7.35 Magnetic entropy as function of temperature at 1.35 T and 1 T (x=0.30)
179 | P a g e
60
264.95
269.85
274.75
Magnetization (emu/g)
45 280.15
285.25
290.45
296.05
300.55
30 305.45
310.45
315.55
320.55
325.55
15
La0.7Ca0.15Sr0.15MnO3
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)
Fig: 7.37 Magnetic entropy as function of temperature at 1.35 T and 1 T (x=0.50)
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)
Magnetic entropy (J/kgK)
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
La0.70Ca0.21Sr0.09MnO3 256 (TS=12800C) 1.35 2.79 Present work
La0.70Ca0.21Sr0.09MnO3 256 (TS=12800C) 1 2.13 Present work
La0.70Ca0.15Sr0.15MnO3 303 (TS=12800C) 1.35 2.72 Present work
La0.70Ca0.15Sr0.15MnO3 303 (TS=12800C) 1 2.10 Present work
10 1.35(T)
5(T)
Magnetic entropy (J/kgK)
6
(293, 5.00)
2
260 280 300 320 340
Curie Temperature (K)
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
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187 | P a g e
Chapter Eight Study of La0.7(Ca1-xBax)o.3MnO3 Perovskite
8.1 Introduction
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:
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].
189 | P a g e
La0.7(Ca0.80Ba0.20)0.3MnO3 (12800 C) La0.7(Ca0.75Ba0.25)0.3MnO3(12800 C)
(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
-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
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.
La0.7(Ca1-xBax)0.3MnO3
Intensity (a.u.)
x=0.25
x=0.20
x=0.10
x=0.05
x=0.00
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.
5.52
(P) 7.760 c
5.51
Lattice parameter c (Å)
Lattice parameter a, b (Å)
5.50
7.755
(Q)
5.49
5.48 7.750
La0.7(Ca1-xBax)0.3MnO3
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
233.6
233.2
232.8
0.000 0.025 0.050 0.075
Ba content
170
165
Bond angle(deg.)
160
155
150
145
0.000 0.025 0.050 0.075
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
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.
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
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
Transition temperature (K)
190
180
170
160
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)
x=0.10
50
Magnetization (emu/g)
25
-25 T=10 K
-50
60
40
Magnetization (emu/g)
X=0.15
20
-20
T=10 K
-40
-60
-900 -600 -300 0 300 600 900
Magnetic Field (Oe)
Magnetization (emu/g)
20
-20
T=10 K
-40
-900 -600 -300 0 300 600 900
Magnetic Field (Oe)
Fig: 8.21 Hysteresis loop of La0.7Ca0.225Ba0.075MnO3 sample
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
Magnetization (emu/g)
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
Magnetization (emu/g)
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
Curie temperature (K)
190
180
170
160
150
0.025 0.050 0.075
Ba content
Fig: 8.24 Curie temperatures as a function of Ba content
207 | P a g e
210
190
180
170
160
150
1.160 1.165 1.170 1.175 1.180 1.185
Ionic Radius of A-site (Å)
210
Ba series
200
Curie Temperature (K)
190
180
170
160
4950
M2(emu/g)2
4400
T=207K
3850
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
La0.7Ca0.225Ba0.075MnO3
6000
5000
M2(emu/g)2
T=1620K
4000
3000
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
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
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)
Fig: 8.32 The temperature dependence AC susceptibility (real part) for x=0.10 measured
at different AC frequencies.
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
measured at different AC frequencies.
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
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)
Fig: 8.35 The t emperature de pendence A C s usceptibility (imaginary part) for x = 0.15
measured at different AC frequencies.
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
measured at different AC frequencies.
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)
Fig: 8.37 The t emperature de pendence A C s usceptibility (imaginary part) for x = 0.25
measured at different AC frequencies.
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
RCP = |Δ Sm|max. δ Tfwhm 8.2
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
Magnetization (emu/g)
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
Magnetic Entropy (J/kgK)
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
Magnetization (emu/g)
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
Magnetic Entropy (J/kgK)
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
Magnetization (emu/g) 75
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
Magnetic Entropy (J/kgK)
3.00
2.25
1.50
0.75
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
1.50
0.75
4.50
3.75
Magnetic entropy (J/kgK)
Ba series
3.00 ∆H=1T
(207, 2.48)
2.25
1.50
0.75
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) 2 3.92 Present work
La0.70Ca0.285Ba0.015MnO3 207(TS=12800C) 1.35 3.21 Present work
La0.70Ca0.285Ba0.015MnO3 207 (TS=12800C) 1 2.48 Present work
La0.70Ca0.255Ba0.045MnO3 162(TS=12800C) 5 2.64 Present work
La0.70Ca0.255Ba0.045MnO3 162(TS=12800C) 4 2.34 Present work
La0.70Ca0.255Ba0.045MnO3 162 (TS=12800C) 3 1.75 Present work
La0.70Ca0.255Ba0.045MnO3 162(TS=12800C) 2 1.30 Present work
0
La0.70Ca0.255Ba0.045MnO3 162(TS=1280 C) 1.35 0.96 Present work
La0.70Ca0.255Ba0.045MnO3 162 (TS=12800C) 1 0.73 Present work
La0.70Ca0.225Ba0.075MnO3 164(TS=12800C) 5 3.67 Present work
La0.70Ca0.225Ba0.075MnO3 164(TS=12800C) 4 3.11 Present work
La0.70Ca0.225Ba0.075MnO3 164 (TS=12800C) 3 2.55 Present work
La0.70Ca0.225Ba0.075MnO3 164(TS=12800C) 2 1.89 Present work
La0.70Ca0.225Ba0.075MnO3 164(TS=12800C) 1.35 1.33 Present work
La0.70Ca0.225Ba0.075MnO3 164 (TS=12800C) 1 0.98 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
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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.
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°.
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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.
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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
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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
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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
Fk is the structure factor, Pk is a f actor describing the effects of preferred orientation (for
where fj the scattering factor of the j’th atom and hk, rj and Bj are matrices representing the
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
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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
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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)
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Publications
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Conference Proceedings
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