Materials with new or improved properties are crucial for technological development. To provide the foundation for future successful products, it is important to prepare and characterise new chemical compounds that could show unusual properties. The properties of magnetic materials are closely related to their crystal, magnetic and electronic structures. This thesis focuses on the novel synthesis and structural characterisation of a number of new ternary or pseudo-ternary silicides and germanides of manganese with iridium, cobalt or palladium. To provide a more complete picture of the complex magnetic properties, crystal and magnetic structure refinements by the Rietveld method of X-ray and neutron powder diffraction data are complemented by single-crystal X-ray diffraction, electron diffraction, magnetisation measurements and Reverse Monte Carlo simulations of magnetic short-range order. The experimental results are corroborated by first-principles electronic structure and total energy calculations. A commensurate non-collinear antiferromagnetic structure is found for most compounds of the solid solution Mn3Ir1-yCoySi1-xGex. The non-collinearity is a result of geometric frustration in a crystal structure with magnetic Mn atoms located on a three-dimensional network of triangles. The close structural similarity to the β-modification of elemental manganese, which does not order magnetically, inspired a closer theoretical comparison of the Mn3Ir1-yCoySi1-xGex propertieswith β-Mn. Magnetic frustration is also observed for Mn4Ir7-xMnxGe6, and is an important factor underlying the dramatic change from commensurate antiferromagnetic order to spin glass properties induced by a small variation in Mn concentration. Magnetic short-range order with dominant antiferromagnetic correlation is observed for Mn8Pd15Si7, and results from a random distribution of Mn atoms in-between the geometrically frustrated magnetic moments on the Mn octahedra. An incommensurate cycloidal magnetic structure, observed for IrMnSi, is stabilised by an electronic structure effect, which also accounts for the non-collinearity of the Mn3IrSi type magnetic structure.

Ce travail de thèse se situe dans la thématique des oxydes dérivés de la pérovskite ayant des propriétés de conduction mixte tels que les structures de type K2NiF4, les pérovskites doubles et la brownmillérite. Cette aptitude à conduire à la fois l'oxygène et les électrons présente un intérêt pour des dispositifs électrochimiques fonctionnant à haute température et notamment en tant qu'électrode pour les piles à combustible à oxyde solide. Plus précisément, cette thèse concerne la synthèse et l'étude cristallochimique avancée de la réactivité de ces matériaux essentiellement par les grands instruments par le biais de la diffraction de neutrons (NPD) et des rayons X synchrotron. Le travail préliminaire à ces études implique de la synthèse inorganique par voie solide ou par voie sol-gel, l'analyse thermogravimétrique et la titration iodométrique. Des cellules de réactivité originales ont été développées spécialement à l'ISCR pour l'étude in situ du comportement redox sous différents flux gazeux et en fonction de la température à la fois dans le cadre de la diffraction des neutrons et rayons X synchrotron. L'étude in situ par NPD des composés La2-xSrxMnO4±δ où x = 2,0 et x = 0,8 qui dérivent du composé de cathode de référence La1-xSrxMnO3 a permis de suivre l'évolution structurale en fonction du δ en conditions réductrices pour x = 2,0 et en conditions oxydantes pour x = 0,8. L'étude DRX synchrotron de Pr2NiO4,22 a permis de mettre en évidence la symétrie monoclinique à température ambiante alors que les études précédentes annonçaient une symétrie orthorhombique. Les variations structurales notamment la transition vers la phase HTT sont accompagnées d'une modulation incommensurable qui persiste jusqu'à au moins 900 °C. L'étude des pérovskites doubles NdBaCo2−xMnxO5+δ où 0 ≤ x ≤ 2 a permis de montrer que ces matériaux présentent des conductivités électriques totales très prometteuses pour des applications en tant que cathode de SOFC. De plus, la confrontation de la dynamique moléculaire et de la NPD combinée à la MEM pour le composé x = 0 a permis d'élucider le mécanisme de diffusion de l'oxygène dans cette famille de composés. L'étude par NPD de la réduction de LaSrFeCoO6 vers LaSrFeCoO5 de structure brownmillérite a permis de mettre en évidence que la structure réduite persiste à haute température et l'évolution de la mise en ordre des moments magnétiques lors du refroidissement de LaSrFeCoO5. / This thesis is focused on oxides related to perovskite such as K2NiF4 structure-type, double perovskite and brownmillerite with mixed conduction properties. This ability to conduct both oxygen ions and electrons is relevant for electrochemical devices operating at high temperature, particularly as an electrode for solid oxide fuel cell. Specifically, this thesis deals with the synthesis and advanced crystal structure characterization of the reactivity of these materials mainly through large scale facilities by means of neutron powder diffraction (NPD) and X-ray synchrotron. Preliminary work in these studies involves inorganic synthesis by solid-state or by sol-gel route, thermogravimetric analysis and the iodometric titration. Original reactivity cells have been developed at the ISCR to study redox behavior under different gas flow and as a function of temperature for both neutron diffraction and X-ray synchrotron experiment. In situ study by NPD of La2-xSrxMnO4 ± δ compounds where x = 2.0 and x = 0.8 which derived from the compound cathode reference La1-xSrxMnO3 allowed to follow the structural evolution as a function of δ in reducing conditions for x = 2.0 and oxidizing conditions for x = 0.8. The synchrotron study of Pr2NiO4.22 helped to highlight the monoclinic symmetry at room temperature while previous studies announced an orthorhombic symmetry. Besides, structural changes including the transition to the HTT phase are accompanied by an incommensurable modulation that persists at least up to 900 °C. The study of double perovskites NdBaCo2-xMnxO5+δ where 0 ≤ x ≤ 2 showed that these materials exhibit a promising electrical conductivities for SOFC applications as cathode. In addition, the comparison of the molecular dynamics and NDP combined with MEM for x = 0 compound has elucidated the oxygen diffusion mechanism in these compounds. The study by NPD in reducing condition of LaSrFeCoO6 to the brownmillerite LaSrFeCoO5 has showed that the reduced structure persists at high temperatures and allowed to follow the evolution in the ordering of the magnetic moments while cooling LaSrFeCoO5.

In recent years, additive manufacturing (AM) has been one of the essential production techniques in the engineering community. Rapid integration of this technique drew a bead on the reliability of the microstructural and mechanical properties of engineering components. However, due to the nature of the layer-by-layer approach of AM, complex thermal gradients can cause inhomogeneous microstructure and significant residual stresses (RS). These, expectedly, can lead to a dramatic reduction in material performance. Therefore, especially for alloys like Ni-based Inconel 718 (IN718) used in critical applications, the characterization and later optimization of the DED process on material properties become essential. Nevertheless, empirical and conventional approaches are needed to improve, or new techniques should be introduced. In this regard, this study aims to understand better the evolution of the mechanical and microstructural properties of IN718 during and post-DED processes. For this purpose, an in-situ 2D neutron diffraction strain monitoring was carried out during the DED of IN718. The strain contributions originated from microstructural, thermal, and stress-based events during deposition and cooling periods at different positions concerning melt pool were investigated. Stabilization of different positions and processing regions on the sample as a function of the temperature profile, build height, and microstructural events are examined. Laboratory-scale microstructural studies were performed on wire-DED parts to observe the process parameter dependency of precipitation, composition, and morphology of microstructural constituents. Moreover, these findings were benchmarked with neutron powder diffraction measurements to relate the crystallographic behavior with macroscopic ones. Solidification under different cooling rates and heat treatments was carried out using the neutron powder diffraction technique to comprehend the precipitation dynamics and explain the microstructural events during and after the DED process. Laboratory scale and neutron diffraction tensile characterization tests were performed to observe and relate the mechanical response of wire- DED IN718 at different temperatures and microstructural conditions.:Keywords i Abstract iii Table of Contents v List of Figures ix List of Tables xvii List of Abbreviations xix Acknowledgments xxi Chapter 1: Introduction 1 1.1 Residual Stress in Polycrystalline Materials 1 1.1.1 Residual Stress Determination 3 1.2 Neutron Scattering 5 1.2.1 Neutron-Matter Interaction 6 1.2.2 Strain Measurement by Neutron Diffraction 7 1.2.3 SALSA Neutron Strain Diffractometer 14 1.2.4 Neutron Powder Diffraction 16 1.2.5 D20 Neutron Powder Diffractometer 17 1.2.6 Peak Analysis in Diffraction Measurements 18 1.3 Nickel Superalloys 22 1.3.1 Physical Metallurgy of IN718 23 1.4 Metal Additive Manufacturing 33 1.4.1 Direct Energy Deposition (DED) 34 1.4.2 Process Monitoring in Metal AM 36 1.5 Context and Aim of the Study 40 Chapter 2: Materials and Experimental Methods 43 2.1 IN718 Feedstock Material 43 2.2 Fabrication Process by wire-DED Method 43 2.2.1 Post Processing of IN718 via Solution Treatment and Aging 47 2.2.2 Preparation of Tensile Specimens 48 2.3 Microstructural Characterization 49 2.3.1 Electron Microscopy Studies 49 2.3.2 Differential Scanning Calorimetry Analysis 50 2.3.3 Lattice Parameter Evolution of IN718 with Temperature 52 2.3.3.1 Data Reduction for Phase Analysis 54 2.4 Mechanical Characterization 57 2.4.1 Neutron Diffraction 2D Strain Monitoring during IN718 wire-DED 57 2.4.1.1 Temperature Data Treatment and Processing Regions 61 2.4.1.2 Neutron Data Acquisition and Analysis 64 2.4.2 Residual Stress Mapping of Samples for Mechanical Characterization 69 2.4.3 Macro-scale Tensile Characterization at Room and High Temperatures 71 2.4.4 Neutron Diffraction Tensile Characterization Testing 72 2.4.4.1 Neutron Data Processing Procedure 77 Chapter 3: Results and Discussion 79 3.1 Microstructural Characterization of Feedstock Wire 79 3.1.1 Metallography of IN718 Feedstock Wire 79 3.1.2 Simulation of Phase Precipitations in IN718 80 3.1.3 Thermal Stability of IN718 Feedstock Wire 82 3.1.3.1 Differential Scanning Calorimetry 82 3.1.3.2 Lattice Parameter Evolution during Melting & Solidification 83 3.1.4 Discussion 91 3.2 Microstructure of IN718 wire-DED Parts 94 3.2.1 IN718-DED Cylindrical Walls 94 3.2.2 IN718 -DED Prisms 103 3.2.3 Discussion 108 3.3 Heat Treatments of IN718 Wire-DED Parts 112 3.3.1 Time and Temperature Impact into Laves Phase Dissolution 112 3.3.2 Lattice Parameter Evolution of IN718 during Solution and Aging Treatments 115 3.3.3 Discussion 118 3.4 Mechanical Characterization of IN718 wire-DED 122 3.4.1 Neutron Diffraction 2D Strain Monitoring during IN718 wire-DED 122 3.4.1.1 Bragg Angle Evolution 122 3.4.1.2 Evolution of Bragg Angle Position in MP Processing Region 123 3.4.1.3 Evolution of Bragg Angle Position in the NMP Processing Region 126 3.4.1.4 Evolution of Bragg Angle Position in FF Processing Region 129 3.4.2 Discussion 131 3.4.2.1 Comparison of Equilibrium State of IN718 through In-situ and Ex-situ Investigations 135 3.4.3 Reference (d0) Approaches for Strain Calculations 136 3.4.3.1 Stable processing regime reference 136 3.4.3.2 Neutron powder diffraction reference 137 3.4.4 Evolution of Strain Contributions during IN718 wire-DED by Using Stable Reference (d0) Approach 140 3.4.4.1 Strain Evolution in MP Processing Region 141 3.4.4.2 Strain Evolution in NMP Processing Region 143 3.4.4.3 Strain Evolution in FF Processing Region 145 3.4.5 Evolution of Strain Contributions during IN718 wire-DED by Using Neutron Powder Diffraction Reference d0 Approach 148 3.4.6 Discussion 151 3.4.7 Tensile Characterization 153 3.4.7.1 Macro-scale Tensile Behavior 153 3.4.7.2 Residual Stress State in In-situ Tensile Test Specimens 155 3.4.7.3 Lattice-scale Tensile Behavior 158 3.4.8 Discussion 169 3.4.8.1 Residual Stress State prior to Tensile Test Characterization 169 3.4.8.2 Macro-scale Tensile Behavior of IN718 at Room and High Temperatures 169 3.4.8.3 Lattice-dependent Behavior As-built and Direct-aged Condition as a function of Applied Stresses 175 Chapter 4: Summary Discussion 182 4.1 Microstructural Considerations 182 4.1.1 Comparison of Materials and Extrapolation of Properties 182 4.2 Thermal Stability of IN718 Feedstock Wire and DED Parts 183 4.2.1 Matrix, Phase Precipitation, and CTE Evolution as a Function of Temperature 183 4.2.2 Heat Treatments of IN718 DED materials 184 4.3 Fabrication and Neutron Strain Monitoring Considerations 185 4.3.1 Temperature Gradients and Regions of Interest 185 4.3.2 In-situ Neutron Monitoring of Bragg Angle Evolution of γ-matrix 185 4.3.3 2D Strain Evolution 186 4.4 Tensile Mechanical Behaviour at Room and High-Temperature Considerations 189 4.4.1 Macro-scale Characterization 189 4.4.2 Lattice-scale Neutron Diffraction Characterization 189 Chapter 5: Conclusions 191 Bibliography 196 / In den letzten Jahren hat sich die additive Fertigung (AM) zu einer der wichtigsten Produktionstechniken in der Ingenieurwelt entwickelt. Die schnelle Integration dieser Technik hat die Zuverlässigkeit der mikrostrukturellen und mechanischen Eigenschaften von technischen Komponenten deutlich verbessert. Aufgrund des schichtweisen Ansatzes der AM können jedoch komplexe thermische Gradienten eine inhomogene Mikrostruktur und erhebliche Eigenspannungen (RS) verursachen. Diese können erwartungsgemäß zu einer dramatischen Verringerung der Materialleistung führen. Daher sind insbesondere bei Legierungen wie Inconel 718 (IN718) auf Ni-Basis, die in kritischen Anwendungen eingesetzt werden, die Charakterisierung und spätere Optimierung des DED-Prozesses auf die Materialeigenschaften von entscheidender Bedeutung. Dennoch müssen empirische und konventionelle Ansätze verbessert werden, oder es sollten neue Techniken eingeführt werden. In diesem Zusammenhang zielt diese Studie darauf ab, die Entwicklung der mechanischen und mikrostrukturellen Eigenschaften von IN718 während und nach dem DED-Prozess besser zu verstehen. Zu diesem Zweck wurde während des DED-Prozesses von IN718 eine in-situ 2D-Neutronenbeugungsmessung der Dehnung durchgeführt. Die Dehnungsbeiträge, die von mikrostrukturellen, thermischen und spannungsbasierten Ereignissen während der Abscheidungs- und Abkühlungsperioden an verschiedenen Positionen des Schmelzbades herrühren, wurden untersucht. Die Stabilisierung verschiedener Positionen und Verarbeitungsbereiche auf der Probe als Funktion des Temperaturprofils, der Aufschmelzhöhe und der mikrostrukturellen Ereignisse wurde untersucht. Im Labormaßstab wurden mikrostrukturelle Studien an Draht-DED-Teilen durchgeführt, um die Abhängigkeit der Prozessparameter von der Ausscheidung, Zusammensetzung und Morphologie der mikrostrukturellen Bestandteile zu beobachten. Darüber hinaus wurden diese Ergebnisse mit Neutronenpulverbeugungsmessungen verglichen, um das kristallographische Verhalten mit dem makroskopischen Verhalten in Beziehung zu setzen. Die Erstarrung unter verschiedenen Abkühlungsraten und Wärmebehandlungen wurde mit Hilfe der Neutronenpulverbeugungstechnik durchgeführt, um die Ausscheidungsdynamik zu verstehen und die mikrostrukturellen Ereignisse während und nach dem DED-Prozess zu erklären. Es wurden Zugversuche im Labormaßstab und mit Neutronenbeugung durchgeführt, um die mechanische Reaktion von IN718 bei verschiedenen Temperaturen und Mikrostrukturbedingungen zu beobachten und in Beziehung zu setzen.:Keywords i Abstract iii Table of Contents v List of Figures ix List of Tables xvii List of Abbreviations xix Acknowledgments xxi Chapter 1: Introduction 1 1.1 Residual Stress in Polycrystalline Materials 1 1.1.1 Residual Stress Determination 3 1.2 Neutron Scattering 5 1.2.1 Neutron-Matter Interaction 6 1.2.2 Strain Measurement by Neutron Diffraction 7 1.2.3 SALSA Neutron Strain Diffractometer 14 1.2.4 Neutron Powder Diffraction 16 1.2.5 D20 Neutron Powder Diffractometer 17 1.2.6 Peak Analysis in Diffraction Measurements 18 1.3 Nickel Superalloys 22 1.3.1 Physical Metallurgy of IN718 23 1.4 Metal Additive Manufacturing 33 1.4.1 Direct Energy Deposition (DED) 34 1.4.2 Process Monitoring in Metal AM 36 1.5 Context and Aim of the Study 40 Chapter 2: Materials and Experimental Methods 43 2.1 IN718 Feedstock Material 43 2.2 Fabrication Process by wire-DED Method 43 2.2.1 Post Processing of IN718 via Solution Treatment and Aging 47 2.2.2 Preparation of Tensile Specimens 48 2.3 Microstructural Characterization 49 2.3.1 Electron Microscopy Studies 49 2.3.2 Differential Scanning Calorimetry Analysis 50 2.3.3 Lattice Parameter Evolution of IN718 with Temperature 52 2.3.3.1 Data Reduction for Phase Analysis 54 2.4 Mechanical Characterization 57 2.4.1 Neutron Diffraction 2D Strain Monitoring during IN718 wire-DED 57 2.4.1.1 Temperature Data Treatment and Processing Regions 61 2.4.1.2 Neutron Data Acquisition and Analysis 64 2.4.2 Residual Stress Mapping of Samples for Mechanical Characterization 69 2.4.3 Macro-scale Tensile Characterization at Room and High Temperatures 71 2.4.4 Neutron Diffraction Tensile Characterization Testing 72 2.4.4.1 Neutron Data Processing Procedure 77 Chapter 3: Results and Discussion 79 3.1 Microstructural Characterization of Feedstock Wire 79 3.1.1 Metallography of IN718 Feedstock Wire 79 3.1.2 Simulation of Phase Precipitations in IN718 80 3.1.3 Thermal Stability of IN718 Feedstock Wire 82 3.1.3.1 Differential Scanning Calorimetry 82 3.1.3.2 Lattice Parameter Evolution during Melting & Solidification 83 3.1.4 Discussion 91 3.2 Microstructure of IN718 wire-DED Parts 94 3.2.1 IN718-DED Cylindrical Walls 94 3.2.2 IN718 -DED Prisms 103 3.2.3 Discussion 108 3.3 Heat Treatments of IN718 Wire-DED Parts 112 3.3.1 Time and Temperature Impact into Laves Phase Dissolution 112 3.3.2 Lattice Parameter Evolution of IN718 during Solution and Aging Treatments 115 3.3.3 Discussion 118 3.4 Mechanical Characterization of IN718 wire-DED 122 3.4.1 Neutron Diffraction 2D Strain Monitoring during IN718 wire-DED 122 3.4.1.1 Bragg Angle Evolution 122 3.4.1.2 Evolution of Bragg Angle Position in MP Processing Region 123 3.4.1.3 Evolution of Bragg Angle Position in the NMP Processing Region 126 3.4.1.4 Evolution of Bragg Angle Position in FF Processing Region 129 3.4.2 Discussion 131 3.4.2.1 Comparison of Equilibrium State of IN718 through In-situ and Ex-situ Investigations 135 3.4.3 Reference (d0) Approaches for Strain Calculations 136 3.4.3.1 Stable processing regime reference 136 3.4.3.2 Neutron powder diffraction reference 137 3.4.4 Evolution of Strain Contributions during IN718 wire-DED by Using Stable Reference (d0) Approach 140 3.4.4.1 Strain Evolution in MP Processing Region 141 3.4.4.2 Strain Evolution in NMP Processing Region 143 3.4.4.3 Strain Evolution in FF Processing Region 145 3.4.5 Evolution of Strain Contributions during IN718 wire-DED by Using Neutron Powder Diffraction Reference d0 Approach 148 3.4.6 Discussion 151 3.4.7 Tensile Characterization 153 3.4.7.1 Macro-scale Tensile Behavior 153 3.4.7.2 Residual Stress State in In-situ Tensile Test Specimens 155 3.4.7.3 Lattice-scale Tensile Behavior 158 3.4.8 Discussion 169 3.4.8.1 Residual Stress State prior to Tensile Test Characterization 169 3.4.8.2 Macro-scale Tensile Behavior of IN718 at Room and High Temperatures 169 3.4.8.3 Lattice-dependent Behavior As-built and Direct-aged Condition as a function of Applied Stresses 175 Chapter 4: Summary Discussion 182 4.1 Microstructural Considerations 182 4.1.1 Comparison of Materials and Extrapolation of Properties 182 4.2 Thermal Stability of IN718 Feedstock Wire and DED Parts 183 4.2.1 Matrix, Phase Precipitation, and CTE Evolution as a Function of Temperature 183 4.2.2 Heat Treatments of IN718 DED materials 184 4.3 Fabrication and Neutron Strain Monitoring Considerations 185 4.3.1 Temperature Gradients and Regions of Interest 185 4.3.2 In-situ Neutron Monitoring of Bragg Angle Evolution of γ-matrix 185 4.3.3 2D Strain Evolution 186 4.4 Tensile Mechanical Behaviour at Room and High-Temperature Considerations 189 4.4.1 Macro-scale Characterization 189 4.4.2 Lattice-scale Neutron Diffraction Characterization 189 Chapter 5: Conclusions 191 Bibliography 196

Les travaux présentés dans ce manuscrit portent sur la synthèse et la caractérisation de nouveaux matériaux magnétocaloriques à basse de terres rares pour la réfrigération magnétique. Le premier chapitre constitue une introduction aux notions d’effet magnétocalorique et de réfrigération magnétique et dresse un état de l’art des matériaux magnétocaloriques existants. Dans le but d’obtenir des matériaux à forte capacité de réfrigération (RC) et d’identifier des stratégies d’amélioration de ce critère de performance, deux voies de recherche ont été explorées : l’élargissement de la transition magnétique et l’effet de l’élément de transition M et de l’élément p (X) dans les verres métalliques Gd60M30X10 (M = Mn, Fe, Co, Ni, Cu et X = Al, Ga, In) d’une part, et la synthèse de nouveaux siliciures ternaires dans les systèmes R-M-Si (R = Nd, Gd, Tb et M = Co, Ni) à fort potentiel magnétocalorique, d’autre part.Le second chapitre de cette thèse présente les propriétés magnétiques des rubans amorphes à base de gadolinium synthétisés par la technique de melt-spinning, dans lesquels le désordre structural induit un très fort élargissement de la transition magnétique (vis-à-vis de celle du gadolinium par exemple). Il montre dans un premier temps, la faible influence de l’élément p (X) sur les propriétés magnétiques des rubans Gd60Mn30X10 (X = Al, Ga, In). Une seconde partie présente la très forte influence de l’élément de transition M, tant sur la nature de la transition magnétique que sur les propriétés magnétocaloriques des verres métalliques Gd60M30In10 (M = Mn, Fe, Co, Ni, Cu), avec en particulier une température de Curie variant entre 86 (M = Ni) et 220 K (M = Fe) et l’existence d’un phénomène de type cluster-glass en dessous de 35 K lorsque M = Mn. Le chapitre trois de cette thèse se décline en trois parties. La première décrit les conditions de synthèse parfois délicates, notamment dans le choix des températures de recuit, des siliciures R5MSi2, Gd5Si3 et du composé à domaine d’existence Gd3Co2,5 ± xSi1,5 ± y. L’utilisation de la méthode Rietveld pour l’affinement des diffractogrammes de rayons X sur poudre et monocristaux et neutrons a permis de montrer que les composés R5MSi2 adoptent une structure de type Cr5B3 avec la particularité de l’occupation mixte du site 8h par Co et Si à 50 %/50 % et que Gd3Co2,5 ± xSi1,5 ± y adopte une structure de type Er3Ge4 avec des sites mixtes Co/Si en positions 4a et 4c. La seconde partie présente les propriétés magnétiques et magnétocaloriques du siliciure Gd5CoSi2. Ce composé subit une transition ferromagnétique à la température de Curie de 169 K qui s’accompagne d’une variation d’entropie magnétique calculée par l’application de la relation de Maxwell, de -4,7 et 8,7 J kg-1 K-1 pour des variations de champ magnétique respectives de 2 et 5 T. Le troisième volet de ce chapitre décrit les propriétés magnétiques de Nd5CoSi2 et Nd5NiSi2 qui présentent une transition ferromagnétique respectivement à 55 et 44 K. Il décrit également l’affinement de la structure ferromagnétique cantée de Nd5CoSi2 obtenue par des mesures de diffraction neutronique.Il ressort de ces travaux que l’évaluation des matériaux magnétocaloriques par le seul critère de capacité de réfrigération ne mène pas vers les matériaux les plus adaptés à l’application. Il faudrait cibler plus spécifiquement, pour chaque type de cycle de réfrigération envisagé, des critères pragmatiques tels qu’une fenêtre de température d’utilisation autour de la température de Curie ou une valeur de chaleur spécifique optimale afin de mieux guider la recherche de nouveaux matériaux magnétocaloriques. / The studies presented in this manuscript deal with the synthesis and characterization of new rare-earth based magnetocaloric materials for magnetic refrigeration applications. The first chapter is an introduction to the concepts of magnetocaloric effect and magnetic refrigeration and establishes a review of the magnetocaloric materials existing today. Two research axes were explored in order to obtain materials with a high refrigeration capacity (RC) and to identify strategies for improving this performance criterion: the enlargement of magnetic transition and the effect of transition element M and p-element X in the metallic glasses Gd60M30X10 (M = Mn, Fe, Co, Ni, Cu et X = Al, Ga, In) on one hand, and the synthesis of new ternary silicides in the RE-M-Si systems (RE = Nd, Gd, Tb et M = Co, Ni) with high magnetocaloric potential on the other hand. The second chapter of this thesis presents the magnetic properties of Gd-based amorphous ribbons synthesized by the melt-spinning technique, in which the structural disorder induces a very strong enlargement of the magnetic transition (compared to that of pure Gd for instance). In a first part, it shows the weak influence of the p element (X) on the magnetic properties of Gd60Mn30X10 (X = Al, Ga, In) ribbons. A second part presents the very strong influence of the transition element M, either on the nature of the magnetic transition and on the magnetocaloric properties of Gd60M30In10 (M = Mn, Fe, Co, Ni, Cu) metallic glasses with, in particular, a Curie temperature varying between 86 (M = Ni) and 220 K (M = Fe) and the occurrence of a cluster-glass behavior below 35 K when M = Mn. The third chapter of this thesis is composed of three parts. The first one describes the synthesis conditions of RE5MSi2 (RE = Nd, Gd, Tb), Gd5Si3 and of the compound with existence domain Gd3Co2.5 ± xSi1.5 ± y. These syntheses are sometimes delicate, particularly in the choice of annealing temperatures. The use of the Rietveld method to refine the X-ray and neutron powder diffraction patterns allowed showing that RE5MSi2 compounds adopt a Cr5B3 type structure, with a mixed occupation of 8h site by Co and Si at 50 %/50 % and that Gd3Co2.5 ± xSi1.5 ± y adopts an Er4Ge4 type structure with mixed Co/Si occupation in 4a et 4c positions. The second part presents the magnetic and magnetocaloric properties of the Gd5CoSi2 silicide. This compound exhibits a ferromagnetic transition at the Curie temperature TC = 169 K that is accompanied by a magnetic entropy change of -4.7 and 8.7 kg-1 K-1 at 2 and 5 T, respectively, as calculated by the application of Maxwell’s relationship. The third part is this chapter describes the magnetic properties of Nd5CoSi2 and Nd5NiSi2 which order ferromagnetically at 55 and 44 K, respectively. It also presents the refinement of the canted ferromagnetic structure on Nd5CoSi2, obtained by neutron diffraction measurements.These study show that evaluating the magnetocaloric materials by only considering the criterion of refrigeration capacity does not lead to the elaboration of the best materials for the applications. It could be more efficient to target more pragmatic criteria, for each considered refrigeration cycle, such as a temperature window of use around the Curie temperature or an optimal specific heat value in order to lead the research of new magnetocaloric materials at best.

Ferroelectric materials, especially the polycrystalline ceramics, are very promising material for a variety of applications such as high permittivity dielectrics, ferroelectric memories, piezoelectric sensors, piezoelectric/electrostrictive transducers, electrooptic devices and PTC thermistors. Among the ferroelectric based piezoelectric ceramics the lead–zirconate-titanate Pb(Zr1-xTix)O3 (PZT) have dominated transducer and actuator market due to its excellent piezoelectric and dielectric properties, high electromechanical coupling, large piezoelectric anisotropy, ease of processing and low cost. However, the toxicity of lead based compounds has raised serious environmental concerns and therefore has compelled the researchers to look for new lead free alternatives with good piezoelectric and ferroelectric properties. (Na0.5Bi0.5)TiO3 (NBT) and its solid solution is one of the leading lead free piezoceramic ceramics due to their interesting ferroelectric, piezoelectric, electromechanical and dielectric property. The parent compound NBT is a ferroelectric with a moderately high Curie temperature (~250 oC), large ferroelectric polarization (~40µC/cm2) polarization, promising piezoelectric properties with 0.08% strain and longitudinal piezoelectric coefficient (d33) ~ 80 pC/N. X-ray and neutron diffraction studies in the past have shown that NBT exhibits rhombohedral (R3c) at room temperature. Neutron diffraction studies have suggested that NBT undergo a gradual rhombohedral to tetragonal (P4bm) transformation in a temperature region 200-320 ºC. Though the structure and phase transition behavior of NBT has been extensively investigated for over six decades now, this subject has again become debatable in recent few years, with some group reporting formation of orthorhombic phase above room temperature and another group suggesting monoclinic distortion at room temperature using high resolution x-ray diffraction technique. Interestingly the intermediate orthorhombic instability, reported by electron diffraction studies, has never been captured by neutron diffraction method though neutron diffraction is an equally powerful tool for studying (oxygen) octahedral tilts in perovskites. Needless to mention, the understanding of the subtle structural distortions have great significance with regard to the determination of the structure-piezoelectric property correlations in NBT based piezoceramics. The present thesis deals with such subtle structural issues in great detail. The systems investigated in the thesis are Ca and Ba modified NBT. While the Ca modified system was chosen to understand the subtle orthorhombic instability that has been reported above room temperature (only) by detailed electron diffraction work, Ba-modified NBT is the most investigated among the NBT-derived piezoelectric material systems and this thesis attempts to address some of the very complex nature of the structure-piezoelectric property correlation of this system. The first chapter of the thesis provides a brief introduction to the field of ferroelectrics, perovskite structure and their phase transition. A brief exposure to the conventional lead based relaxor ferroelectric and piezoelectric material is provided. A detailed overview of the existing knowledge related to room temperature structure of NBT and its phase transition studies with temperature has been discussed in the later part of this chapter. The second chapter includes various the experimental techniques that have been employed to synthesis and characterize the specimens under investigation. The third chapter deals with the phase transition behaviour of Ca modified NBT as a function of composition and temperature in the dilute concentration region. This work was carried out with the view to obtain a better understanding and compliment the intrinsic high temperature orthorhombic instability in NBT reported by electron diffraction technique. Interestingly, inspite of the fact that neutron diffraction method is a very sensitive tool for investigating subtle change in the nature of octahedral tilt in oxide perovskites, the intermediate orthorhombic distortion proposed by the electron diffraction studies has so far never been captured in any of the neutron diffraction studies. In this work we have verified the genuineness of the intrinsic instability with regard to the non-polar orthorhombic structure using neutron powder diffraction by adopting a special strategy which helped in capturing the characteristic signatures (the superlattice reflections) of the orthorhombic phase in the neutron powder diffraction patterns. It was found that small fraction of Ca-substitution (8-10 mol %) was good enough to amplify the magnitude of the orthorhombic (Pbnm) distortion, without altering the sequence of the structural evolution with temperature of the parent compound (NBT) itself, and stabilizing it at the global length scale at lower temperatures than pure NBT. This chapter presents the innovative approach that was used to extract reliable information about the very complex phase transition behaviour, involving coexistence of the various similar looking but crystallographically different phases in different temperature regimes by Rietveld analysis of temperature dependent neutron powder diffraction pattern in conjunction with temperature dependent dielectric and ferroelectric characterization of the specimens. The detailed study revealed the following sequence of structural evolution with temperature: Cc+Pbnm →Pbnm + P4/mbm → P4/mbm →Pm3 m. The fourth chapter gives a detail account of the structure-property correlations and the phase transition behaviour of (1-x)(Na0.5Bi0.5)TiO3 – (x)BaTiO3 (0≤x≤0.10), the most important solid solution series with NBT as reported in the literature. The phase transformation behaviour of this system has been investigated as a function of composition (0<x≤0.10), temperature, electric field and mechanical-impact by Raman scattering, ferroelectric, piezoelectric measurements, x-ray and neutron powder diffraction methods. The structure of the morphotropic phase boundary (MPB) compositions of this system, which is interesting from the piezoelectric property point of view, has been under controversy for long. While some groups report the structure to be pseudocubic, other groups suggest it to be combination of rhombohedral and tetragonal. A perusal of the literature suggests that the reported nature and composition range of MPB is dependent on the method of synthesis and characterization technique used. In the present study, crystal structure of the NBT-BT solid solution has been investigated at the close interval near the MPB (0.05≤x≤0.10). Though x-ray diffraction study revealed three distinct composition ranges characterizing different structural features in the equilibrium state at room temperature: (i) monoclinic (Cc) + rhombohedral (R3c) for 0≤x≤0.05, (ii) “cubic-like” for 0.06≤x≤0.0675 and (iii) MPB like for 0.07≤x<0.10, Raman and neutron powder diffraction studies revealed identical symmetry for the cubic like and the MPB compositions. Both the cubic like compositions and the MPB compositions exhibit comparatively large d33. In the later part of this chapter this apparent contradiction is resolved by the fact that the cubic like structure transforms irreversibly to MPB after electric poling, a procedure which involves applying high dc electric field (well above the coercive field) to the pellet before carrying out the piezoelectric measurements. The effect of electrical field and mechanical impact has been studied for all the three different composition range, and it was found that electric field and mechanical impact both led to irreversible phase transformation in the same direction, though the transformation with mechanical impact remains incomplete in comparison to electric field. The most pronounced effect was observed for the cubic like compositions 0.06≤x≤0.0675 – they undergo phase separation to rhombohedral and tetragonal phases by electrical and mechanical perturbations. In the non-perturbed state the cubic-like critical compositions mimics features of relaxor ferroelectrics and extremely short coherence length (~ 40-50 Å) of the out-of-phase octahedral tilts. In the poled state this coherence length grows considerably and the system behaves like a normal ferroelectric. This confirmed a strong coupling between the lattice, octahedral tilts and polarization degrees of freedom. Neutron diffraction study of compositions exhibiting cubic-like and the MPB like revealed that the traditional P4bm tetragonal structure model fails to account for the intensity of the superlattice reflections. Thus the tetragonal structure stabilized above room temperature in pure NBT is different from the tetragonal phase observed at room temperature in the NBT-BT system. The results of the effect of mechanical impact and electric field has also been reported in this chapter for the critical composition exhibiting MPB (x=0.07). A detailed structural analysis of the precritical compositions, x≤0.05, revealed coexistence of ferroelectric phases (Cc+R3c) in equilibrium state (annealed specimens). This transforms to single phase (R3c) state after poling. Thus though the precritical (x≤0.05) and critical compositions (0.06≤x<0.10) of NBT-BT exhibits coexistence of ferroelectric phases in the equilibrium state, the fact that the electric poling makes the specimen single phase, R3c, after poling for the precritical compositions and retains the two phase nature of the critical compositions makes the critical compositions exhibit considerably higher piezoelectric response than the precritical compositions. Chapter five is dedicated to phase transition behaviour of the post critical compositions of (1-x)(Na0.5Bi0.5)TiO3–(x)BaTiO3 (0.16≤x≤1) using temperature dependent XRD, dielectric and ferroelectric studies. Though structurally the entire composition range is tetragonal, several notable features were revealed during detailed examination of the structural and dielectric behaviour. This study is also important from the view point that pure BT is a major component of multilayer ceramic capacitors and that an increase in the Curie point would be a welcome step for better temperature stability of the device. NBT does this. The transition temperature increases from 120 ºC for pure BT to 275 ºC for x=0.30 along with simultaneous increase in c/a ratio from 1.009 (pure BT) to 1.02 (x=0.30). Detailed analysis of temperature and frequency dependent dielectric data revealed deviation from Curie-Weiss and suggests a gradual transformation to relaxor-ferroelectric state as the NBT concentration increases in BT. The measure of frequency dispersion ‘γ’ parameter was determined from modified Curie-Weiss law for various compositions in the system. The ferroelectric and piezoelectric properties have also been investigated in detail for this composition range and an attempt has been made to correlate the composition variation of these properties with their structural parameters. This chapter shows a systematic correlation between all physical quantities such as Curie point, piezoelectric coefficient, polarization and tetragonality as a function of composition.

Perovskite based materials have great potentials for various energy applications and the search for new materials for uses in SOFCs has largely been concentrated to this class of compounds. In this search, we have studied perovskite phases in the system La2Co1+z(Ti1-xMgx)1-zO6, with 0  x 0.9 and z = 0.0, 0.2, 0.4, 0.6. Crystal structures were characterized by XRD and, for selected compositions, also by NPD and SAED. They exhibit with increasing x, as well as increasing z, a progressive increase in symmetry from monoclinic to orthorhombic to rhombohedral. The main focus in this work has been on the investigation of structure-property relations for compositions with 0.0 x 0.5 and z = 0. The nominal oxidation state of Co increases for these with increasing x, from Co2+ for x = 0 to Co3+ for x = 0.5. Magnetic measurements and XANES studies showed that the average spin state of Co changes linearly with increasing x, up to x = 0.5, in accordance with varying proportions of Co with two fixed oxidation states, i.e. Co2+ and Co3+. The data suggests that the Co3+ ions have an IS spin state or a mixture of LS and HS spin states for all compositions with nominally only Co2+ and Co3+ ions, possibly with the exception of the composition with x = 0.1, 0.2 and z = 0, for which the data indicate that the spin state might be HS. The XANES data indicate furthermore that for the perovskite phases with z = 0 and x &gt; 0.5, which in the absence of O atom vacancies contain formally Co4+, the highest oxidation state of Co is Co3+, implying that the substitution of Ti4+ by Mg2+ for x ³ 0.5 effects an oxidation of O2- ions rather than an oxidation of Co3+ ions. The thermal expansion was found to increase nearly linearly with increasing oxidation state of Co. This agrees well with findings in previous studies and is attributable to an increase in the ionic radius of Co3+ ions with increasing temperature, due to a thermal excitation from a LS to IS or LS/HS spin states. High temperature electronic conductivity measurements indicate that the electronic conductivity increases with an increase of both relative and absolute amount of Co3+. The latter can be attributed to an increase in the number of Co-O-Co connections. Additional high temperature magnetic measurements for selected samples, whose susceptibilities did not follow a Curie law behaviour up to room temperature, showed effective magnetic moments that did approach plateaus even at high temperatures (900 K). Interpretations of these data are, however, hindered by the samples losing oxygen during the applied heating-cooling cycle. The present study has shown that the investigated system is suitable for further studies, of more fundamental character, which could provide further insight of the structure-property relationships that depend on the oxidation state of Co. / Studies of cobalt based perovskites for cathode materials in solid oxide fuel cells.