This thesis is concerned with the study of two families of materials which contain magnetically frustrated triangular lattices. Each material is concerned with a different use; the first, analogues of YMnO₃, is from a family of materials called multiferroics, the second, A₂MCu₃F₁₂ (where A = Rb¹⁺, Cs¹⁺, M = Zr⁴⁺, Sn⁴⁺, Ti⁴⁺, Hf⁴⁺), are materials which are of interest due to their potentially unusual magnetic properties deriving from a highly frustrated Cu²⁺-based kagome lattice. YFeO₃, YbFeO₃ and InFeO₃ have been synthesised as their hexagonal polymorphs. YFeO₃ and YbFeO₃ have been studied in depth by neutron powder diffraction, A.C. impedance spectroscopy, Mössbauer spectroscopy and magnetometry. It was found that YFeO₃ and YbFeO₃ are structurally similar to hexagonal YMnO₃ but there is evidence for a subtle phase separation in each case. Low temperature magnetic properties are also reported, and subtle correlations between the structural, electrical and magnetic properties of these materials have been found. InFeO₃ was found to adopt a higher symmetry and is structurally similar to the high temperature phase of YMnO₃. TbInO₃ and DyInO₃ have also been synthesised and studied at various temperatures. The phase behaviour of TbInO₃ was analysed in detail using neutron powder diffraction and internal structural changes versus temperature were mapped out – there is also evidence for a subtle isosymmetric phase transition. Neither DyInO₃ nor TbInO₃ show long-range magnetic order between 2 and 300 K, or any signs of ferroelectricity at room temperature. The new compounds Cs₂TiCu₃F₁₂ and Rb₂TiCu₃F₁₂ have both been synthesised and shown to be novel kagome lattice based materials. The former shows a transition from rhombohedral to monoclinic symmetry in the powder form and from rhombohedral to a larger rhombohedral unit cell in the single crystal – a particle size based transition pathway is suggested. For Rb₂TiCu₃F₁₂ a complex triclinic unit cell is found, which distorts with lowering temperature. Both materials show magnetic transitions with lowering temperature. The solid solution Cs₂₋ₓRbₓSnCu₃F₁₂ (x = 0, 0.5, 1.0, 1.5, 2.0) was synthesised and investigated crystallographically, demonstrating a range of behaviours. Rb₂SnCu₃F₁₂ displays a rare re-entrant structural phase transition. In contrast, Cs₀.₅Rb₁.₅SnCu₃F₁₂ shows only the first transition found in the Rb⁺ end member. CsRbSnCu₃F₁₂ adopts a lower symmetry at both room temperature and below. Cs₁.₅Rb₀.₅SnCu₃F₁₂ and Cs₂SnCu₃F₁₂ show a rhombohedral - monoclinic transition, which is similar to that found in Cs₂TiCu₃F₁₂.

Shape memory alloys (SMAs) are a new generation material which exhibits unique nonlinear deformations due to a phase transformation which allows it to return to its original shape after removal of stress or a change in temperature. It shows a shape memory effect (martensitic condition) and pseudoelasticity (austenitic condition) properties depends on various heat treatment conditions. The reason for these properties depends on phase transformation through temperature changes or applied stress. Many technological applications of austenite SMAs involve cyclical mechanical loading and unloading in order to take advantage of pseudoelasticity, but are limited due to poor fatigue life. In this thesis, I investigated two important mechanical feature to fatigue behavior in pseudoelastic NiTi SMA wires using high energy synchrotron radiation X-ray diffraction (SR-XRD). The first of these involved simple bending and the second of these involved relaxation during compression loading. Differential scanning calorimetry (DSC) was performed to identify the phase transformation temperatures. Scanning electron microscopy (SEM) images were collected for the initial condition of the NiTi SMA wires and during simple bending, SEM revealed that micro-cracks in compression regions of the wire propagate with increasing bend angle, while tensile regions tend to not exhibit crack propagation. SR-XRD patterns were analyzed to study the phase transformation and investigate micromechanical properties. By observing the various diffraction peaks such as the austenite (200) and the martensite (100), (110), and (101) planes, intensities and residual strain values exhibit strong anisotropy depending upon whether the sample is in compression or tension during simple bending. This research provides insight into two specific mechanical features in pseudoelastic NiTi SMA wires.

Demands for designing prime reliant, energy-efficient, and high performance thermal barrier coatings (TBCs) in gas turbines have led to a growing interest toward comprehensive microstructural characterization. Over the last decade, Synchrotron X-ray Diffraction (XRD) has established itself as a high-resolution strain measurement method for the thermally grown oxide (TGO) layer of thermal barrier coatings (TBCs). In this work, we present in-situ X-ray strain measurements of the TGO layer on cycled TBC specimens under thermo-mechanical loading using powerful high energy X-rays (~80.7- 86 keV) at Sector I-ID of the Advanced Photon Source at the Argonne National Laboratory. The evolution of TGO stresses was examined over one complete thermal cycle on TBC samples at various stages of the life fraction under various mechanical loads. Synchrotron X-Ray Diffraction under thermo-mechanical loading has shown the existence of strain qualitatively within the diffraction patterns. Quantitative results obtained through Pseudo-Voigt peak fitting over selected peaks show the evolution of strain over a thermal cycle. In initial experiments, it was shown that mechanical loading at 32 MPa resulted in a tensile strain (£22 = 0.00053±0.00039 for 7 minutes) along the [024] atomic plane of a-AbO3 that was brief before going into strain relief in the compressive region but higher in magnitude than the 64 MPa (£22 = 0.00039±0.00024 for 14 minutes). Follow-on experiments indicate the presence of tensile strains within the bond coat region of the TBC system. After initial assessment of the effect of mechanical loading, our findings indicate that the effect of mechanical load during the cycle, often neglected in TBC studies, is of significance to the strain evolution within each cycle. This determination of critical conditions for strain evolution ( e.g. the first cycle) will serve to improve overall accuracy in life prediction of these coatings and contribute to developing methods of improving fatigue behavior.

The durability of Thermal Barrier Coatings (TBCs) used on the turbine blades of aircraft and power generation engines has been known to be affected by sand particle ingression comprised of Calcium-Magnesium-Alumina-Silicate (CMAS). Previous studies have shown that these effects present themselves through variations in the thermomechanical and thermochemical properties of the coating. This study investigated the impact of CMAS ingression on the Yttria Stabilized Zirconia Topcoat (YSZ) and Thermally Grown Oxide (TGO) strain in sprayed Thermal Barrier Coating (TBC) samples of varying porosity with and without CMAS ingression. In-Situ Synchrotron X-ray Diffraction measurements were taken on the sample under thermal loading conditions from which the YSZ and TGO peaks were identified and biaxial strain calculations were determined at high temperature. Quantitative strain results are presented for the YSZ and TGO during a thermal cycle. In-plane strain results for YSZ near the TGO interface for a complete thermal cycle are presented, for a 6% porous superdense sample with CMAS infiltration. The outcomes from this study can be used to understand the role of CMAS on the strain tolerance of the TBC coating. It is well known that under engine operational conditions the development of the TGO layer, with large critical stresses, has been linked to failure of the coating. The growth of the TGO manifests as undulations in a series of peaks and troughs. Understanding the mechanics of the oxide layer at these locations provides significant information with respect to the failure mechanisms of the TBC coating. This study investigated the stress at the peak and trough of a TGO undulation for a cycled Dense Vertically Cracked (DVC) plasma sprayed TBC sample through photo-luminescence (PL) spectroscopy. High resolution nanoscale stress maps were taken nondestructively in the undulation of the TGO. Preliminary results from first line mapping of TGO peak and trough scan, at a resolution of 200 nm, have shown a non-uniform TGO stress variation. The results obtained from this study can be used to understand the stress variation in the peak and trough of a DVC sample's TGO undulation and how it contributes to the life of the TBC coating.

Ce travail de thèse porte sur la déformation bi-axiale contrôlée de nano-composites W/Cu en couches minces déposées sur des substrats polyimides. La nano-structuration est obtenue par stratification de deux matériaux immiscibles (W et Cu) par pulvérisation ionique avec contrôle de la taille des grains au sein du film mince par contrôle de l'épaisseur selon la direction decroissance du film. Nous avons développé une procédure permettant de caractériser le comportement mécanique des échantillons à deux échelles différentes. L'essai de traction biaxial est couplé à la diffraction des rayons X (déformation microscopique) et à la corrélation d'images numériques (déformation macroscopique). Nous avons utilisé une machine de tractionbi-axiale développée dans le cadre d’un projet ANR sur la ligne de lumière DiffAbs du synchrotron SOLEIL. Elle permet de contrôler les contraintes dans des films minces supportés par des substrats polyimides. La confrontation des résultats obtenus par ces deux techniques dans le domaine d'élasticité a montré que la déformation est intégralement transmise via l’interfacefilm - substrat. La seconde étape de notre travail a consisté à étudier les déformations du nanocomposite W/Cu au-delà du domaine d’élasticité. Nous avons mis en évidence trois domaines de déformation associés à différents mécanismes de déformation. La limite d'élasticité du nanocomposite W/Cu a été déterminée en comparant la déformation élastique du film mince à la déformation macroscopique du substrat. Enfin, l'étude de la limite d'élasticité du nanocomposite W/Cu pour différents ratios de force a révélé un comportement fragile du nanocomposite W/Cu. / This thesis focuses on the biaxial deformation of W/Cu nanocomposite thin films deposited on polyimide substrates. The grain size in the thin film is controlled by stratification of two immiscible materials (W and Cu) employing sputtering techniques. We developed a procedure to characterize the mechanical behavior of samples at two different scales. A biaxial tensile test is coupled to X-ray diffraction (microscopic deformation) and digital image correlation (macroscopic deformation) techniques. We used a biaxial tensile setup developed in the framework of an ANR project on the DiffAbs beamline at synchrotron SOLEIL allowing forthe control of stresses in thin films supported by polyimide substrates. By comparing the strains obtained by these two techniques, the applied strain is determined to be transmitted unchanged in the elastic domain through the film - substrate interface. The second part of our work was to study the deformation of W/Cu nanocomposite beyond the elastic range. We have highlighted three domains of deformation associated with different deformation mechanisms. The elastic limit of the W/Cu nanocomposite was determined by comparing the elastic deformation of the thin film to the macroscopic deformation of the substrate. Finally, the elastic limit of W/Cu nanocomposite was studied for different load ratios. The overall results emphasized the brittle behavior of these nanocomposites.

Ce travail de thèse propose d'étudier les effets de taille et de microstructure sur les propriétés mécaniques de films minces d'or nanostructurés déposés sur des substrats flexibles lors d'essais de traction bi-axiale. Les couches minces d'or sont déposées sur du polyimide par pulvérisation ionique, technique qui permet de contrôler la taille des grains selon la direction de croissance dans les films minces en contrôlant l'épaisseur de ces derniers. Nous avons ensuite réalisé des expériences de déformation in-situ sur ces couches minces grâce à la machine de traction bi-axiale installée sur la ligne de lumière DiffAbs du synchrotron SOLEIL, source de rayons X intense qui permet de mesurer par diffraction les déformations dans les films minces polycristallins. La première étape de ce travail a été d'effectuer des expériences de traction bi-axiale pour des chargements dits « pas à pas » en imposant différents ratios de force sur deux séries de couches minces d’or d'épaisseurs différentes afin d'étudier la limite d'élasticité en fonction du chemin de chargement choisi et de tracer une surface de charge pour les deux séries d'échantillons d'or étudiés. La deuxième étape de ce travail a consisté à valider un mode de chargement dit « continu » en comparant les propriétés mécaniques d'une même série d'échantillons d'or obtenus avec ces deux types de chargements : « pas à pas » et « continu ». Une fois validé, nous avons réalisé des expériences de traction bi-axiale sur différentes séries d'échantillons d'or possédant différentes tailles grains et architecture afin de mettre en évidence un effet de taille sur les propriétés mécaniques de films minces nanométriques. / The main purpose of this thesis is to study the size and microstructure effects on the mechanical response of gold nanostructured thin films deposited on flexible substrates during biaxial tensile tests. Gold thin films are deposited onto polyimide substrates by sequenced ion sputtering technique in order to control the grain size in the growth direction. We have carried out in situ deformation experiments using the biaxial tensile device installed on the diffractometer of the DiffAbs beamline at synchrotron SOLEIL (Saint-Aubin, France), an intense X-rays source which allows to determine applied strains in polycrystalline thin films thanks to x-ray diffraction measurements. In a first step, we performed tensile biaxial tests for different load ratio using “step by step” procedure on two series of gold thin films showing different thicknesses in order to study the mechanical response analyzing the yield surface that can be extracted with the biaxial device. In a second step, we validated a continuous loading procedure which allows gaining a factor of 10 in the time frame. Validation is made by comparing the mechanical properties of two series of gold thin films investigated using “step by step” loading and “continuous” loading. After validation of the continuous loading procedure, tensile biaxial tests have been performed on different series of gold thin films with different grain size and architecture in order to put in highlight a size effect on the mechanical behavior of nanolayered thin films.