Les piles à combustible Solid Oxide Fuel Cell sont des systèmes de production d’électricité. Une cellule élémentaire est un multicouche constitué de matériaux céramiques et de métal. Elles sont très sensibles aux contraintes mécaniques générées lors des cycles thermiques et d’oxydo-réduction, limitant leur durée de vie.Ce travail a porté sur la détermination expérimentale des contraintes résiduelles dans des cellules SOFC à anode support en fonction des sollicitations du système. Parallèlement à des mesures in-situ en température, une approche multi-échelles a été développée pour évaluer les hétérogénéités de contraintes dans l’électrolyte liées à la forte anisotropie élastique de la zircone yttriée qui le constitue. Différentes techniques ont été mise en œuvre afin de couvrir les 3 ordres de contraintes. Les mesures à l’échelle macroscopique ont été effectuées par diffraction de rayons X de laboratoire (méthode des sin²(Ψ)). La microdiffraction de rayonnement synchrotron en mode faisceau blanc et monochromatique a permis, après un important travail d’amélioration du protocole de mesure et d’analyse, de déterminer les tenseurs complets de contraintes et déformations grain à grain dans l’électrolyte. Les déformations intra-granulaires ont été évaluées par une technique d’EBSD.Les résultats obtenus ont permis d’analyser les mécanismes principaux qui régissent les évolutions de contraintes dans l’électrolyte. Des hétérogénéités de contraintes entre grains liées à leurs orientations cristallographiques ont été mises en évidence. Au-delà du problème des SOFC, les techniques mises en œuvre ouvrent la voie aux validations expérimentales des modèles mécaniques poly-cristallins. / The Solid Oxide Fuel Cells (SOFC) are high-performance electrochemical devices for energy conversion. A single cell is composed of layers made of different ceramic materials and metal. The mechanical integrity of the cell is a major issue during its lifetime. Damage of the cells is mainly due to the high operating temperature, the “redox” behavior of the anode and the brittleness of the involved materials. In this work, residual stresses in the electrolyte of a planar anode-supported SOFC have been experimentally measured for different treatments of the cell. In situ analysis at various temperatures has been performed. A multi-scale approach has been developed to study the expected strain-stress heterogeneities in the electrolyte due to the strong elastic anisotropy of the involved material (yttria-stabilized zirconia). Different techniques have been used to determinate stresses at the 3 different orders. Macroscopic stresses were studied using the Sin2 method on a laboratory X-ray goniometer. The complete strain and stress tensors of individual grains in the electrolyte have been determinate, after various improvements in the technique, by combining the diffraction of white and monochromatic micro beams produced by synchrotron source. Strain variation into grains has been evaluated using EBSD.This study has identified the main phenomena that control the stresses variation in the electrolyte layer. Stresses heterogeneities from grain to grain have been found and linked to the crystallographic orientation. Beyond SOFC’s considerations, the techniques that have been developed should permit an experimental validation of mechanical modeling to polycrystalline materials.

The primary aim of this research was to develop and improve the experimental method and data interpretation for strain measurements using diffraction methods to gain a better understanding of micromechanical deformation and anisotropy of lattice strain response. Substantial part of the research was devoted to the development of the laboratory high energy X-ray diffractometer (HEXameter) for bulk residual strain evaluation. White beam energy dispersive X-ray diffraction was chosen as the principal diffraction mode due to its extreme efficiency in utilising X-ray flux and its ability to capture large segments of diffraction patterns. The specimens that have been examined were real engineering components, mechanically deformed specimens and thermally treated specimens, ranging from dynamic in-situ measurements to ex-situ materials engineering. For the real engineering components, a wedge coupon from the trailing edge of a Ti64 wide fan blade and a turbine combustion casing were examined. Among the mechanically deformed specimens that have been measured were shot-peened steel plates, elasto-plastically bent bars of Mg alloy and cold expanded Al disks. Amongst the thermally deformed specimens, laser-formed steel plates, thermal spray coatings, a manual inert gas weld of Al plates, a friction stir weld of Al plates and Ni tubes and a quenched Ni superalloy cylinder used for strain tomography were studied. In-situ loading experiments have also been carried out, such as experiments on pointwise mapping of grain orientation and strain using the 3DXRD microscope at the ESRF and in-situ loading experiments on titanium alloy, rheo-diecast and high pressure diecast Mg alloy, IN718 Ni-base superalloy and Al2024 aluminium alloy. Experimental results from X-Ray diffraction and strain tomography were used to achieve a better understanding of the material properties. Some results were compared with polycrystal Finite Element model predictions. Amongst the most prominent research achievements are the development on the HEXameter laboratory instrument, including: (i) the development of special collimation systems for the detectors and the source tube; (ii) the development of a twin-detector setup (that allows for simultaneous determination of strain in two mutually orthogonal directions); (iii) improved alignment procedures for better performance; and (iv) the adaptation of instrumentation for efficient scanning of both large and small components, that included choosing and adapting translation devices, programming of the translation system and designing sample mounting procedures. In this research several approaches to data treatment were investigated. Quantitative phase analysis, single peak fitting (using custom Matlab routines and GSAS) and full pattern fitting (with individual pattern data refined by GSAS and batch refinement done by invoking GSAS via a Matlab routine) were applied. Different Matlab routines were written for specific experimental setups; and various analysis methods were selected and used for refinement depending on the requirements of the measurement results interpretation. 16 papers were published, ensuring that the results of this thesis are readily available to other researchers in the field.

Many physical properties, for example structural or magnetic, of a material are directly dependent on elemental composition. Tailoring of properties through highly accurate composition control is possible in thin films. This work exemplifies such tailoring. A short review is given of the current status for research in the area of permanent magnets, focusing on rare earth element free alternatives, where FeNi in the L10 phase is a possible candidate. Epitaxial FeNi L10 thin films were successfully synthesized by magnetron sputtering deposition of monoatomic layers of Fe and Ni on HF-etched Si(001) substrates with Cu or Cu100-xNix/Cu buffers. The in-plane lattice parameter aCuNi of the Cu100-xNix buffer layer was tuned by the Ni content. Through matching of aFeNi to aCuNi, the strain state (c/a)FeNi was controlled, where c is the out-of-plane lattice parameter. The 001 reflection indicative of chemical order, as measured by resonant x-ray diffraction, was in most cases split in two peaks due to a composition modulation of Fe and Ni. This chemical disorder contributed to that the uniaxial magnetocrystalline anisotropy energy, KU≈0.35 MJ/m3, was smaller than predicted. In later experiments the composition modulation could partly be compensated for. Remaining discrepancies with respect to predicted KU values were attributed to additional disorder induced by surface roughness of the buffer layer. The interface sharpness between Fe and Ni was explored by producing epitaxial symmetric multilayers with individual layer thicknesses n = 4-48 monolayers (ML). For n ≤ 8 ML the films had pure fcc structure, with antiferromagnetic Fe layers. For n ≥ 8 ML the Fe layers relaxed to bcc structure. A combinatorial sputter chamber, which has the capability to deposit samples with composition and thickness gradients, was assembled. A model for simulation of composition and thickness across large substrates, for the conditions in this chamber, is presented. The model is verified by comparison to experimental data. Some challenges inherent in combinatorial sputtering are discussed, and two experimental studies employing the technique are presented as examples. These investigated magnetic and structural properties of Tb-Co films, with 7-95 at.% Tb, and of amorphous and crystalline ternary gradient Co-Fe-Zr films, respectively.

Les complexes de la famille des ansa-chromocènes sont relativement peu nombreux, mais ils ont tout de même démontré des réactivités intéressantes comme la possibilité de coordonner une molécule de monoxyde de carbone au centre métallique sans être sous pression constante de gaz, ce qui n’est pas le cas pour l’homologue chromocène. L’ansa-chromocène le plus surprenant est sans doute le Me2Si(C5Me4)2Cr, car il est le seul qui ne comporte pas de ligand autre que celui de type ansa. Cependant, ce composé a été obtenu sans que le mécanisme de la réaction ne soit compris et prouvé, seul un mécanisme proposé a été publié. Au cours de cette étude, le mécanisme proposé a tout d’abord été infirmé grâce à de nombreuses expériences qui ont mené à l’élaboration d’un nouveau mécanisme. Par la suite, la réactivité du Me2Si(C5Me4)2Cr a été approfondie en le faisant réagir avec divers réactifs. Aucun produit d’addition oxydante n’a été isolé, mais la réaction avec l’isonitrile forme un complexe asymétrique avec deux isonitriles coordonnés. La détermination du moment magnétique du composé Me2Si(C5Me4)2Cr confirme la présence de deux électrons non-pairés à la température de la pièce et évoque la possibilité d’une transition à S=2 à température plus élevée. La synthèse de nouveaux complexes de type ansachromocène insaturé a été tentée avec d’autres ligands ansa, et la réaction avec [C2H4(C9H6)2]Li2 mène à un complexe dimérique avec des ligands indényles pontés. / Only a few ansa-chromocenes complexes are known but some of them have shown interesting reactivities such as the ability to coordinate a carbon monoxide molecule to the chromium center without being under continuous gas pressure, which is not the case for the chromocene analogue. The most surprising ansa-chromocene is without doubt Me2Si(C5Me4)2Cr, because it is the only example of an ansa-chromocene lacking additional ligands. However, the compound was obtained by accident and the mechanism of its formation was neither well established nor understood. Only a tentative mechanism was published. During the course of the present study, the proposed mechanism has been disproved by a series of experiments that led to the elaboration of a new mechanism. The reactivity of Me2Si(C5Me4)2Cr has been studied by reactions with various compounds. No oxidative addition product was isolated, but the reaction with isonitrile yielded an asymmetric complex with two isonitriles coordinated to chronium. The determination of the magnetic moment of this complex confirmed two unpaired electrons at room temperature and indicated the possibility of an S=2 transition at higher temperature. The synthesis of new unsaturated ansa-chromocene complexes has been attempted with other ansa ligands, and the reaction with [C2H4(C9H6)2]Li2 led to a dimeric complex with bridged indenyl ligands.

In this thesis, the discharge products formed at the cathode and the performance and cell chemistry of sodium-oxygen batteries have been studied. This was carried out using different NaOTf salt concentrations. The influence of different salt concentrations on sodium-oxygen batteries was investigated since it has been shown that increasing the salt concentration beyond conventional concentrations could result in advantages such as increased stability of the electrolytes towards decomposition, higher thermal stability and lower volatility. An increase in salt concentration has also been shown to influence the electrochemical potential window. The solubility of NaOTf was investigated in two different solvents, DME and diglyme. NaOTf was found to be more soluble in DME compared to diglyme but due to the volatile nature of DME, three different concentrations of NaOTf were prepared with diglyme as solvent. Experimentation involved discharging the batteries to either maximum or limited capacity. The discharge products were examined and characterized using XRD and SEM. The main discharge product was identified as sodium superoxide although sodium peroxide dihydrate was also identified in one battery. A trend of higher capacity and voltage plateaus with higher salt concentration was also found. The influence of trace amounts of water was suggested as one explanation as it works as a catalyst, promoting sodium superoxide cube growth due to improved transportation of superoxide. Another or contributing explanation could be a possible change in donor number with increased salt concentration, resulting in higher solubility and longer lifetime of superoxide, promoting the growth of sodium superoxide cubes.

Eutrophication due to excess loading of phosphorus (P) is a leading cause of water quality degradation within the United States. The aim of this study was to investigate P removal and recovery with 12 materials (four calcite varieties, wollastonite, dolomite, hydroxylapatite, eggshells, coral sands, biochar, and activated carbon. This was accomplished through a series of batch experiments with synthetic wastewater solutions ranging from 10-100 mg PO₄-P/ L. The results of this study were used to establish large-scale, calcite-based column filter experiments located in the Rubenstein School of Environment and Natural Resources' Eco-Machine. Influent and effluent wastewater samples were routinely collected for 64 days. Measures of filter performance included changes in pH, percent reduction and mass adsorbed of P. After the columns reached saturation, filter media was analyzed for the mineralogical content by X-ray powder diffraction (XRD). In the batch experiments, P removal and recovery varied among the media and across treatments. The best performing minerals were calcite, wollastonite, and hydroxylapatite. Eggshells, activated carbon, and coral sands also reduced and adsorbed P. The remaining materials had the lowest reductions and adsorption of P. Results from batch experiments informed the design of large column filters within the Rubenstein School of the Environment and Natural Resources' Eco-Machine. Removal and adsorption rates of P by the three column filters were similar. The columns achieved an average P reduction of 12.53% (se = 0.98) and an average P adsorption of 0.649 mg PO₄-P/ kg media (se = 0.03) over a 4-h hydraulic retention time. Paired T-tests showed that P reductions were statistically significant (p-value < 0.05) on the majority of sampling dates until the columns reached saturation. Saturation was reached after 31 days for two of the columns and 36 days for the third column. The filter media consistently buffered the pH of the wastewater to approximately 6.0-7.0 with no indication of diminishing buffer capacity after saturation. XRD analysis was not able to detect any P species within the crystalline structure of the filter media. This research contributes to the understanding of how the selected media perform during P removal and recovery programs, while providing information on the performance of large column filters operating within advanced, ecologically engineered wastewater treatment systems.

The crystal structure of a new bismuth-based light-absorbing material for the application in solar cells was determined by single crystal X-ray diffraction for the first time. (CH3NH3)3(Bi2I9) (MBI) is a promising alternative to recently rapidly progressing hybrid organic–inorganic perovskites due to the higher tolerance against water and low toxicity. Single crystal X-ray diffraction provides detailed structural information as an essential prerequisite to gain a fundamental understanding of structure property relationships, while powder diffraction studies demonstrate a high degree of crystallinity in thin films.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Afin de mieux comprendre les évolutions structurales mises en évidence dans les oxydes lamellaires de formule générale Li1+x(Ni0.425Mn0.425Co0.15)O2 utilisés comme électrode positive pour batterie lithium-ion, la structure du composé Li2MnO3 a été étudiée en détail. Obtenu selon différentes voies de synthèses, réalisées à différentes températures, ce matériau qui peut être considéré comme un matériau model à fait l’objet d’une étude cristallographique où l’utilisation de la microscopie électronique a été privilégiée. Deux types de défauts ont été identifiés. D’une part, l’existence de fautes d’empilement au sein du matériau a été démontrée. Leurs conséquences sur les clichés de diffraction électronique et les diagrammes de diffraction des rayons-X ont étés expliquées permettant d’unifier les controverses présentent à ce sujet dans la littérature. D’autre part, l’étude de la stabilité thermique du composé Li2MnO3 a mis en évidence l’apparition de défauts de type « phase spinelle » en surface des grains lorsque la température de traitement thermique devient supérieure ou égale à 900°C. Le traitement du matériau par la voie acide a pu être étudié et le mécanisme de désintercalation chimique du lithium par la voie acide a finalement pu être précisé. Il est montré que ce mécanisme est le même quelle que soit la taille des particules. / In order to get a better understanding of the complex structural evolutions occurring in the layered oxides like Li1+x(Ni0.425Mn0.425Co0.15)O2 materials when they are used as positive electrodes in lithium batteries, the structure of Li2MnO3 has been studied in detail. Obtained from several synthesis ways, annealed at various temperatures, this compound that can be considered as a model one regarding these complex materials has been the object of a crystallographic study where the use of electron microscopy was privileged. Two kinds of defects could be identified. From one part, the existence of stacking faults in the Li2MnO3 material has been proved and they have been visualized for the first time. Their consequences on X ray and electron diffraction patterns are explained allowing the unification of discrepancies existing in the bibliography. For other part, the study of the thermal stability of Li2MnO3 evidenced the appearance of spinel type defects when the annealing treatment is performed above 900°C. Finally the delithiation by acid leaching is studied and the lithium extraction mechanism is clarified. It is shown that this mechanism is the same whatever the particle size is.

The thesis deals with the application of nondestructive testing methods (acoustic emission, electron microscopy, X-ray diffraction topography) to description and identification of stages in the fatigue process in aluminium alloys. The main contribution of this dissertation thesis consists of the approach and evaluation methodology of cyclic damage in the materials. It dealt especially with the verification of measured data by using data obtained using other nondestructive methods. The experimental results show that the field of nondestructive testing materials can fundamentally uncover the process of fatigue damage and improve current knowledge in this area. Combination of used methods has become a powerful tool for the identification and monitoring of the whole fatigue degradation process of materials.