Optimization of Li-ion solid electrolytes

The synthesis and optimization of two Li-ion solid electrolytes were studied in this work. Different combinations of precursors were used to prepare La0.5Li0.5TiO3 via mechanosynthesis. Despite the ability to form a perovskite phase by the mechanochemical reaction it was not possible to obtain a pure La0.5Li0.5TiO3 phase by this process. Of all the seven combinations of precursors and conditions tested, the one where La2O3, Li2CO3 and TiO2 were milled for 480min (LaOLiCO-480) showed the best results, with trace impurity phases still being observed. The main impurity phase was that of La2O3 after mechanosynthesis (22.84%) and Li2TiO3 after calcination (4.20%). Two different sol-gel methods were used to substitute boron on the Zr-site of Li1+xZr2-xBx(PO4)3 or the P-site of Li1+6xZr2(P1-xBxO4)3, with the doping being achieved on the Zr-site using a method adapted from Alamo et al (1989). The results show that the Zr-site is the preferential mechanism for B doping of LiZr2(PO4)3 and not the P-site. Rietveld refinement of the unit-cell parameters was performed and it was verified by consideration of Vegard’s law that it is possible to obtain phase purity up to x = 0.05. This corresponds with the phases present in the XRD data, that showed the additional presence of the low temperature (monoclinic) phase for the powder sintered at 1200ºC for 12h of compositions with x ≥ 0.075. The compositions inside the solid solution undergo the phase transition from triclinic (PDF#01-074-2562) to rhombohedral (PDF#01-070-6734) when heating from 25 to 100ºC, as reported in the literature for the base composition. Despite several efforts, it was not possible to obtain dense pellets and with physical integrity after sintering, requiring further work in order to obtain dense pellets for the electrochemical characterisation of Li Zr2(PO4)3 and Li1.05Zr1.95B0.05(PO4)3.

Coupling of magnetic, strain and electric polarization fields in the structure of multiferroic material

The comprehensive study on the coupling of magnetism, electrical polarization and the crystalline lattice with the off-stoichiometric effects in self-doped multiferroic hexagonal h-LuMnxO3±δ (0.92≤x≤1.12) ceramic oxides was carried out for the PhD work. There is a complex coupling of the three ferroic degrees. The cancelation of the magnetic moments of ions in the antiferromagnetic order, electric polarization with specific vortex/antivortex topology and lattice properties have pushed researchers to find out ways to disclose the underlying physics and chemistry of magneto-electric and magneto-elastic couplings of h-RMnO3 multiferroic materials. In this research work, self-doping of Lu-sites or Mn-sites of h-LuMnxO3±δ ceramics prepared via solid state route was done to pave a way for deeper understanding of the antiferromagnetic transition, the weak ferromagnetism often reported in the same crystalline lattices and the ferroelectric properties coupled to the imposed lattice changes. Accordingly to the aim of the PhD thesis, the objectives set for the sintering study in the first chapter on experimental results were two. First, study of sintering off-stoichiometric samples within conditions reported in the bibliography and also extracted from the phase diagrams of the LuMnxO3±δ, with a multiple firings ending with a last high temperature step at 1300ºC for 24 hours. Second, explore longer annealing times of up to 240 hours at the fixed temperature of 1300 ºC in a search for improving the properties of the solid solution under study. All series of LuMnxO3±δ ceramics for each annealing time were characterized to tentatively build a framework enabling comparison of measured properties with results of others available in literature. XRD and Rietveld refinement of data give the evolution the lattice parameters as a function to x. Shrinkage of the lattice parameters with increasing x values was observed, the stability limit of the solid solution being determined by analysis of lattice parameters. The evolution of grain size and presence of secondary phases have been investigated by means of TEM, SEM, EDS and EBSD techniques. The dependencies of grain growth and regression of secondary phases on composition x and time were further characterized. Magnetic susceptibility of samples and magnetic irreversibility were extensively examined in the present work. The dependency of magnetic susceptibility, Neel ordering transition and important magnetic parameters are determined and compared to observation in other multiferroics in the following chapter of the thesis. As a tool of high sensitivity to detect minor traces of the secondary phase hausmannite, magnetic measurements are suggested for cross-checking of phase diagrams. Difficulty of previous studies on interpreting the magnetic anomaly below 43 K in h-RMnO3 oxides was discussed and assigned to the Mn3O4 phase, with supported of the electron microscopy. Magneto-electric coupling where AFM ordering is coupled to dielectric polarization is investigated as a function of x and of sintering condition via frequency and temperature dependent complex dielectric constant measurements in the final chapter of the thesis. Within the limits of solid solubility, the crystalline lattice of off-stoichiometric ceramics was shown to preserve the magneto-electric coupling at TN. It represents the first research work on magneto-electric coupling modified by vacancy doping to author’s knowledge. Studied lattices would reveal distortions at the atomic scale imposed by local changes of x dependent on sintering conditions which were widely inspected by using TEM/STEM methods, complemented with EDS and EELS spectroscopy all together to provide comprehensive information on cross coupling of distortions, inhomogeneity and electronic structure assembled and discussed in a specific chapter. Internal interfaces inside crystalline grains were examined. Qualitative explanations of the measured magnetic and ferroelectric properties were established in relation to observed nanoscale features of h-LuMnxO3±δ ceramics. Ferroelectric domains and topological defects are displayed both in TEM and AFM/PFM images, the later technique being used to look at size, distribution and switching of ferroelectric domains influenced by vacancy doping at the micron scale bridging to complementary TEM studies on the atomic structure of ferroelectric domains. In support to experimental study, DFT simulations using Wien2K code have been carried out in order to interpret the results of EELS spectra of O K-edge and to obtain information on the cation hybridization to oxygen ions. The L3,2 edges of Mn is used to access the oxidation state of the Mn ions inside crystalline grains. In addition, rehybridization driven ferroelectricity is also evaluated by comparing the partial density of states of the orbitals of all ions of the samples, also the polarization was calculated and correlated to the off-stoichiometric effect.

Amélioration de la résolution spatiale de simulations de neige du modèle SNOWPACK dans un contexte de l'accès à la nourriture du caribou de Peary

Le caribou de Peary, désigné en voie de disparition, n’est pas épargné par les changements climatiques. Par le passé, des hivers successifs caractérisés par des conditions météorologiques extrêmes ont entrainé des déclins importants de population en quelques années, pouvant aller jusqu’à 98 %. L’augmentation des épisodes de redoux hivernaux et de pluies sur neige réduit les conditions d’accès à la nourriture de cette sous-espèce. Ces conditions ont pour conséquence d’augmenter la densité des couches de neige dans le manteau neigeux, ce qui empêche le caribou d’avoir accès au fourrage couvrant le sol en hiver. Dans cet esprit, l’outil de spatialisation de SNOWPACK dans l’Arctique (OSSA) développé dans Ouellet et al. (2016) permet la spatialisation des conditions d’accès à la nourriture du caribou de Peary en utilisant le modèle de simulation du couvert nival SNOWPACK. Le paramètre du couvert nival utilisé est l’épaisseur cumulée au-delà d’un seuil fixe de densité durant la saison hivernale (ECD). L'OSSA fournit un résultat d’une résolution spatiale de 32 km puisque les données météorologiques utilisées sont les données de réanalyses du North American Regional Reanalysis (NARR) qui possède une résolution de 32 km. Cette résolution grossière ne permet pas de documenter et prédire la migration locale des différentes populations sur les îles de l'archipel arctique canadien. L’objectif principal de ce projet est donc d’évaluer le potentiel d'une approche de raffinement spatial de l'OSSA à une résolution de 1 km. Afin d’affiner la résolution spatiale de la simulation de l’ECD, des données de pente et de l’albédo du sol à une résolution de 1 km ont été utilisées. Avant d’effectuer les simulations à haute résolution, la sensibilité de l’ECD à ces deux paramètres du terrain a été testée. Les simulations préliminaires ont permis de démontrer que plus la pente est élevée, plus l’ECD sera faible. Également, il a été identifié que la pente va affecter l’ECD à partir d’un seuil de 3 degré. L’albédo du sol a aussi un impact significatif sur l’ECD, mais à un niveau moins important que la pente. Finalement, la comparaison des résultats à faible et haute résolution a pu démontrer que l’approche de raffinement spatial appliquée permet d’obtenir une information plus détaillée des conditions d’accès à la nourriture du caribou de Peary. Les résultats d’ECD obtenus à 1 km de résolution montrent des écarts avec l’ECD à 32 km de résolution pouvant dépasser les 2000 cm. Finalement, cette étude montre l’intérêt d’automatiser cette approche afin de pouvoir spatialiser les conditions d’accès à la nourriture à une résolution de 1 km et de prédire certaines micro-variabilités dans les déplacements futurs des caribous de Peary en fonction des changements climatiques.

Le pilocentrisme de la France d’Ancien Régime : évolution des représentations de la pilosité de François 1er à Louis XVI

Thèse réalisée en cotutelle avec la direction de Jean-Jacques Courtine à l'Université de Paris III Sorbonne Nouvelle sous la discipline anthropologie et avec la direction de Dominique Deslandres à l'Université de Montréal sous la discipline histoire

GeoGebraTUTOR : développement d’un système tutoriel autonome pour l’accompagnement d’élèves en situation de résolution de problèmes de démonstration en géométrie plane et genèse d’un espace de travail géométrique idoine

Travaux d'études doctorales réalisées conjointement avec les travaux de recherches doctorales de Nicolas Leduc, étudiant au doctorat en génie informatique à l'École Polytechnique de Montréal.

Celdas de pilas de oxidó solido, avance en el procesado de materiales

Póster presentado en el XIV Congreso Nacional de Materiales (CNMAT) en Gijón (España), del 8 al 10 de Junio de 2016

Preparación y caracterización de biomateriales híbridos de hidroxiapatito con fosfonato (2-Hidroxi fosfonoacetato)

El hidroxiapatito es el biomineral de los tejidos duros de los mamíferos y por ello ha sido ampliamente estudiado como biomaterial en cementos óseos, recubrimientos de metales implantables y scaffold en ingeniería de tejidos. En este trabajo, se estudia un proceso síntesis y caracterización de un derivado de este material, donde el ion fosfonato: 2- hidroxifosfonoacetato sustituye parcialmente al ion fosfato [1-10%]. El proceso de síntesis de hidroxiapatito consiste en dos etapas: (1) una reacción a 100ºC entre el ácido fosfórico (añadido lentamente) y una mezcla de hidróxido de calcio + 2-hidroxifosfonoacetato de calcio (Relación Ca/P=1.67). (2) un tratamiento térmico de los sólidos obtenidos en (1) a 150ºC. Los productos finales se han caracterizado mediante análisis químico, análisis termogravimétrico, difracción de rayos-X con análisis de Rietveld, microscopía SEM y determinación de la superficie específica y porosidad. En las fases cristalinas, el grado de pureza de los hidroxiapatitos oscila entre 91-100%. Todos presentan estructura monoclínica, en contraste con la estructura hexagonal que habitualmente se obtiene aplicando métodos de síntesis similares. Esta variación se atribuye a la presencia de fosfonato. El contenido de éste también influye en la morfología y en la porosidad de los materiales, siendo las muestras con más fosfonato las más porosas. Los materiales, al menos aquellos con una cantidad menor o igual 5% de fosfonato, muestran una biocompatibilidad similar a un material de hidroxiapatito de referencia.

Estudo da moagem de alta energia e sinterização de pós compósitos W-Cu

The Tungsten/copper composites are commonly used for electrical and thermal objectives like heat sinks and lectrical conductors, propitiating an excellent thermal and electrical conductivity. These properties are dependents of the composition, crystallite size and production process. The high energy milling of the powder of W-Cu produces an dispersion high and homogenization levels with crystallite size of W very small in the ductile Cu phase. This work discusses the effect of the HEM in preparation of the W-25Cu composite powders. Three techniques of powder preparation were utilized: milling the dry with powder of thick Cu, milling the dry with powder of fine Cu and milling the wet with powder of thick Cu. The form, size and composition of the particles of the powders milled were observed by scanning electron microscopy (SEM). The X-ray diffraction (XRD) was used to analyse the phases, lattice parameters, size and microstrain of the crystallite. The analyse of the crystalline structure of the W-25Cu powders milled made by Rietveld Method suggests the partial solid solubility of the constituent elements of the Cu in lattice of the W. This analyse shows too that the HEM produces the reduction high on the crystallite size and the increase in the lattice strain of both phases, this is more intense in the phase W