L'étude des propriétés optiques des matériaux semiconducteurs et, notamment, des composés émettant dans l'ultra-violet (UV) constitue depuis quelques années une thématique de recherche de plus en plus importante du fait des applications potentielles de ces matériaux en optoélectronique. Dans cette perspective, étudier les propriétés optiques du nitrure de bore hexagonal (hBN) et des nanotubes de nitrure de bore (BN) est particulièrement intéressant, étant donné leur caractère semiconducteur à grand gap (autour de 6 eV). <br /> L'objectif de cette étude est d'analyser les propriétés optiques de ces matériaux et, plus particulièrement, leurs effets excitoniques, en développant des méthodes de caractérisation optique adaptées pour observer des émissions UV.<br />Les techniques expérimentales de photoluminescence et de cathodoluminescence développées au cours de cette thèse ont tout d'abord permis de comprendre les propriétés de luminescence du hBN. Ainsi, nous avons pu confirmer la présence d'excitons libres émettant à 5.77 eV. Ensuite, en corrélant ces mesures optiques avec des analyses structurales en microscopie électronique en transmission de cristaux individuels, nous avons mis en évidence l'existence d'excitons liés à des défauts structuraux bien déterminés et émettant autour de 5.5 eV. Une fois les propriétés de luminescence du matériau massif connues, nous avons analysé de la même manière différents types de nanotubes de BN multifeuillets. Ces mesures ont pour la première fois montré que ces nano-objets émettent également dans l'UV. En se basant sur notre étude de la luminescence de hBN, nous proposons une interprétation pour l'origine de leurs émissions lumineuses UV.

<p>This thesis explores the possibilities of avoiding the issues generally associated with compression of noisy imagery, through the usage of vector quantization. By utilizing the learning aspects of vector quantization, image processing operations such as noise reduction could be implemented in a straightforward way. Several techniques are presented and evaluated. A direct comparison shows that for noisy imagery, vector quantization, in spite of it's simplicity, has clear advantages over MPEG-4 encoding.</p>

Transition metal oxides exhibit potential in various application fields due to the special d-electrons. Solid state chemistry focuses on discovering the structure-property relationships. The work in this thesis mainly discusses compounds with hexagonal or brownmillerite-type structure and their practical properties. Hexagonal YIn[subscript 1-x]Fe[subscript x]O��� (x = 0-0.3, 0.7-1.0) phases have been prepared and characterized. All phases appear to have the ferroelectric structure known for YInO���. The color of the phases changes from yellow to orange to dark red with increasing Fe content. Magnetic measurements confirm high-spin Fe����� for all phases. Similarly, solid solution YAl[subscript 1-x]Fe[subscript x]O��� (x = 0-0.4, 0.7-1.0) phases were successfully synthesized through the sol-gel method. The Al-rich compounds present paraelectric YAlO��� structure while the Fe-rich side samples exhibit YFeO��� structure. The color of the compounds appear to be yellow with small Fe content and change to brown which has higher Fe content. Brownmillerite-type oxides Ba���In[subscript 2-x]Mn[subscript x]O[subscript 5+x] (x = 0.1-0.7) have been prepared and characterized. Magnetic measurements confirm that Mn in as prepared samples is substituting as Mn������ for all values of x with observed paramagnetic spin-only moments close to values expected for two unpaired electrons. Neutron diffraction structure refinements show Mn������ occupies tetrahedral sites for orthorhombic (x = 0.1) and tetragonal (x = 0.2) phases. For Mn ��� 0.3 samples, neutron refinements show the phases are cubic with disordered cations and oxygen vacancies. The colors of the phases change from light yellow (x = 0) to intense turquoise (x =0.1), to green (x = 0.2, 0.3) or dark green (x ��� 0.4). Solid solution Ba���In[subscript 2-x]Fe[subscript x]O[subscript 5+y] (x = 0.1-1.5) also exhibit brownmillerite-type structure. The color of the compounds appear to be green with small Fe content and change to black with higher Fe content (x ��� 0.3). Magnetic measurements and M��ssbauer spectroscopy conclude the mixed valence of Fe�����/Fe������ for all the phases. Nonstoichiometry compound YCu���.���Ti���.���O[subscript 3-��] has been prepared and characterized. Structure study indicates that oxygen vacancy is favored under the synthesis condition. This change in oxygen content was further studied in the Mn-doped system. And the effect of stoichiometric difference in the Mn-doped samples was not as obvious as the initial compound. The disorder in the cation site enhanced the tolerance of the structure in the aspect of oxygen content. The hexagonal phases LnCu���.���Ti���.���O��� (Ln = Y, Tb-Lu) phases were prepared by the traditional solid state reactions. The prepared compounds were reduced at high temperature in the reduction atmosphere created by the H���/N��� gas mixture. Study on the structure and properties changes by reduction was conducted by X-ray diffraction, optical measurement, magnetic measurement and thermalgravimetric analysis. And we observed some evidence of the presence of Cu��� in the reduced phase by these characterization methods. Solid solution YMn[subscript x]Ti[subscript y]O[subscript 3-��] (y = 0.1-0.4) was successfully prepared through conventional solid state approach. All the samples showed hexagonal structure. But the structure transition from ferroelectric P6���cm to paraelectric P6���/mmc occurred when Ti amount is higher than 0.2. Based on the neutron diffraction refinement, the lattice expanded in the ab plane but contracted along the c axis direction. / Graduation date: 2013

Unintentional drop of munitions could be encountered during the storage, transportation, and loading processes. In such an impact, malfunctioning of crucial components of munitions is the worst scenario that may be encountered and level of loads should not reach to critical levels. From two possible methods, experimental one is not frequently applied owing to high cost of money and time. On the contrary, particularly in last couple of years, interest is shifted to numerical simulations such as finite element method. In this thesis, foam materials will be investigated as energy absorbers to reduce the effect of loads during the impact. However, modeling the behavior of foam materials by FE codes is a challenging task. In other words, more than a few material parameters which are not commonly specified in literature are sufficient to represent the behavior of foams in an appropriate way. For this reason, material characteristics of the selected two foam materials, expanded polypropylene and v polyethylene, have been obtained in this study. Characterization of EPP and PE is followed by the selection of the appropriate material models in LS-DYNA which is a nonlinear explicit finite element code. Drop tests of munitions on which initially specified foam materials are integrated were done to identify the load levels. Validation of drop tests which are explained in detail in this thesis has been accomplished by LS-DYNA. Final section of the thesis is related to optimization of the foam geometry which will provide reducing load levels to allowable limits. After optimization studies, three alternative geometries which succeed in to reduce loads to allowable load levels were reached. Finally, one of three alternatives is selected considering cost and manufacturing difficulties.

This thesis explores the possibilities of avoiding the issues generally associated with compression of noisy imagery, through the usage of vector quantization. By utilizing the learning aspects of vector quantization, image processing operations such as noise reduction could be implemented in a straightforward way. Several techniques are presented and evaluated. A direct comparison shows that for noisy imagery, vector quantization, in spite of it's simplicity, has clear advantages over MPEG-4 encoding.

Formation of hexagonal boron nitride (h-BN) by carbothermic reduction of B2O3 under nitrogen atmosphere at 1500oC was investigated. Reaction products were subjected to powder X-ray diffraction analysis, chemical analysis and were examined by SEM. B4C was found to exist in the reaction products of the experiments in which h-BN formation was not complete. One of the aims of this study was to investigate the role of B4C in the carbothermic production of h-BN. For this purpose, conversion reaction of B4C into h-BN was studied. B4C used in these experiments was produced in the same conditions that h-BN was formed, but under argon atmosphere. It was found that formation of h-BN from B4C&ndash / B2O3 mixtures was slower than activated C&ndash / B2O3 mixtures. It was concluded that B4C is not a necessary intermediate product in the carbothermic production of h-BN. Some additives are known to catalytically affect the h-BN formation. The second aim of this study was to examine the catalytic effect of some alkaline earth metal oxides and carbonates, some transition metal oxides and cupric nitrate. It was found that addition of 10wt% CaCO3 into the B2O3+C mixture was optimum for increasing the rate and yield of h-BN formation and decreasing the B4C amount in the products and that the reaction was complete in 2 hours. CaCO3 was observed to be effective in increasing the rate and grain size of the formed h-BN. Addition of cupric nitrate together with CaCO3 provided a further increase in the size of the h-BN grains.

Nous décrivons une nouvelle méthode de Chimie Douce permettant de préparer des oxydes possédant des structures ouvertes à canaux ou à feuillets par destruction à l'aide du dioxyde d'azote des ions ammoniums présents au sein de composé de départ. Un trioxyde de tungstène hexagonal a ainsi pu être préparé, permettant ensuite l'intercalation d'étain par voie organométallique.<br />La destruction des ions ammoniums a aussi mené, dans le cas de composés du cérium, à l'obtention d'oxyde de cérium finement divisé.<br />Cette méthode présente l'avantage de pouvoir être utilisée dans le cas de composés peu stables comme l'iodate d'ammonium.<br />Divers essais avec des ions alkyle-ammoniums beaucoup plus volumineux permettent aussi d'envisager l'accès à des oxydes de structures plus ouvertes.

Ziel der Diplomarbeit ist es, eine Dispersion aus Monomer und Silika-Partikeln auf ein festes Substrat aufzutragen, die so erhaltenen Versuchsträger mit dem Monomer/Partikel-Film (Modell Monomer/Partikel/festes Substrat) anschließend mit dem Rasterkraftmikroskop abzubilden und anschließend hinsichtlich der Oberflächenkrümmung und dem Kontaktwinkel zu untersuchen. Durch die Kontaktwinkelmessung am Dreiphasenpunkt soll eine erste Charakterisierung der kapillaren Oberfläche erfolgen, die jedoch nur ein Teilschritt bis zur vollständigen Optimierung von durch partikel-assistierte Benetzung hergestellte poröse Membranen ist.

This thesis presents a comprehensive study of the compressive response of hexagonal honeycomb panels from the initial elastic regime to a fully crushed state. Expanded aluminum alloy honeycomb panels with a cell size of 0.375 in (9.53 mm), a relative density of 0.026, and a height of 0.625 in (15.9 mm) are laterally compressed quasi statically between rigid platens under displacement control. The cells buckle elastically and collapse at a higher stress due to inelastic action. Deformation then first localizes at mid-height and the cells crush by progressive formation of folds; associated with each fold family is a stress undulation. The response densifies when the whole panel height is consumed by folds. The buckling, collapse, and crushing events are simulated numerically using finite element models involving periodic domains of a single or several characteristic cells. The models idealize the microstructure as hexagonal, with double walls in one direction. The nonlinear behavior is initiated by elastic buckling while inelastic collapse that leads to the localization observed in the experiments occurs at a significantly higher load. The collapse stress is found to be mildly sensitive to various problem imperfections. For the particular honeycomb studied, the collapse stress is 67% higher than the buckling stress. It was also shown that all aspects of the compressive behavior can be reproduced numerically using periodic domains with a fine mesh capable of capturing the complexity of the folds. The calculated buckling stress is reduced when considering periodic square domains as the compatibility of the buckles between neighboring cells tends to make the structure more compliant. The mode consisting of three half waves is observed in every simulation but its amplitude is seen to be accented at the center of the domains. The calculated crushing response is shown to better resemble measured ones when a 4x4 cell domain is used, which is smoother and reproduces decays in the amplitude of load peaks. However, the average crushing stress can be captured with engineering accuracy even from a single cell domain. / text

Le projet de thèse, mené en collaboration avec le laboratoire Medesis Pharma, porte sur la mise au point de deux formulations pharmaceutiques, une microémulsion inverse et un gel colloïdal, à base de Pécéol®, lécithine, éthanol et eau. Le lithium indiqué dans le traitement de maladies neurodégénératives a été utilisé comme un modèle de principe actif hydrophile dans le cadre de ce projet. Ce travail a été initié par l’étude du comportement de phases du mélange quaternaire Pécéol®/lécithine/éthanol/eau, mettant essentiellement l’accent sur les différents paramètres impliqués dans les transitions de phases, dans le but de déterminer le rôle du Pécéol® et de la lécithine dans la structuration du système.- L’étude des propriétés structurales de la microémulsion, dans le domaine riche en Pécéol®, a montré que la structure du système n’est pas cohérente avec un modèle classique de micelles sphériques, l’hypothèse d’une structure localement lamellaire a été proposée. Les propriétés de solubilisation de la microémulsion ont été évaluées par l’élaboration d’une série de diagrammes de phases pseudo-ternaires, en faisant varier le rapport éthanol/lécithine. Une efficacité optimale a été obtenue pour un rapport éthanol/lécithine égal à 40/60. La formulation optimisée est capable d’incorporer efficacement le lithium (Li), à des concentrations acceptables sans altérer la stabilité du système. L’étude des propriétés d’incorporation du Li dans la microémulsion a montré que le mécanisme d’encapsulation est compatible avec un modèle d’interactions de type drug-surfactant. Les résultats des études de stabilité de la microémulsion vide et chargée en Li menées selon les conditions ICH sont satisfaisants.- La structuration du gel clair, dans le domaine riche en lécithine, a été suivie par des analyses de rhéologie et de microscopie en lumière polarisée en fonction du rapport lécithine/Pécéol®. Les résultats ont montré que les propriétés rhéologiques du gel peuvent être modifiées en ajustant le rapport lécithine/Pécéol®. La caractérisation de la structure du gel clair par diffraction de rayons X aux petits angles (SAXS) et cryofracture conjuguée à la microscopie électronique en transmission (FF-TEM) a mis en évidence une structure anisotrope hexagonale H2. Alors que dans le domaine riche en eau, une structure anisotrope hexagonale inverse H2 et lamellaire Lα a été mise en évidence. Les propriétés rhéologiques modulables du gel dans le domaine riche en lécithine ainsi que sa grande capacité de rétention d’eau, sont particulièrement intéressantes pour une application du gel clair dans le domaine de pharmaceutique et/ou cosmétique. / This thesis project, carried out in collaboration with Medesis Pharma laboratory, is about the development of two pharmaceutical formulations, a reverse microemulsion and a colloidal gel, based on Pécéol®, lécithine, ethanol and water. The indicated lithium in the treatment of neurodegenerative diseases has been used as a hydrophilic principal active model for this project. This work started with the study of the phase behavior of the four component system Pécéol®/lecithin/éthanol/water, focusing primarily on the various parameters involved in phase transitions in order to determine the role of Pécéol® and lecithin in the structuring of the system.- The study of the structural properties of the reverse microemulsion, in the Pécéol® rich domain, showed that the system structure is not coherent with a classical model of spherical micelles, a hypothesis of a local lamellar structure was proposed. The solubilization properties of the microemulsion were evaluated following the development of a series of pseudo-ternary phase diagrams, by varying the ethanol/lecithin ratio. Optimal efficiency was obtained for an ethanol/lecithin ratio of 40/60. The optimized formulation is capable of effectively incorporating lithium (Li) to acceptable concentrations without altering the stability of the system. The study of the incorporation properties of Li in the microemulsion has shown that the encapsulation mechanism is compatible with drug-surfactant binding model. The results of the stability studies of the free and Li loaded microemulsion, conducted according to ICH conditions, are satisfactory.- The gel structuring was followed, in the lecithin rich domain, through rheological and optical microscopy analyses, according to lecithin/Pécéol® ratio. Results showed that the rheological properties of the gel can be modified by adjusting the lecithin/Pécéol® ratio. Moreover, the characterization of the gel structure through Small Angle X-Ray Scattering (SAXS) and Freeze Fracture-Transmission Electron Microscopy (FF-TEM) showed an inverse hexagonal phase H2. While, in the water rich region, an inverse hexagonal H2 and lamellar Lα phases were identified. The adjustable rheological properties of the clear gel, and its great water solubilisation capacity, are particularly interesting for the application of the gel in pharmaceutical and/or cosmetic fields.