Neste trabalho realizamos um estudo do comportamento do momento magnético e do deslocamento isomérico de uma impureza intersticial de Fe em hospedeiros metálicos de valências 4 (Ti, Zr), 3 (Sc, Y). Investigamos também impurezas intersticiais e substitucionais de Mo e Fe em hospedeiros divalentes. Para realizar este estudo fizemos cálculos de estrutura eletrônica utilizando o RS-LMTO-ASA (\"Real Space - Linear Muffin-Tin Orbital - Atomic Spherical Approximation\"), um método de primeiros princípios dentro da aproximação do funcional densidade local, implementado no espaço real. Calculamos o momento magnético no sítio da impureza nos sistemas acima e constatamos que a impureza intersticial de Fe é não magnética nos hospedeiros de valências 4 e 3, e que tanto as impurezas intersticiais como as substitucionais podem apresentar momento magnético nos hospedeiros divalentes. Mostramos que para os sistemas divalentes o momento magnético depende fortemente da relaxação. Os nossos resultados são explicados através de um modelo simples, baseado no modelo de Wolff. Investigamos também o comportamento do deslocamento isomérico no sítio da impureza de Fe nesses vários sistemas. Constatamos que os nossos resultados concordam razoavelmente bem com os dados experimentais e explicam o comportamento das tendências observadas. / In the present work, we have studied the magnetic moments and the behavior of the isomer shift at the interstitial Fe impurity site in Ti, Sc, Zr and Y hosts. We have also investigated interstitial and substitutional Fe and Mo impurities in Ca, Sr and Yb hosts. To perform the calculations, we have used the RS-LMTO-ASA scheme, a first principles method, within the local spin density approximation, implemented in real space. We calculated the magnetic moments at the impurity site in the above systems and all the substitucional impurities are found to be magnetic. The results show that interstitial Fe is non-magnetic in the tri- and tetravalent hosts, but interstitial Fe and Mo impurities could develop local magnetic moment in divalent hosts. \'We show that the magnetic moment at the impurity site in these divalent hosts is strongly dependent on lattice relaxation. The results can be explained using simple arguments based on Wolff model. We have investigated in a systematic way the behavior of the isomer shift of Fe impurities in these systems. We observed that our results are in generally good agreement with experiment and lead to better understanding of the observed trends in terms of the volume occupied by the Fe in each host.

Neste trabalho realizamos um estudo do comportamento do momento magnético e do deslocamento isomérico de uma impureza intersticial de Fe em hospedeiros metálicos de valências 4 (Ti, Zr), 3 (Sc, Y). Investigamos também impurezas intersticiais e substitucionais de Mo e Fe em hospedeiros divalentes. Para realizar este estudo fizemos cálculos de estrutura eletrônica utilizando o RS-LMTO-ASA (\"Real Space - Linear Muffin-Tin Orbital - Atomic Spherical Approximation\"), um método de primeiros princípios dentro da aproximação do funcional densidade local, implementado no espaço real. Calculamos o momento magnético no sítio da impureza nos sistemas acima e constatamos que a impureza intersticial de Fe é não magnética nos hospedeiros de valências 4 e 3, e que tanto as impurezas intersticiais como as substitucionais podem apresentar momento magnético nos hospedeiros divalentes. Mostramos que para os sistemas divalentes o momento magnético depende fortemente da relaxação. Os nossos resultados são explicados através de um modelo simples, baseado no modelo de Wolff. Investigamos também o comportamento do deslocamento isomérico no sítio da impureza de Fe nesses vários sistemas. Constatamos que os nossos resultados concordam razoavelmente bem com os dados experimentais e explicam o comportamento das tendências observadas. / In the present work, we have studied the magnetic moments and the behavior of the isomer shift at the interstitial Fe impurity site in Ti, Sc, Zr and Y hosts. We have also investigated interstitial and substitutional Fe and Mo impurities in Ca, Sr and Yb hosts. To perform the calculations, we have used the RS-LMTO-ASA scheme, a first principles method, within the local spin density approximation, implemented in real space. We calculated the magnetic moments at the impurity site in the above systems and all the substitucional impurities are found to be magnetic. The results show that interstitial Fe is non-magnetic in the tri- and tetravalent hosts, but interstitial Fe and Mo impurities could develop local magnetic moment in divalent hosts. \'We show that the magnetic moment at the impurity site in these divalent hosts is strongly dependent on lattice relaxation. The results can be explained using simple arguments based on Wolff model. We have investigated in a systematic way the behavior of the isomer shift of Fe impurities in these systems. We observed that our results are in generally good agreement with experiment and lead to better understanding of the observed trends in terms of the volume occupied by the Fe in each host.

Ce travail de thèse a pour but de montrer comment des caractérisations nanomécaniques en AFM peuvent apporter une meilleure compréhension des relations structure-propriétés dans les polymères. Dans ce contexte, la technique elle-même et sa base théorique sont d'abord analysées pour mettre en œuvre une méthodologie robuste afin d'effectuer des mesures reproductibles. Deux études principales sont menées sur un thème commun : la compréhension des interactions entre les biopolymères et les liquides ioniques (ILs). Tout d'abord, la compatibilisation des mélanges PBAT/PLA par deux ILs différents (à savoir il-Cl et il-TMP) est étudiée. Les images AFM d'adhésion et de module local mettent en évidence les différentes microstructures, et soulignent que la compatibilisation résulte principalement d'une modification de l'interface PBAT/PLA, devenant une interphase cohésive. Ceci est dû à une interaction spécifique avec les cations et les anions de chaque liquide ionique, qui se situent préférentiellement au niveau de ces interphases. La deuxième étude porte plus précisément sur la modification du PBAT semi-cristallin par de petites quantités des mêmes liquides ioniques. Alors que il-TMP forme des nodules dissipatifs dispersés dans la matrice et une interphase cohésive avec celle-ci, il-Cl, miscible dans la phase amorphe du PBAT, augmente la mobilité de la chaîne dans la MAF (i.e. fraction amorphe mobile) et l'entrave dans la RAF confinée (i.e. fraction amorphe rigide), conduisant à des modifications intéressantes des propriétés macroscopiques. En plus de montrer certaines capacités intéressantes des ILs comme additifs dans les polymères, ces résultats dévoilent également un potentiel exceptionnel des caractérisations nanomécaniques en AFM pour la compréhension en profondeur des relations structure-propriétés dans les matériaux. / This thesis work aims to show how nanomechanical characterizations in AFM can provide a better understanding of structure-properties relationships in polymers. In this context, the technique itself and the associated theoretical basis are first analyzed to implement a robust methodology in order to perform reproducible, quantitative measurements. Two main studies are carried out around a common topic: the understanding of the interactions between biopolymers and ionic liquids (ILs). First, the compatibilization of PBAT/PLA blends by two different ILs (namely il-Cl and il-TMP) is studied. Adhesion and local modulus mappings evidence the resulting microstructures, and highlight that the compatibilization mainly results from a modification of the PBAT/PLA interface, becoming a coherent interphase. This is due to specific interaction with the cations and the anions of each IL, which are preferentially located at those interphases. The second study is more specifically about the understanding of the modification of semicrystalline PBAT by the addition of small amounts of the same ionic liquids. While il-TMP forms dissipative nodules dispersed into the matrix with a cohesive interphase between both, il-Cl, miscible into the amorphous phase of PBAT, amplifies the chain mobility in the bulky MAF (i.e. Mobile Amorphous Fraction) and hinders it in the confined RAF (i.e. Rigid Amorphous Fraction), leading to interesting macroscopical properties modifications. More than showing some interesting capabilities of ILs as additives in polymers, those results also show an outstanding potential of AFM nanomechanical mappings for the in-deep understanding of structure-properties relationships in materials.

Cette thèse est consacrée à l'analyse mathématique de l'équation d'Euler incompressible à surface libre. On se concentre sur la propriété dispersive et sur la théorie de Cauchy à faible régularité. Une grande part de la thèse est consacrée à l'étude de l'équation des ondes de gravité-capillarité. On établit des critères d'explosion et la persistance de régularité dans les espaces de Sobolev. En démontrant les estimations de Strichartz pour les solutions à faible régularité, on obtient des théories de Cauchy pour les données initiales dont la vitesse peut être non-lipschitzienne. Dans une autre part de la thèse, on étudie la propriété dispersive des équations des ondes de surface. Plus précisément, on s'intéresse aux estimations de Strichartz. On démontre que, pour les solutions raisonnablement régulières, les équations des ondes de surface non linéaires obéissent aux mêmes estimations de Strichartz comme dans le cas des équations linéarisées. / This dissertation is devoted to the mathematical analysis of the water waves systems. We focus on the dispersive property and the Cauchy problem for rough initial data. One of the main objects of study is the gravity-capillary water waves system. We establish blow-up criteria and the persistence of Sobolev regularity. By proving Strichartz estimates for rough solutions, we obtain Cauchy theories for non-Lipschitz initial velocity. In another part of the dissertation, we study the dispersive property of the fully nonlinear water waves systems. More specifically, we are interested in Strichartz estimates. We prove for sufficiently smooth solutions that the nonlinear systems obey the same Strichartz estimates as their linearizations do.

We formulate Local Shape Descriptor selection for model-based object recognition in range data as an optimization problem and offer a platform that facilitates a solution. The goal of object recognition is to identify and localize objects of interest in an image. Recognition is often performed in three phases: point matching, where correspondences are established between points on the 3-D surfaces of the models and the range image; hypothesis generation, where rough alignments are found between the image and the visible models; and pose refinement, where the accuracy of the initial alignments is improved. The overall efficiency and reliability of a recognition system is highly influenced by the effectiveness of the point matching phase. Local Shape Descriptors are used for establishing point correspondences by way of encapsulating local shape, such that similarity between two descriptors indicates geometric similarity between their respective neighbourhoods. We present a generalized platform for constructing local shape descriptors that subsumes a large class of existing methods and allows for tuning descriptors to the geometry of specific models and to sensor characteristics. Our descriptors, termed as Variable-Dimensional Local Shape Descriptors, are constructed as multivariate observations of several local properties and are represented as histograms. The optimal set of properties, which maximizes the performance of a recognition system, depend on the geometry of the objects of interest and the noise characteristics of range image acquisition devices and is selected through pre-processing the models and sample training images. Experimental analysis confirms the superiority of optimized descriptors over generic ones in recognition tasks in LIDAR and dense stereo range images. / Thesis (Ph.D, Electrical & Computer Engineering) -- Queen's University, 2009-09-01 11:07:32.084