Effect of architecture at nanoscale on the macroscopic properties of polymer materials has long been a field of major interest, as evidenced by inhomogeneities in networks, multimodal network topologies, etc. The primary purpose of this research is to establish the architecture-property relationship of polymer networks by studying the physical and mechanical responses of a series of topologically different PTHF networks. Monodispersed allyl-terminated PTHF precursors were synthesized through ¡°living¡± cationic polymerization and functional end-capping. Model networks of various crosslink densities and inhomogeneities levels (unimodal, bimodal and clustered) were prepared by endlinking precursors via thiol-ene reaction. Thermal characteristics, i.e., glass transition, melting point, and heat of fusion, of model PTHF networks were investigated as functions of crosslink density and inhomogeneities, which showed different dependence on these two architectural parameters. Study of freezing point depression (FPD) of solvent confined in swollen networks indicated that the size of solvent microcrystals is comparable to the mesh size formed by intercrosslink chains depending on crosslink density and inhomogeneities. Relationship between crystal size and FPD provided a good reflection of the existing architecture facts in the networks. Mechanical responses of elastic chains to uniaxial strains were studied through SANS. Spatial inhomogeneities in bimodal and clustered networks gave rise to ¡°abnormal butterfly patterns¡±, which became more pronounced as elongation ratio increases. Radii of gyration of chains were analyzed at directions parallel and perpendicular to stretching axis. Dependence of Rg on ¦Ë was compared to three rubber elasticity models and the molecular deformation mechanisms for unimodal, bimodal and clustered networks were explored. The thesis focused its last part on the investigation of evolution of free volume distribution of linear polymer (PE) subjected to uniaxial strain at various temperatures using a combination of MD, hard sphere probe method and Voronoi tessellation. Combined effects of temperature and strain on free volume were studied and mechanism of formation of large and ellipsoidal free volume voids was explored.

A in uência do caráter inomogêneo da região-fonte na ampli cação da Radiação Quilom étrica das Auroras é investigada. Inicialmente é feita uma revisão de trabalhos relevantes publicados a respeito do mesmo tema geral, tanto os que concernem aos dados observacionais como os que concernem aos modelos teóricos e simulações numéricas. Esta revisão é precedida pelo estabelecimento de conceitos e de nições pertinentes ao tema. São consideradas duas abordagens distintas na determinação da ampli cação da radiação na região-fonte. A primeira considera o plasma localmente homogêneo, enquanto a segunda toma em conta, explicitamente, a contribuição dos gradientes dos parâmetros do plasma. A ampli cação da radiação é determinada pela avaliação do tensor dielétrico do plasma e pela evolução da radia ção através do estudo de traçado de raios. Os parâmetros do plasma são obtidos através de uma formulação autoconsistente que toma em conta uma queda de potencial elétrico ao longo das linhas de campo geomagnético. Utiliza-se um modelo de lâmina auroral em que o campo magnético ambiente é considerado localmente homogêneo. O modelo teórico subjacente adotado é o do maser de elétron-cíclotron. O principal resultado obtido revela uma diminuição na ampli cação nal por um fator em torno de três, quando os gradientes dos parâmetros do plasma são considerados explicitamente. Este resultado pode ter implicações na capacidade do maser de elétron-cíclotron em explicar os níveis de radiação mais elevados observados. / The in uence from source region inhomogeneous character on ampli cation of Auroral Kilometric Radiation is investigated. Firstly, a review over relevant works published about the same general theme is made, concerning about observational data as well theoretical models and numerical simulations. This review is preceded by the establishment of de nitions and concepts related to the theme. Two distinct approaches are considered in determining the ampli cation of radiation across the source region. First approach takes the plasma as locally homogeneous, while second approach account, explicitly, for gradients on plasma parameters. The ampli cation is obtained through evaluation of the dielectric tensor and the evolution of radiation through ray tracing. Plasma parameters are obtained using a self-consistent formulation which account for an electric potential drop along geomagnetic eld lines. An auroral slab model is used where the ambient magnetic eld is taken as locally homogeneous. The subjacent theoretical model adopted is the electron-cyclotron maser. The main result obtained reveals a reduction on nal ampli cation by a factor about three, when plasma parameters gradients are explicitly accounted. This nding may have implications on capability of electron-cyclotron maser for explanation the most intense levels of radiation observed.

A in uência do caráter inomogêneo da região-fonte na ampli cação da Radiação Quilom étrica das Auroras é investigada. Inicialmente é feita uma revisão de trabalhos relevantes publicados a respeito do mesmo tema geral, tanto os que concernem aos dados observacionais como os que concernem aos modelos teóricos e simulações numéricas. Esta revisão é precedida pelo estabelecimento de conceitos e de nições pertinentes ao tema. São consideradas duas abordagens distintas na determinação da ampli cação da radiação na região-fonte. A primeira considera o plasma localmente homogêneo, enquanto a segunda toma em conta, explicitamente, a contribuição dos gradientes dos parâmetros do plasma. A ampli cação da radiação é determinada pela avaliação do tensor dielétrico do plasma e pela evolução da radia ção através do estudo de traçado de raios. Os parâmetros do plasma são obtidos através de uma formulação autoconsistente que toma em conta uma queda de potencial elétrico ao longo das linhas de campo geomagnético. Utiliza-se um modelo de lâmina auroral em que o campo magnético ambiente é considerado localmente homogêneo. O modelo teórico subjacente adotado é o do maser de elétron-cíclotron. O principal resultado obtido revela uma diminuição na ampli cação nal por um fator em torno de três, quando os gradientes dos parâmetros do plasma são considerados explicitamente. Este resultado pode ter implicações na capacidade do maser de elétron-cíclotron em explicar os níveis de radiação mais elevados observados. / The in uence from source region inhomogeneous character on ampli cation of Auroral Kilometric Radiation is investigated. Firstly, a review over relevant works published about the same general theme is made, concerning about observational data as well theoretical models and numerical simulations. This review is preceded by the establishment of de nitions and concepts related to the theme. Two distinct approaches are considered in determining the ampli cation of radiation across the source region. First approach takes the plasma as locally homogeneous, while second approach account, explicitly, for gradients on plasma parameters. The ampli cation is obtained through evaluation of the dielectric tensor and the evolution of radiation through ray tracing. Plasma parameters are obtained using a self-consistent formulation which account for an electric potential drop along geomagnetic eld lines. An auroral slab model is used where the ambient magnetic eld is taken as locally homogeneous. The subjacent theoretical model adopted is the electron-cyclotron maser. The main result obtained reveals a reduction on nal ampli cation by a factor about three, when plasma parameters gradients are explicitly accounted. This nding may have implications on capability of electron-cyclotron maser for explanation the most intense levels of radiation observed.

The electrical properties of ZnO and contacts to ZnO have been investigated using different techniques. Temperature dependent Hall (TDH) effect measurements have been used to characterize the as-received melt grown ZnO samples in the 20 – 330 K temperature range. The effect of argon annealing on hydrogen peroxide treated ZnO samples has been investigated in the 200 – 800oC temperature range by the TDH effect measurement technique. The experimental data has been analysed by fitting a theoretical model written in Matlab to the data. Donor concentrations and acceptor concentrations together with the associated energy levels have been extracted by fitting the models to the experimentally obtained carrier concentration data by assuming a multi-donor and single charged acceptor in solving the charge balance equation. TDH measurements have revealed the dominance of surface conduction in melt grown ZnO in the 20 – 40 K temperature range. Surface conduction effects have proved to increase with the increase in annealing temperature. Surface donor volume concentrations have been determined in the 200 – 800oC by use of theory developed by D. C. Look. Good rectifying Schottky contacts have been fabricated on ZnO after treating the samples with boiling hydrogen peroxide. Electrical properties of these Schottky contacts have been investigated using current-voltage (IV) and capacitance-voltage (CV) measurements in the 60 – 300 K temperature range. The Schottky contacts have revealed the dominance of predominantly thermionic emission at room temperature and the existence of other current transport mechanisms at temperatures below room temperature. Polarity effects on the Schottky contacts deposited on the O-polar and Zn-polar faces of ZnO have been demonstrated by the IV technique on the Pd and Au Schottky contacts at room temperature. Results obtained indicate a strong dependence of the Schottky contact quality on the polarity of the samples at room temperature. The quality of the Schottky contacts have also indicated their dependence on the type of metal used with the Pd producing contacts with the better quality as compared to the Au. Schottky barrier heights determined using temperature dependent IV measurements have been observed to increase with increasing temperature and this has been explained as an effect of barrier inhomogeneities, while the ones obtained from CV measurements have proved to follow the negative temperature coefficient of the II – VI semiconductor material, i.e. a decrease in barrier height with increasing temperature. However, the values have proved to be larger than the energy gap of ZnO, an effect that has been explained as caused by an inversion layer. Copyright / Dissertation (MSc)--University of Pretoria, 2010. / Physics / unrestricted

Dans le cadre des recherches menées sur les SFR (Sodium cooled Fast Reactor), le CEA souhaite développer une instrumentation innovante et spécifique à ces réacteurs. Le travail présenté concerne la mesure par ultrasons, de la température du sodium à la sortie des têtes des assemblages du coeur du réacteur. Cette instrumentation implique la propagation d'ultrasons dans du sodium liquide, thermiquement inhomogène et turbulent. Le milieu provoque des déviations du faisceau acoustique qu'il faut prévoir et quantifier pour envisager d'employer les ultrasons comme moyen de mesure dans un coeur de réacteur SFR.Pour cela un code nommé AcRaLiS (Acoustic Ray in Liquid Sodium) a été implémenté. Une étude thermo-hydraulique précise du sodium a tout d'abord été menée afin de proposer une description adaptée du milieu et de choisir le modèle de propagation acoustique adéquat. Puis une implémentation a été réalisée afin de permettre la simulation rapide de la propagation d'ondes de plusieurs mégahertz dans ce milieu particulier. Ce code prévoit les déviations et l'évolution de l'intensité du faisceau acoustique. Deux expériences ont ensuite été conçues et réalisées pour vérifier ce code. La première, nommée UPSilon, innove en remplaçant le sodium par de l'huile de silicone afin d'avoir une inhomogénéité thermique stable pendant l'expérience. Elle permet de déterminer la validité du code AcRaLiS dans des inhomogénéités thermiques. La seconde, nommée IKHAR, permet d'étudier en eau l'influence de la turbulence sur la propagation d'ondes, en exploitant les instabilités de Kelvin-Helmholtz. Les conclusions et les perspectives sont présentées en élargissant à d'autres domaines d'application. / In the frame of research on Sodium cooled Fast nuclear Reactor (SFR), CEA aims to develop an innovative instrumentation, specific to these reactors. The present work relates to the measurement of the sodium temperature at the outlet of the assemblies of the reactor's core by an ultrasonic method. This instrumentation involves the propagation of ultrasonic waves in liquid sodium, thermally inhomogeneous and turbulent. Environment causes deviations of the acoustic beam that must be understood to predict and quantify to consider ultrasound as a measure means in a core of SFR reactor. To determine the magnitude of these influences, a code named AcRaLiS (Acoustic Ray in Liquid Sodium) has been implemented. In a first step, a thermal-hydraulic study specific to the medium, was conducted to provide an adequate description of the environment and choose a suitable acoustic propagation model. Then an implementation has been performed to allow rapid simulations of the wave propagation at several megahertz in this particular environment. This code provides ultrasounds deviations and changes in beam intensity.Two experiments were designed and conducted to verify the code. The first, named UPSilon innovates by replacing sodium by silicone oil in order to have a stable thermal inhomogeneity during the experiment. It allows to determine the validity of the code AcRaLiS with thermal inhomogeneities. The second, called IKHAR allows to study the influence of water turbulence on the propagation of waves, using the Kelvin-Helmholtz instabilities. Conclusions and perspectives are presented, including perspectives for other application domains.

Die vorliegende Arbeit befasst sich mit der Untersuchung von Schottky-Kontakten auf halbleitenden Zinkoxid- und β-Galliumoxid-Dünnfilmen. Nach einer kurzen Einführung in die verwendeten Materialsysteme und die Theorie von Schottky-Kontakten werden die Eigenschaften von verschiedenartig hergestellten Schottky-Kontakten auf Zinkoxid aufgezeigt. Dazu werden typischerweise Strom-Spannungs- und Kapazitäts-Spannungs-Messungen genutzt. Für die Zinkoxid-basierten Schottky-Kontakte konnte anhand verschiedenartig hergestellter Schottky-Kontakte gezeigt werden, dass deren Barrierenformation maßgeblich von Sauerstoffvakanzen nahe der Metall-Halbleiter-Grenzfläche beeinflusst wird. Zur Realisierung von Galliumoxid-basierten Schottky-Kontakten wurden zunächst die Eigenschaften von undotierten und Silizium-dotierten Galliumoxid-Dünnfilmen untersucht. Diese Dünnfilme sind mittels gepulster Laserabscheidung auf c-plane Saphir hergestellt. Als Prozessparameter sind in dieser Arbeit die Wachstumstemperatur, der Sauerstoffpartialdruck in der Kammer und der Silizumgehalt bspw. in Bezug auf Leitfähigkeit, Oberflächenmorphologie oder Kristallinität zur Realisierung von Schottky-Kontakten optimiert. Auf diesen Dünnfilmen wurden mit verschiedenen Herstellungsverfahren, wie thermischer Verdampfung, (reaktiver) Kathodenzerstäubung oder (reaktiver) Distanz-Kathodenzerstäubung, Metall- bzw. Metalloxid-Schottky-Kontakte aufgebracht. Dabei werden unter anderem die elektrischen Eigenschaften direkt nach der Herstellung und deren Entwicklung im weiteren zeitlichen Verlauf untersucht. Des Weiteren werden die Temperaturstabilität oder aber die Spannungsstabilität der Schottky-Kontakte studiert. Ein Vergleich zu Schottky-Kontakten auf β-Galliumoxid-Volumenmaterial wird anhand mittels reaktiver Distanz-Kathodenzerstäubung hergestellter Platinoxid-Dioden durchgeführt.

Le but de ce travail est d'étudier l'influence de la microstructure de roches poreuses hétérogènes sur le comportement à l'échelle macroscopique. Ainsi, nous avons caractérisé la microstructure et les propriétés micromécaniques (grâce à des tests de nano-indentation) de deux roches oolithiques poreuses (calcaire de Lavoux et minerai de fer) pour calculer leurs propriétés mécaniques et thermiques effectives. Les roches oolithiques sont constituées d'un assemblage de grains poreux (oolithes), de pores et de cristaux intergranulaires. La microscopie électronique à balayage et la tomographie 3D aux rayons X ont été utilisées pour identifier les différents composants de ces roches. Une attention particulière a été accordée à la tomographie aux rayons X car cette méthode analytique permet de caractériser le réseau poreux (taille, distribution spatiale et fraction volumique), ainsi que la forme des oolithes et des cristaux inter-oolithiques. La nouveauté de ce travail réside dans la prise en compte de la forme 3D réelle des pores. Par conséquent, nous avons approximé les oolites poreuses par des sphères et les pores de forme irrégulière par des ellipsoïdes. Cette approximation a été réalisée grâce à l'analyse en composantes principales (ACP), qui fournit les propriétés géométriques telles que la longueur des demi-axes et l'orientation des ellipsoïdes résultants. La sphéricité des oolites approximées a été calculée et les valeurs proches de 1 nous ont permis de considérer les oolithes comme des sphères. Pour vérifier l'approximation dans le cas des pores, nous avons évalué la contribution de ces pores tridimensionnels de forme irrégulière aux propriétés élastiques et thermiques effectives. Ainsi, les tenseurs de contribution de souplesse pour les pores irréguliers 3D et leurs approximations ellipsoïdales ont été calculés en utilisant la méthode des éléments finis (FEM). Ces tenseurs ont été comparés et une erreur relative a été estimée pour évaluer la précision de l'approximation. Cette erreur produit une distance maximale de 4,5% entre les deux solutions pour les pores et les ellipsoïdes, ce qui vérifie la procédure d'approximation proposée basée sur ACP. La méthode numérique FEM a été vérifiée en comparant la solution numérique des tenseurs de contribution des ellipsoïdes à la solution analytique basée sur la théorie d'Eshelby. La différence entre ces deux solutions ne dépasse pas 3%. La même méthode numérique a été utilisée pour calculer les tenseurs de contribution de résistivité thermique. Les tenseurs de souplesse et de résistivité calculés ont été utilisés pour évaluer les propriétés élastiques effectives (module élastique et coefficient de cisaillement) et la conductivité thermique effective en considérant le schéma d'homogénéisation de Maxwell en deux étapes. Les résultats ont montré une influence importante de la porosité sur les propriétés effectives. Enfin, les résultats obtenus pour les pores irréguliers ont été comparés à ceux des ellipsoïdes et ils ont montré un bon accord avec un écart maximal de 4% ce qui vérifie l'approximation des pores de forme irrégulière par des ellipsoïdes triaxiaux / The aim of this work is to study the influence of the microstructure of heterogeneous porous rocks on the behavior at the macroscopic scale. Thus, we characterized the microstructure and micromechanical properties (thanks to nano-indentation tests) of two porous oolitic rocks (Lavoux limestone and iron ore) to calculate their effective mechanical and thermal properties. Oolitic rocks are constituted by an assemblage of porous grains (oolites), pores and inter-granular crystals. Scanning electron microscopy and X-ray 3D Computed Tomography were used to identify the different components of these rocks. Particular attention was given to X-Ray computed tomography since this analytical method allows the characterization of the porous network (size, spatial distribution, and volume fraction), and the shapes of oolites and inter-oolitic crystals. The novelty of this work lies in taking into account the 3D real shape of pores. Hence, we approximated porous oolites by spheres and irregularly shaped pores by ellipsoids. This approximation was performed thanks to the principal component analysis (PCA), which provides the geometrical properties such as length of semi-axes and orientation of resulting ellipsoids. The sphericity of the approximated oolites was calculated and the values close to 1 allowed us to consider oolites as spheres. To verify the approximation in the case of pores, we evaluated the contribution of these irregularly shaped three-dimensional pores to the overall elastic properties. Thus, compliance contribution tensors for 3D irregular pores and their ellipsoidal approximations were calculated using the finite element method (FEM). These tensors were compared and a relative error was estimated to evaluate the accuracy of the approximation. This error produces a maximum discrepancy of 4.5% between the two solutions for pores and ellipsoids which verifies the proposed approximation procedure based on PCA. The FEM numerical method was verified by comparing the numerical solution for compliance contribution tensors of ellipsoids to the analytical solution based on Eshelby’s theory. The difference between these two solutions does not exceed 3%. The same numerical method was used to calculate thermal resistivity contribution tensors. Calculated compliance and resistivity contribution tensors were used to evaluate effective elastic properties (bulk modulus and shear coefficient) and effective thermal conductivity by considering the two-step Maxwell homogenization scheme. The results showed an important influence of the porosity on effective properties. Finally, the results obtained for irregular pores were compared to those for ellipsoidal ones and they showed a good agreement with a maximum deviation of 4% which verifies once again the approximation of irregularly shaped pores by tri-axial ellipsoids

Die vorliegende Arbeit befasst sich mit der Untersuchung von Schottky-Kontakten auf halbleitenden Zinkoxid- und β-Galliumoxid-Dünnfilmen. Nach einer kurzen Einführung in die verwendeten Materialsysteme und die Theorie von Schottky-Kontakten werden die Eigenschaften von verschiedenartig hergestellten Schottky-Kontakten auf Zinkoxid aufgezeigt. Dazu werden typischerweise Strom-Spannungs- und Kapazitäts-Spannungs-Messungen genutzt. Für die Zinkoxid-basierten Schottky-Kontakte konnte anhand verschiedenartig hergestellter Schottky-Kontakte gezeigt werden, dass deren Barrierenformation maßgeblich von Sauerstoffvakanzen nahe der Metall-Halbleiter-Grenzfläche beeinflusst wird. Zur Realisierung von Galliumoxid-basierten Schottky-Kontakten wurden zunächst die Eigenschaften von undotierten und Silizium-dotierten Galliumoxid-Dünnfilmen untersucht. Diese Dünnfilme sind mittels gepulster Laserabscheidung auf c-plane Saphir hergestellt. Als Prozessparameter sind in dieser Arbeit die Wachstumstemperatur, der Sauerstoffpartialdruck in der Kammer und der Silizumgehalt bspw. in Bezug auf Leitfähigkeit, Oberflächenmorphologie oder Kristallinität zur Realisierung von Schottky-Kontakten optimiert. Auf diesen Dünnfilmen wurden mit verschiedenen Herstellungsverfahren, wie thermischer Verdampfung, (reaktiver) Kathodenzerstäubung oder (reaktiver) Distanz-Kathodenzerstäubung, Metall- bzw. Metalloxid-Schottky-Kontakte aufgebracht. Dabei werden unter anderem die elektrischen Eigenschaften direkt nach der Herstellung und deren Entwicklung im weiteren zeitlichen Verlauf untersucht. Des Weiteren werden die Temperaturstabilität oder aber die Spannungsstabilität der Schottky-Kontakte studiert. Ein Vergleich zu Schottky-Kontakten auf β-Galliumoxid-Volumenmaterial wird anhand mittels reaktiver Distanz-Kathodenzerstäubung hergestellter Platinoxid-Dioden durchgeführt.