Techn. University, Diss., 2007--Darmstadt.

Thesis (Ph. D.)--University of Washington, 2004. / Vita. Includes bibliographical references (leaves 152-158).

Nanoscale materials behave differently than their bulk counterparts due, in part, to the reduced length scales and the increased surface to core atom ratio. As the length scales decrease, the surface atoms become increasingly important as they make up a larger percentage of the total number of atoms. These surface atoms have magnetic properties that differ from the core atoms due to a surface anisotropy that alters the interparticle, intraparticle, and exchange interactions. In this work, we have synthesized three different nanoscale systems that will allow us to explore the physics of the different interactions. Cu/gamma-Fe2O3 core/shell nanoparticles were chosen because the gamma-Fe2O3 cores have vacancies in their B-sites, broken coordination at the surface, and experience superexchange interactions. As a comparison, multiphase undoped and V-doped SiO2/FeCo nanoparticles were chosen as these nanoparticles do not suffer from vacancies or surface disorder and experience both direct exchange interactions from the nanoparticle core and superexchange interactions between the FeCo core and the metal silicate interfacial phase. Finally, Fe nanocrystallites were grown in a Cu matrix as they present no vacancies or surface disorder, and they are single phase. We observed that the interfacial phases that form in these core/shell and nanocrystallite/matrix nanoscale systems alters significantly the physics of the magnetism. The overall magnetic properties, the elemental magnetism, and the atomic magnetism were all observed to be altered by this interfacial phase, along with the interparticle and intraparticle interactions. In addition, the thickness of this interfacial phase, and thus the strength of its affect, was controlled by controlling the thickness of the shells or the amount of intermixing in the case of the nanostructured thin film. / February 2016

La necesidad inicial de interpretar espectros atómicos condujo a físicos y químicos a un continuo desarrollo de modelos para entender el orden, llamado configuración electrónica, al interior del átomo. Desde el modelo de Bohr se acepta que una señal en el espectro corresponde a una transición electrónica; en nuestros días la complejidad de los niveles de energía generados por electrones desapareados en un orbital puede entenderse por los acoplamientos de L y S en el caso de átomos livianos. El presente artículo detalla la amplitud del uso de tales diagramas y procura ser una referencia en la asimilación de este método y sus resultados. / A first need for the interpretation of atomic spectra lead physicist and chemists towards a continuous development of models in order to understand the order, known as electronic configuration, within an atom. Since Bohr's model, it was accepted that a signa! in a spectrum corresponds to an electronic transition; nowadays the complexity of energy levels, generated by unpaired electrons in an orbital, can be understood in terms of L and S coupling in lighter atoms. This article details the extent of the use of such diagrams, expecting to be a reference in order to achieve the method and its results.

No description available.

Dans le cadre de l’étude du couplage entre la plasticité et les interactions de l’hydrogène avec les matériaux métalliques, l’objectif de ce travail de thèse est l’implémentation dans le code de calcul par éléments finis Abaqus© de la loi de diffusion de l’hydrogène couplée aux champs mécaniques, tenant compte notamment du piégeage dû à la déformation plastique. La stratégie d’implémentation retenue permet de résoudre simultanément les problèmes de diffusion et de mécanique ; elle s’est appuyée sur les travaux de la littérature, et a nécessité le développement de procédures en fortran 77, et en particulier, de procédures utilisateur UMAT et UMATHT permettant de définir respectivement le comportement mécanique, et un flux de matière. Ces procédures ont été confrontées avec succès à plusieurs cas de la littérature. Les outils développés ont été appliqués à l’étude numérique d’un essai de pliage en U, utilisé pour la caractérisation de la rupture différée par fragilisation par l’hydrogène de tôles minces prédéformées plastiquement. Une étude paramétrique portant sur les conditions de l’essai, les conditions limites en hydrogène et la relation entre plasticité, hydrogène piégé et hydrogène diffusif a été menée. Enfin, une transposition à l’échelle du polycristal 3D a été effectuée, en utilisant une procédure UMAT de comportement polycristallin modifiée. Une étude sur les paramètres constitutifs d’un Volume Elémentaire Représentatif a été réalisée, puis, une étude de l’essai en U à l’échelle du polycristal effectuée grâce à un transfert de conditions limites entre un calcul global et le VER, afin de simuler l’effet de l’anisotropie cristalline sur les champs de concentration d’hydrogène. / In the framework of the coupling between plasticity and hydrogen interactions with the metallic material, the aim of this thesis is to implement in the finite element code Abaqus © the hydrogen diffusion law coupled with the mechanical fields, accounting particularly for the trapping caused by the plastic strain. The chosen implementation strategy allows to simultaneously solve the diffusion and mechanical problems. It is based on works from the literature and needs the development of procedures in fortran 77, in particular the user procedures UMAT and UMATHT allowing the definition of the mechanical behavior and the material flux respectively. These procedures were confronted with several cases in literature. The developed procedures were applied to the numerical study of the U-bend test, used for characterizing the delayed cracking caused by hydrogen embrittlement. A parametric study on test conditions, boundary conditions on hydrogen and relationship between plasticity, trapped hydrogen, diffusive hydrogen was carried out. Finally, a transposition to the scale of a 3D polycristal was performed using a modified UMAT procedure with crystalline elastoviscoplasticity. A numerical study on the relevant parameters for defining a Representative Volume Element was carried out. Then, the simulation of a virtual u-bend test at the polycristal scale was performed thanks to a boundary condition transfer between global calculation and the RVE, in order to simulate the effect of crystal anisotropy on hydrogen concentration field.

The purpose of this research is to test the effects of methyltrimethoxysilane coupling agent on composite material containing calcium sulfite obtained from the Southern Illinois Power Co-operative. This scrubber material and the miscanthus plant are of interest due to their use in coal burning power plants to reduce toxic emission. When calcium sulfate is passed through coal fire gas emissions it absorbs mercury and sulfur. In these composites it is used as filler to reduce cost. Miscanthus is a source of both cellulose reinforcement and some natural resin. This plant has low care requirements, little mineral content, useful energy return, and positive environmental effects. Under investigation is whether a post-cure procedure or a silane coupling agent will positively impact the composite. Hot pressing alone may not be enough to fully cure the phenolic. It is hoped that the silane will increase the strength characteristics of the composite by enhancing adhesion between the calcium sulfite and phenolic resin. Possible effects on the miscanthus by the silane will also be tested. Phenolic is being utilized because of its recycling and biodegradable properties along with cost effectiveness in mass production. Composite mechanical performance was measured through 3-point bending to measure flexural strength and strain at breakage. A dynamic mechanical analyzer (DMA) was used to find thermomechanical properties. The post-cure was found to be effective, particularly on the final composite containing silane. When methyltrimethoxysilane was added to the miscanthus prior to fabrication, it was found to reduce flexural strength and density. However the addition of methyltrimethoxysilane to the calcium sulfite altered thermo-mechanical properties to a state more like pure phenolic, with added flexibility and thermal stability.

Severe ozone depletion in the polar lower stratosphere has been linked to significant changes in tropospheric circulation patterns in the both hemispheres. Observed Southern Hemisphere circulation changes are easily reproduced in climate models and may be achieved by either increasing ozone depleting substances in a chemistry-climate model(CCM) or by imposing observed ozone losses as a zonally-symmetric perturbation in a prescribed-ozone global circulation model (GCM). In the Northern Hemisphere however, only the CCM method produces a circulation response in agreement with analysis of observations, while the GCM method is unable to produce any significant tropospheric circulation changes from imposing observed zonal-mean Arctic ozone losses. Confidence in a mechanistic link between Arctic stratospheric ozone change and changes in tropospheric circulation is greatly increased if the change can be reproduced using a GCM in addition to being reproducible in a CCM. This thesis demonstrates that by allowing ozone to vary along longitude, and by imposing ozone depletion during a realistic timeframe, the GCM method can produce circulation changes compatible with both the CCM method and observations. An equivalent-latitude coordinate allows the prescribed ozone field, and imposed ozone losses, to follow the polar vortex as it is systematically disturbed or displaced off the pole throughout the winter, producing a realistic circulation response in the troposphere in contrast to when ozone and its imposed losses are zonally-symmetric. Timing the imposed ozone depletion with the breakup of the polar vortex reveals that the appearance of the circulation response is very sensitive to the relative timing of these events and to the pre-existing dynamical state of the polar vortex. These results demonstrate that prescribing ozone as a zonally symmetric climatology within a GCM, as has been recent practice in the literature, is only representative of the Southern Hemisphere and is inappropriate for accurately representing processes within the Arctic stratosphere. Moreover this work demonstrates that these dynamically-evolving zonal asymmetries in ozone, which are not present in zonally-symmetric ozone schemes, play a crucial role in allowing perturbations in the Arctic stratosphere to influence the troposphere and surface conditions.

Since the discovery of giant magnetoresistance in 1980s, Spintronics became an exciting field which studies numerous phenomena including the spin transport in magnetic heterostructures, magnetization dynamics and the interplay between them. I have investigated different topics during my graduate research. In this dissertation, I summarize all my projects including spin pumping, spin convertance and spin injection into ballistic medium. First, we develop a linear response formalism for spin pumping effect. Spin pumping refers that a precessing emits a spin current into its adjacent nonmagnetic surroundings, which was originally proposed using scattering theory. The newly developed formalism is demonstrated to be identical the early theory in limiting case. While our formalism is convenient to include the effects of disorders and spin-orbit coupling which can resolve the quantitative controversies between early theory and experiments. Second, the spin pumping experiments indicates a much smaller spin Hall angle compared with the results obtained via the spin transfer torque measurements. We found that such issues can be resolved when taking into consideration the effects of non-local conductivity. And we conclude neither of the two methods measures the real spin Hall angle while the spin pumping methods provides much accurate estimations. Third, we developed the spin transport equations in weak scattering medium in the presence of spin-orbit coupling. Before this, all spin dependent electron transport has been modeled by the conventional spin diffusion equation. While recent spin injection experiments have seen the failure of spin diffusion equation. As the experimental fitting using spin diffusion models led to unrealistic conclusions. At last, we study the spin convertance in anti-ferromagnetic multilayers, where the spin information can be mutually transferred between ferromagnetic/anti-ferromagnetic and conduction electrons. Our theory successfully explained the experiment results that the insertion of thin NiO film between YIG/Pt largely enhances the spin Seebeck currents.

Abstract The present thesis deals with the nuclear magnetic resonance (NMR) spectroscopy of small solutes applied to the studies of liquid crystals and molecular sieves. In this method, changes induced by the investigated environment to the static spectral parameters (i.e. nuclear shielding, indirect and direct spin-spin coupling and quadrupole coupling) of the solute are measured. The nuclear shielding of dissolved noble gases is utilized for the studies of thermotropic liquid crystals. The relation between the symmetry properties of mesophases and the nuclear shielding is described. The different interaction mechanisms perturbing the observed noble gas nuclear shielding are discussed, particularly, the role of long-range attractive van der Waals interactions is brought out. The suitability of the noble gas NMR spectroscopy to the studies of lyotropic liquid crystals is investigated in terms of nuclear shielding and quadrupole coupling interactions. In molecular sieve systems, the effect of inter- and intracrystalline motions of solutes on their NMR spectra is discussed. A novel method for the measurement of the intracrystalline motions is developed. The distinctions in the 13C shielding of methane adsorbed in AlPO4-11 and SAPO-11, two structurally similar molecular sieves differing in composition, are indicated.