Made available in DSpace on 2014-10-09T12:28:34Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:03Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IEA/T / Universidade Karlsruhe, Alemanha

abstract: III-nitride alloys are wide band gap semiconductors with a broad range of applications in optoelectronic devices such as light emitting diodes and laser diodes. Indium gallium nitride light emitting diodes have been successfully produced over the past decade. But the progress of green emission light emitting devices has been limited by the incorporation of indium in the alloy, mainly due to phase separation. This difficulty could be addressed by studying the growth and thermodynamics of these alloys. Knowledge of thermodynamic phase stabilities and of pressure - temperature - composition phase diagrams is important for an understanding of the boundary conditions of a variety of growth techniques. In this dissertation a study of the phase separation of indium gallium nitride is conducted using a regular solution model of the ternary alloy system. Graphs of Gibbs free energy of mixing were produced for a range of temperatures. Binodal and spinodal decomposition curves show the stable and unstable regions of the alloy in equilibrium. The growth of gallium nitride and indium gallium nitride was attempted by the reaction of molten gallium - indium alloy with ammonia at atmospheric pressure. Characterization by X-ray diffraction, photoluminescence, and secondary electron microscopy show that the samples produced by this method contain only gallium nitride in the hexagonal phase. The instability of indium nitride at the temperatures required for activation of ammonia accounts for these results. The photoluminescence spectra show a correlation between the intensity of a broad green emission, related to native defects, and indium composition used in the molten alloy. A different growth method was used to grow two columnar-structured gallium nitride films using ammonium chloride and gallium as reactants and nitrogen and ammonia as carrier gasses. Investigation by X-ray diffraction and spatially-resolved cathodoluminescence shows the film grown at higher temperature to be primarily hexagonal with small quantities of cubic crystallites, while the one grown at lower temperature to be pure hexagonal. This was also confirmed by low temperature photoluminescence measurements. The results presented here show that cubic and hexagonal crystallites can coexist, with the cubic phase having a much sharper and stronger luminescence. Controlled growth of the cubic phase GaN crystallites can be of use for high efficiency light detecting and emitting devices. The ammonolysis of a precursor was used to grow InGaN powders with different indium composition. High purity hexagonal GaN and InN were obtained. XRD spectra showed complete phase separation for samples with x < 30%, with ~ 9% indium incorporation in the 30% sample. The presence of InGaN in this sample was confirmed by PL measurements, where luminescence from both GaN and InGaN band edge are observed. The growth of higher indium compositions samples proved to be difficult, with only the presence of InN in the sample. Nonetheless, by controlling parameters like temperature and time may lead to successful growth of this III-nitride alloy by this method. / Dissertation/Thesis / Ph.D. Physics 2011

Abstract This thesis is about the relationship between a body of nineteenth-century American literature and the science of thermodynamics that was emerging between the 1820s and 1870s, changing the way people thought about the physical universe and the possibilities and limitations that it presented for human action. Its basic premise is that thermodynamic energy, as it emerged in the nineteenth century as a quantifiable phenomenon, was not a self-revealing natural fact, but the “hybrid” product of a “cultural field” that included literature among other of its essential points of mediation. Through readings of works by Herman Melville, Ralph Waldo Emerson, Henry David Thoreau, Nathaniel Hawthorne, Rebecca Harding Davis, Mark Twain, Robert Montgomery Bird and Thomas Josiah Dimsdale, it argues that literature throughout this period was very much occupied with questions and concerns that were reflected in the scientific and technological investigations that led to the creation of the laws of energy. Specifically, it argues that energy’s conservative and/or dissipative tendencies, which, besides representing objective descriptions of energetic behaviour, also reflected real possibilities and limitations for human action, were a major concern of writers at this time. Their work, it is argued, reveals humanly and historically meaningful aspects of what, in the laws of thermodynamics, would become ahistorical scientific facts, proving that literature and science, belonging to a greater “cultural field,” follow parallel lines of investigation indicative of larger cultural problematics.

This thesis explores the algebraic and geometric structure of the Legendre transform and its application in various field of mathematics and physics. Specifically linear transformation as a mathematical process and motivating it in terms related to phenomena in mathematics and physics. The Legendre transform provides a change of variables to express equations of the motion or other physical relationships in terms of most convenient dynamical quantities for a given experiment or theoretical analysis. In classical mechanics the Legendre transform generates the Hamiltonian function of a system from the Lagrangian function or vice versa. In thermodynamics the Legendre transform allows thermodynamic relationships to be written in terms of alternative sets of independent variables. Here we review the properties of Legendre transform and why it is so important in mathematics and physics.

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abstract: Deoxyribonucleic acid (DNA) has emerged as an attractive building material for creating complex architectures at the nanometer scale that simultaneously affords versatility and modularity. Particularly, the programmability of DNA enables the assembly of basic building units into increasingly complex, arbitrary shapes or patterns. With the expanding complexity and functionality of DNA toolboxes, a quantitative understanding of DNA self-assembly in terms of thermodynamics and kinetics, will provide researchers with more subtle design guidelines that facilitate more precise spatial and temporal control. This dissertation focuses on studying the physicochemical properties of DNA tile-based self-assembly process by recapitulating representative scenarios and intermediate states with unique assembly pathways. First, DNA double-helical tiles with increasing flexibility were designed to investigate the dimerization kinetics. The higher dimerization rates of more rigid tiles result from the opposing effects of higher activation energies and higher pre-exponential factors from the Arrhenius equation, where the pre-exponential factor dominates. Next, the thermodynamics and kinetics of single tile attachment to preformed “multitile” arrays were investigated to test the fundamental assumptions of tile assembly models. The results offer experimental evidences that double crossover tile attachment is determined by the electrostatic environment and the steric hindrance at the binding site. Finally, the assembly of double crossover tiles within a rhombic DNA origami frame was employed as the model system to investigate the competition between unseeded, facet and seeded nucleation. The results revealed that preference of nucleation types can be tuned by controlling the rate-limiting nucleation step. The works presented in this dissertation will be helpful for refining the DNA tile assembly model for future designs and simulations. Moreover, The works presented here could also be helpful in understanding how individual molecules interact and more complex cooperative bindings in chemistry and biology. The future direction will focus on the characterization of tile assembly at single molecule level and the development of error-free tile assembly systems. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2016

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Thesis (MTech (Mechanical Engineering))--Cape Peninsula University of Technology, 2010 / Development of safe storage for reactive combustible materials to prevent possible human and environmental hazards as well as ensure and enhance industrial safety can significantly benefit from mathematical modelling of systems. In the recent past, models with varying degrees of sophistication have been developed and applied to the problem of predicting thermal criticality conditions, temperature and concentration profiles of such system. In this thesis, a model showing the temperature history of an nth order exothermic oxidation reaction in a slab of combustible material with variable pre-exponential factor, taking the consumption of the reactant into account in the presence of a convective heating and oxygen exchange at the slab surface with the ambient is presented Both transient and steady state problems are tackled The critical regime separating the regions of explosive and non-explosive paths of a one step exothermic chemical reaction is determined The governing nonlinear partial differential equations are solved numerically by method of lines (MOL), with finite difference schemes used for the discretisation of the spatial derivatives. Moreover, both fourth order Runge-Kutta numerical integration coupled with shooting methods and perturbation techniques together with a special type of Hermite-Pade series summation and improvement method were employed to tackle the steady state problem. The crucial roles played by the boundary conditions in determining the location ofthe maximum heating were demonstrated. In chapter one, the relevant applications together with previous published work on the problem were highlighted The basic mathematical theory and equations needed to tackle the problem were derived in Chapter two. In chapter three, the transient model problem was formulated, analysed and discussed. The steady state problem was formulated and solved in Chapter four. Furtherwork and concluding remarks were highlighted in Chapter five.

abstract: DNA nanotechnology is one of the most flourishing interdisciplinary research fields. Through the features of programmability and predictability, DNA nanostructures can be designed to self-assemble into a variety of periodic or aperiodic patterns of different shapes and length scales, and more importantly, they can be used as scaffolds for organizing other nanoparticles, proteins and chemical groups. By leveraging these molecules, DNA nanostructures can be used to direct the organization of complex bio-inspired materials that may serve as smart drug delivery systems and in vitro or in vivo bio-molecular computing and diagnostic devices. In this dissertation I describe a systematic study of the thermodynamic properties of complex DNA nanostructures, including 2D and 3D DNA origami, in order to understand their assembly, stability and functionality and inform future design endeavors. It is conceivable that a more thorough understanding of DNA self-assembly can be used to guide the structural design process and optimize the conditions for assembly, manipulation, and functionalization, thus benefiting both upstream design and downstream applications. As a biocompatible nanoscale motif, the successful integration, stabilization and separation of DNA nanostructures from cells/cell lysate suggests its potential to serve as a diagnostic platform at the cellular level. Here, DNA origami was used to capture and identify multiple T cell receptor mRNA species from single cells within a mixed cell population. This demonstrates the potential of DNA nanostructure as an ideal nano scale tool for biological applications. / Dissertation/Thesis / Ph.D. Chemistry 2014

Este trabalho consiste basicamente em dois experimentos: Determinação da equação de estado de um gás frio aprisionado, e na comparação das temperaturas de uma amostra de átomos confinadas em dois tipos de armadilhas magneto-ópticas. No primeiro experimento utilizamos a generalização do conceito de pressão e volume que foram redefinidos de maneira apropriada para alcançamos uma equação de estado. Experimentalmente nossa amostra apresentou um desvio do esperado para um gás ideal, dessa forma utilizamos uma expansão virial com as novas definições de pressão e volume para investigar as interações entre os átomos. Já no segundo experimento utilizamos uma técnica que mede transiente temporal da absorção do feixe pelos átomos através de um fotodetector para a obtenção da temperatura. Neste experimento obtemos temperaturas equivalentes para as duas armadilhas. / This work consists of two experiments: Determination of the state equation a trapped cold gas, and the comparison of the temperatures of confined atoms in two types of magneto-optical traps. For the first experiment we generalized and defined a new pressure and volume concept and we reached a state equation. Experimentally our sample presented a deviation of the ideal gas, in that way we used a virial expansion with the new pressure and volume definitions to investigate the interactions among the atoms. In the second experiment we used a technique that measures temporal variation of the absorption of a probe beam that crosses the atoms by a photodetector, witch gives us the information about the temperature. We have found equivalent temperatures for the two traps.