Filmes finos de óxido de nióbio têm sido usados em muitas aplicações tecnológicas. Existem pelo menos três óxidos estáveis de nióbio: NbO, NbO2 e Nb2O5 e cada um deles tem propriedades específicas. O Nb2O5 é a forma termodinamicamente mais estável e apresenta propriedades físicas e químicas únicas, como alto índice de refração, band gap largo, excelente estabilidade química e resistência à corrosão, baixa absorção óptica no campo da luz visível até regiões próximas ao infra-vermelho, sendo amplamente utilizados como filtros de interferência óptica de alta qualidade. Neste trabalho foram depositados filmes de óxido de nióbio por meio da técnica de sputtering reativo sobre substratos de silício e borossilicato. Os filmes finos foram obtidos com vazão de oxigênio variando entre 15 e zero sccm. O objetivo deste trabalho foi a caracterização das propriedades ópticas dos filmes. Foram avaliados o índice de refração e a espessura pela técnica de elipsometria, o band gap pelo método de Tauc e a razão atômica e a densidade superficial por meio de Espectrometria de Retroespalhamento Rutherford (RBS). Foram obtidos espectros de transmitância e refletância por Espectrofotometria UV/Vis/NIR e o coeficiente de extinção foi calculado pelo método de Hong. Todos estes parâmetros são importantes para aplicação em dispositivos ópticos. Nos filmes depositados com vazão de oxigênio de 15 sccm foi observado que o índice de refração aumenta com o aumento da espessura dos filmes e que o composto formado foi Nb2O5. Para uma vazão de 2,0 sccm foi encontrado o composto NbO2 e o filme apresentou alta absorção ótica. Os resultados sugerem que outros óxidos de nióbio ou nióbio metálico foram incorporados nos filmes conforme o fluxo de oxigênio foi diminuído. Foi observada uma relação direta entre a diminuição da vazão de oxigênio durante a deposição e um aumento da quantidade de nióbio nos filmes, acompanhados de um aumento do índice de refração e da densidade superficial. / Niobium oxide thin films have been used in many technological applications. There are at least three stable niobium oxides: NbO, NbO2 and Nb2O5 and each one has specific properties. The Nb2O5 is the most stable thermodynamically form having unique physical and chemical properties such as high refractive index, wide band gap, excellent chemical stability and corrosion resistance, low optical absorption in the field of visible light to near the infrared regions, being widely used as high quality optical interference filters. In this work niobium oxide thin films were deposited by reactive sputtering technique on silicon and borosilicate substrates. The films were obtained by using oxygen flow rates varying from 15 up to zero sccm. The objective of this work was the optical characterization of niobium oxide films. The refractive index and the thickness were evaluated by ellipsometry technique, the band gap by TAUC method and the atomic ratio and the surface density by means of Rutherford backscattering spectrometry (RBS). Spectral transmittance and reflectance spectrophotometry by UV / Vis / NIR curves were obtained and the extinction coefficient was calculated by the method of Hong. All of these parameters are important for application in optical devices. In the films deposited with oxygen flow of 15 sccm it was observed that the refractive index increases with increasing thickness of the films and analyzes indicated that Nb2O5 forms for when a flow rate of 15 sccm is used. For a flow rate of 2.0 sccm it was found NbO2 and a high optical absorption. As the flow of oxygen used in the deposition of the films was decreased, there were signs that were incorporated in the films other oxides of niobium or niobium metal itself. A direct relationship between decreased of oxygen flow during deposition and a increase in niobium quantity in the films, accompanied by an increase in the refractive index and surface density was observed.

Atualmente, a caracterização dos resíduos radioativos gerados na operação do reator nuclear de pesquisas IEA-R1 está em curso. O reator IEA-R1 é um reator do tipo piscina aberta, moderado e refrigerado por água leve, utilizando dois leitos de resinas de troca iônica e de carvão ativado para purificação de água de refrigeração. Estes meios filtrantes são substituídos quando já não são capazes de manter a qualidade da água dentro dos limites exigidos e são tratados como rejeitos radioativos. Contendo produtos de fissão, ativação e actinídeos que escapam do núcleo do reator para a água da piscina, apresentam altas taxas de dose devido à quantidade de emissores gama de meias-vidas curtas e intermediárias, emissores alfa, elementos transurânicos de meia-vida longa bem como emissores beta puros. A caracterização destes rejeitos, consequentemente, requer métodos de análise radioquímica que incluem a amostragem e o processamento das amostras, resultando em doses elevadas para os trabalhadores. Nesse contexto, o objetivo deste trabalho consistiu em correlacionar os resultados das análises radioquímicas de amostras de rejeitos, com os resultados das medições radiométricas, utilizando a modelagem das taxas de dose em diferentes distâncias da superfície dos embalados. As taxas de dose medidas foram comparadas com os resultados de cálculos . Massa, volume e geometria das fases sólidas e líquidas de cada um dos tambores também foram determinadas, uma vez que o teor de água varia amplamente entre diferentes tambores, e são essenciais para estimar as atividades totais em cada tambor. / The characterization of the radioactive wastes generated in the operation of the nuclear research reactor IEA-R1 is currently ongoing. The IEA-R1 is an open pool type reactor, moderated and cooled by light water that uses two beds of ion-exchange resins and activated charcoal to remove impurities from the cooling water. These filter media are replaced when they are no longer able to maintain water quality within the required limits and are treated as radioactive waste. They contain the actinides and the fission and activation products that leaked into the reactor pool water. They give off high dose rates due to the amount of gamma-emitters present and are a long-term radiation safety concern because of their content of long-lived alpha- and beta-emitters. The characterization of these wastes requires radiochemical analysis methods, which include the sampling and processing of samples, resulting in high exposure to the workers. The objective of this study was to correlate the results of activity concentrations obtained in previous radiochemical analyses with the results of measurements of dose rates at various distances from the package surfaces, aiming at reducing the exposure of personnel by avoiding more sampling and sample analysis operations. Mass, volume and geometry of solid and liquid phases of each drum, which vary widely among different drums, were also estimated and use to determine total activity. The measured and calculated dose rates were compared to confirm the activity estimates.

A caracterização no estado sólido de insumos farmacêuticos constitui uma parte muito importante no entendimento de suas propriedades físicas, químicas e farmacológicas. A partir da análise estrutural por difração de raios X em monocristal, pode-se identificar a conformação no estado sólido do fármaco, assim como sua densidade eletrônica. Estes estudos podem ser complementados com dados provenientes da Modelagem Molecular, que compreende um número de ferramentas e métodos computacionais e teóricos que têm como objetivos compreender e prever o comportamento de sistemas reais. Nesse contexto, visando compreender melhor as propriedades de estado sólido apresentadas pelo fármaco anti-filariose dietilcarbamazina (DEC), foi obtido um novo sal, o maleato de dietilcarbamazina (DEC maleato), cujas propriedades foram comparadas com as das estruturas já reportadas, DEC citrato e DEC pura. A DEC maleato foi caracterizada por difração de raios X em monocristal, espectroscopias Raman e Infravermelho e análise térmica. A DEC maleato cristaliza no grupo espacial triclínico PI com dois confôrmeros da molécula de DEC na unidade assimétrica, ambos exibindo caudas etílicas na conformação syn em relação ao anel piperazina, diferentemente do que ocorre na DEC citrato e na DEC pura, nas quais esses fragmentos moleculares apresentam uma conformação anti. A principal interação intermolecular entre o fármaco e o ácido maleico é do tipo N-H•••O, que caracteriza a formação do sal e, consequentemente, do par iônico (DEC)+(maleato)-. Além disso, uma rede complexa de interações intermoleculares não-clássicas do tipo C-H•••O estão presentes entre as moléculas de DEC, DEC-maleato e maleato-maleato, levando a um empacotamento cristalino na forma de um sanduíche, onde os confôrmeros da DEC acomodam-se em colunas intercaladas por bicamadas de íons maleato. Não foram observadas transições de fase estruturais em função da temperatura entre 100 K e temperatura ambiente. No entanto, devido à variação conformacional observada entre as moléculas de DEC, cálculos quânticos foram realizados na fase gasosa, otimizando as conformações moleculares tanto da molécula de DEC neutra quanto da carregada a fim de determinar as características de sua estrutura eletrônica utilizando o método da Teoria do Funcional de Densidade, com o funcional híbrido B3LYP e o conjunto de função de base 6-31++G. Através dos cálculos teóricos foram obtidas quatro novas conformações, uma para DEC neutra e três da carregada, para as quais analisou-se as energias de conformação, os espectros vibracionais simulados e por fim os mapas de potencial eletrostático e os orbitais de fronteira. / The solid state characterization of active pharmaceutical ingredients (API) constitutes an important part in understanding their physical, chemical and pharmacological properties. From the structural analysis by single crystal X-ray diffraction, the API conformation in the solid form, as well as its electronic density, can be identified. These studies can be supplemented with data from the Molecular Modeling, which includes a number of theoretical and computational tools used to understand and to predict the behavior in real systems. In this context, aiming to better comprehend the solid state properties exhibited by the anti-filarial drug diethylcarbamazine (DEC), a new salt was obtained, the diethylcarbamazine maleate (DEC maleate), and its properties were compared with the ones of the reported structures, DEC citrate and pure DEC. The DEC maleate was characterized by single crystal X-ray diffraction, infrared and Raman spectroscopy and thermal analysis. DEC maleate was found to crystallize in the triclinic space group PI with two very similar conformers of the DEC molecule in the asymmetric unit, both exhibiting the ethylic chains in conformation syn in relation to the piperazine ring, unlike what happens to DEC citrate and pure DEC, where these chains are anti related. The main intermolecular interaction between the API and the maleic acid is of the type NH•••O, characterizing the salt formation, and thus, the ionic pair (DEC)+(maleate)-. Moreover, a complex network of no-classical intermolecular interactions of the type CH•••O occur between DEC-DEC, DEC-maleate, and maleate-maleate molecules, leading to a sandwich like crystal packing, where DEC conformers are accommodated in columns intercalated by maleates bilayers. No phase transitions were observed for the molecule structure in function of temperature between 100 K and room temperature. However, due conformational variations observed among DEC molecules of the three structures, quantum calculations were performed in the gas phase, optimizing the molecular conformations of both, the neutral and the charged DEC molecules to determine the characteristics of the electronic structure using the method of Density Functional Theory with the B3LYP hybrid functional and basis set 6-31++G. new conformations it were found, for which geometrical characteristics, conformation energies, vibrational spectra simulation and finally the electrostatic potential maps and the frontier orbitals, were analyzed.

Esta dissertação apresenta os resultados da investigação geotécnica de uma área que apresenta processos erosivos, na cidade de Bauru, interior de São Paulo, com o objetivo de caracterizar o solo local e definir quais os principais fatores responsáveis pela evolução desses processos. Eles tiveram início com o desmatamento, impermeabilização do solo, deságüe de águas pluviais e esgoto e atingiram grandes dimensões com a implantação de loteamentos, com projeto inadequado e falta de obras de infra-estrutura de drenagem. Com observações de campo, ensaios in situ e laboratório, o fenômeno foi estudado com o intuito de se estabelecer um mecanismo que explique o processo erosivo. No local ocorrem desde solos residuais jovens de arenito, a residuais maduros, muito evoluídos por processos pedogenéticos e em alguns pontos se tem também solos transportados. Foram realizados ensaios de caracterização, de erodibilidade e mecânicos em três amostras distintas e representativas de solos do local, além de ensaios de campo SPT e CPT. Esses solos foram classificados como uma areia pouco argilosa de coloração variável e quase sempre se encontram em condição não saturada. Os resultados dos ensaios de erodibilidade mostraram que os três métodos empregados classificaram os solos como altamente erodível, sendo o método mais interessante aquele proposto por Nogami & Villibor (1979) para os solos estudados. A sucção exerce papel importante na resistência desses solos e a saturação das amostras promoveu a redução significativa da coesão. A água é o agente deflagrador e principal responsável pela evolução do processo erosivo, tanto pelo escoamento superficial como pelo escoamento subsuperficial. O seu fluxo no interior do maciço carreia material e modifica a distribuição granulométrica do solo, alterando também suas propriedades. O mecanismo de evolução se inicia com o aumento do teor de umidade do solo pela ação da chuva podendo, em alguns pontos, chegar-se a saturação, provocando a diminuição da resistência através da anulação do efeito da coesão. Uma vez saturado e com o fluxo de d\'água, o solo pode perder sua estrutura por erosão interna retrogressiva, assim é facilmente destacado e carreado, provocando a instabilidade dos taludes e evolução do processo erosivo. / This dissertation presents geotechnical site characterization results of an erosion process area, in Bauru city, inland of São Paulo State, Brazil. The objective is to characterize the local soil and define the major causing factors for the erosion process evolution, which initiated with deforestation, soil sealing and discharge of pluvial and sewer water. The erosion turned huge with an urban setting with inappropriate design and no drainage infrastructure jobs. This phenomenon was studied by field observation, in situ and laboratory tests to establish a mechanism to explain the erosion process. Young residual soils of sandstone, mature residual soil weathered by pedogenetic processes and transported soils occur in the site. Characterization, erodibility and mechanical tests were carried out on three typical and distinct soils as well as SPT and CPT testing. The soils were classified as clayey sand with variable colors, almost always in unsaturated condition. Erodibility test results from three different methods classified the soils as very high erodibility, and Nogami and Villibor (1979) method was the most interesting for the studied soil. Suction plays an important role in the shear strength and soil saturation significantly reduced cohesion. Water is the trigging agent and the major responsible for the erosive process evolution, even by superficial or groundwater flow. The flow inside the soil mass changes the grain size distribution of the soil and also modifies their properties. The evolution mechanism begins increasing the soil water content by the rain and it can, in some places, reach soil saturation reducing shear strength turning cohesion equal to zero. Since the soil is saturated and with water flow, it can loose its structure by piping, so it\'s easily detached and dragged along causing slope instability and evolution of erosion process.

Orientador: Maria Regina Wolf Maciel / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-23T03:12:51Z (GMT). No. of bitstreams: 1 Rocha_EricaRobertaLovo_D.pdf: 2034684 bytes, checksum: b50381e5062bfd908c1e80ed673fd6d9 (MD5) Previous issue date: 2013 / Resumo: Com o objetivo de satisfazer a demanda do mercado por derivados de petróleo de alto valor agregado, investimento em tecnologias que envolvem o melhor aproveitamento de petróleos pesados e seus resíduos tem sido realizado. Dentre os processos em desenvolvimento para aumentar a conversão de resíduo e a produção de frações de maior valor comercial destaca-se a destilação molecular, que permite obter cortes e resíduos a temperaturas superiores aquelas alcançadas por métodos padronizados, sem o risco de degradação térmica das amostras. O presente trabalho teve como finalidade o fracionamento de três resíduos atmosféricos e um resíduo de vácuo utilizando o protótipo nacional de destilador molecular, desenvolvido pelo grupo de pesquisa do LOPCA/LDPS/VALPET/UNICAMP, e a determinação das propriedades das frações obtidas para avaliar a qualidade da separação e as características dos produtos. Utilizando planejamento experimental, os efeitos da temperatura de destilação (TDM) e da vazão de alimentação no rendimento da destilação (%D) foram analisados, mostrando que a TDM e a variável mais significativa do processo. Em seguida, os dados operacionais dos experimentos no destilador molecular foram correlacionados por meio da correlação DESTMOL e estendeu-se a curva de Ponto de Ebulição Verdadeiro (PEV) dos petróleos ate valores próximos a 700 °C, com boa continuidade em relação à curva PEV convencional. Além disso, a destilação molecular promoveu ganhos em termos de rendimento de destilado que variaram entre 9,7% e 11,6% para os petróleos estudados. O conjunto de caracterizações das frações de petróleo mostrou que o processamento dos resíduos de petróleo no destilador produziu produtos com diferenças significativas das propriedades em relação à amostra inicial, nos quais os componentes mais pesados foram concentrados nos resíduos da destilação molecular, enquanto os componentes mais leves foram separados na corrente destilada (corte). Logo, o protótipo nacional de destilador molecular mostrou ser adequado para a separação de resíduos de petróleo e para a obtenção de frações com intervalos de temperatura e rendimentos acima dos atingidos pelas destilações padronizadas / Abstract: In order to supply the demand for high value petroleum products, investments in technologies involving the best use of heavy oils and petroleum residues have been carried out. Among the processes in development to increase the conversion of petroleum residues and the production of higher commercial value fractions stands up the molecular distillation process which is able to obtain petroleum cuts and petroleum residues at temperatures higher than those achieved by standard methods, without risk of thermal degradation of the samples. The present work aimed the fractionation of three atmospheric residues and one vacuum residue using the national molecular distiller prototype, developed by the research group of LOPCA/ LDPS/VALPET/UNICAMP, and the determination of the fractions properties to evaluate the quality of separation and the characteristics of the products. Using experimental design, the effects of distillation temperature (TDM) and feed flow rate on the yield of distillation (%D) were analyzed, showing that TDM is the most significant variable of the process. Thereafter, the operational data of the molecular distiller experiments were correlated by DESTMOL and the True Boiling Point (TBP) curve of the oil was extended to temperatures near to 700 ° C, with great continuity related to the conventional TBP curve. In addition, molecular distillation process presented gains in distillate yield that varied between 9.7% and 11.6% for the studied oils. The set of petroleum fractions characterization showed that the processing of petroleum residue in the distiller produced products with significant differences compared to the properties of the initial sample, in which the heavier components were concentrated in the molecular distillation residues, while the lighter components were separated in the distillate stream (cuts). Therefore, the national molecular distiller prototype demonstrated to be suitable for the petroleum residues separation and for obtaining fractions with temperature ranges and distillate yields above of the achieved by standard distillations / Doutorado / Desenvolvimento de Processos Químicos / Doutora em Engenharia Quimica

Orientador: Antonio José Ramirez Londono / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-20T13:37:33Z (GMT). No. of bitstreams: 1 TorresLopez_EdwarAndres_D.pdf: 14707024 bytes, checksum: 982b5dbc99d5f7bbef2ea2c34019eea4 (MD5) Previous issue date: 2012 / Resumo: Neste trabalho foram realizadas juntas soldadas dissimilares de aço carbono AISI SAE 1020 e a liga de alumínio AA6063-T5, com 2 mm de espessura, empregando o processo de soldagem por atrito com pino não consumível (SAPNC). As juntas soldadas a topo foram realizadas empregando ferramenta de WC-14Co, com diâmetro de ombro e pino de 25,0 e 5,7 mm, respectivamente, e comprimento de pino de 1,35 mm. Foram empregadas velocidades de rotação e avanço de 300 RPM e 150 mm.min-1, respectivamente, para três deslocamentos da ferramenta: +0,5, +1,0 e +1,5 mm. A caracterização microestrutural foi realizada por meio de microscopia óptica e eletrônica de varredura e de transmissão, difração de elétrons retroespalhados (EBSD), espectrometria de raios X dispersiva em energia (X-EDS) e difração de raios X (DRX). Para relacionar os parâmetros de soldagem com a microestrutura das juntas soldadas, foram elaborados os perfis da história térmica durante a soldagem. Juntas soldadas consolidadas foram obtidas para deslocamentos tangenciais da ferramenta (DT) de +1,0 e +1,5 mm, sendo descartado o DT de +0,5 mm por resultarem em penetração heterogênea ao longo da junta. As juntas realizadas no presente trabalho podem ser consideradas como de baixo aporte térmico. Esta condição evitou a formação da denominada zona de menor dureza na zona termicamente afetada (ZTA) do lado do alumínio e de compostos intermetálicos AlxFey na interface alumínio-aço. Na zona misturada, foram obtidas evidências da presença de dois mecanismos de recristalização dinâmica diferentes. No lado de avanço da zona misturada foi identificado o mecanismo de recristalização dinâmica geométrica, enquanto no lado de retrocesso o mecanismo ativo foi recristalização dinâmica continua / Abstract: In this work dissimilar AISI SAE 1020 mild steel and aluminum alloy AA6063-T5 joints, with 2 mm thickness, were friction stir welded (FSW). The welded joints were conducted employing WC-14Co tools, with shoulder and pin diameter of 25.0 and 5.7 mm respectively, and pin length of 1.35 mm. Rotation and weld speeds of 300 RPM and 150 mm.min-1 were employed, for three tool offsets: 0.5, 1.0 and 1.5 mm. The microstructural characterization was performed through optical, scanning and transmission electron microscopy, electron backscatter diffraction (EBSD), energy dispersive X-ray spectroscopy (X-EDS) and x-ray diffraction (DRX). In order to correlate the welding parameters with the final microstructure of the joints, thermal history profiles were collected during welding. Consolidated welded joints were obtained for tool offsets (DT) of +1.0 and +1.5 mm, being discarded the +0.5 mm offset by to produce heterogeneous penetration along the welded joint. The joints made in this work can be considered as low-heat input. This condition prevented the formation of the so-called low hardness zone in heat affected zone (HAZ) aluminum side, and the formation of intermetallic compounds AlxFey in the aluminum-steel interface. In the stir zone evidences of the presence of two different dynamic recrystallization mechanisms were observed. In the advance side of the stir zone, the geometric dynamic recrystallization was identify as working mechanism, while in retreating side of the stir zone, the active mechanism is the so-called continuous dynamic recrystallization / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

Abstract The aim of this thesis is the knowledge of the most relevant deactivation mechanisms of Pd/Rh three-way catalysts under different ageing conditions, the deactivation correlation of laboratory scale ageing and engine bench/vehicle ageings, and the evaluation of the deactivation correlation. In the literature review, the phenomena involved in the three-way catalyst operation and its deactivation are considered. In the experimental section, ageing-induced phenomena in the catalyst are studied and deactivation correlations between laboratory scale and engine bench/vehicle ageings are presented, based on the results of several surface characterization techniques. The effects of ageing atmosphere and temperature, and time are considered in particular. Fresh and aged catalysts used in this study were metallic monoliths designed for Euro IV emission limits. Thermal ageings were carried out in the reductive, oxidative and inert atmospheres in the temperature range of 800°C to 1200°C, and in the presence of water vapour (hydrothermal ageing). The engine ageing was carried out in the exhaust gas stream of a V8 engine during a 40 hour period. The ageing procedure composed of rich and stoichiometric air-to-fuel ratios carried out consecutively. The vehicle ageing was accomplished under real driving conditions (100 000 kilometres). According to the results, deactivation of a Pd/Rh monolith is a combination of several ageing phenomena. The most important deactivation mechanisms are the sintering of active phase, the collapse in surface area and ageing-induced solid-solid phase transitions in the bulk washcoat. Furthermore, poisoning is a relevant deactivation mechanism of the vehicle-aged catalyst. High ageing temperature, gas phase composition and exposure time are essential variables to the deactivation of a Pd/Rh three-way catalyst. This thesis presents an approach to discover the deactivation correlation between the laboratory scale ageing and under the vehicle's operation in an engine bench or on-road. Based on the characterization results, the accelerated laboratory scale air ageing does not correspond to the ageing-induced changes in the catalyst under the vehicle's operation. Therefore, there is a need for a modified ageing cycle and according to the results, a deactivation correlation between the laboratory scale ageing and the engine bench ageing can be presented as a function of ageing temperature and atmosphere, and time. Instead, after the vehicle operation, the deactivation correlation cannot be presented based solely on the studied variables because, after 100 000 kilometres of driving, the role of poisoning should be taken into account in the ageing cycle. The results of this thesis can be utilized and applied in the development of laboratory scale ageing cycles, which corresponds closely to the ageing-induced changes in the catalyst during the vehicle operation. This enables a rather fast testing of the catalyst's performance and reduces the cost during the manufacturing of catalysts.

Silicon Carbide is a wide bandgap semiconductor with excellent physical and opto-electrical properties. Among these excellent properties are its radiation hardness, high temperature operation and high electric field breakdown. SiC can therefore be used in the fabrication of electronic devices capable of operating in harsh environments, e.g. radiation detectors. Like any other semiconductor, the success of SiC in device fabrication depends on elimination of defects that are detrimental to desired devices or controlled introduction of desired energy levels. The first step in so doing is understanding the defects that are either found in as grown material, introduced during device fabrication or introduced during device operation. In this study nickel ohmic and Schottky contacts were resistively fabricated on n-type 4H-SiC with a net doping density of 4 × 1014 cm-3. Current-Voltage (I-V), Capacitance-Voltage (C-V), Deep Level Transient Spectroscopy (DLTS) and Laplace-DLTS measurement techniques were used to electrically characterize the fabricated Schottky diodes. The diodes were then irradiated with low energy electrons, alpha particles and protons. The characterization measurements were repeated after irradiation to evaluate the effect of irradiation on the electrical properties of SiC. It was observed from I-V measurements that electron, alpha particle and proton irradiations do not significantly affect the rectification of Ni/SiC Schottky contacts. C-V measurements indicated that the free carrier removal rate is higher for alpha particle irradiation as compared to electron irradiation. The irradiated diodes were annealed in argon ambient and significant recovery in the free carrier concentration was observed below 600 °C. The free carrier concentration of proton irradiated Schottky contacts, which was decreased to below detection levels was also partly recovered after heat treatment of up to 400 °C. DLTS and Laplace-DLTS measurements revealed the presence of four defect levels in as-grown 4H-SiC. These defects have been labelled E0.10, E0.12, E0.17 and E0.69 where the subscripts indicate the activation energies of the respective defects. Electron, alpha particle and proton irradiations were observed to induce three more defect levels with activation energies of 0.42 eV, 0.62 eV and 0.76 eV. Additionally, these irradiations were also observed to enhance the concentration of level E0.69. All the radiation induced defects were annealed out at temperatures below 600 °C. In proton irradiated diodes, another defect with activation energy of 0.31 eV was observed after annealing the irradiated diodes at 625 °C. / Dissertation (MSc)--University of Pretoria, 2014. / lk2014 / Physics / MSc / Unrestricted

Despite the poor understanding of charge transfer in conducting polymers, conducting-polymer-based devices have achieved considerable commercial success. This success is based largely on the reproducibility of the measurable properties. It is the purpose of this study to further clarify charge transfer characteristics of conducting polymers under varying conditions. We studied a conducting polymer called polyaniline. Polyaniline was available in its doped conducting form called emeraldine salt and in its undoped form called emeraldine base. Three types of polyaniline were studies, electrosynthesized (doped by HCI), chemically synthesized (doped by HCI) and commercial polyaniline obtained from Adlrich Company and doped by camphor sulfonic acid. Initially we investigated whether charge transfer was ionic or electronic by observing the change in resistance with time for a fixed applied current. It was concluded that condition in this material is electronic. Electrical measurements were obtained using the four-point probe and the Montgomery methods. The samples investigated were in pellet and film forms. We investigated charge transfer over the temperature regime 30-450 K by applying the following methods: scanning electron microscopy to investigate the surfaces of pellet and film samples, Fourier transform infrared spectroscopy and Raman spectroscopy to investigate the effect of annealing on the molecular structure of the polymer and thermal analysis to investigate the loss of substances from the polymer as a result of the annealing process. The conductivity of the material was also analyzed over the entire temperature regime. The following were observed: • Conductivity in polyaniline is governed my monomer units. • The decrease in conductivity with increase annealing temperature is related to moisture loss, loss of dopant ions and polymer degradation. • The variable range hopping model in three dimensions, satisfactorily describes charge transfer mechanism in polyaniline. • Conductivity in polyaniline is temperature activated. • Conductivity varies with position on the sample surface. • The effect of pellet pressing pressure to conductivity is negligible. • Current-voltage characteristics for polyaniline exhibit non-ohmic behavior at high current values, (>0.2 mA for T <80 K), applied between the current probes of a four-point probe measuring instrument. / Dissertation (MSc (Physics))--University of Pretoria, 2006. / Physics / unrestricted

Essential oils are amongst the most complex samples an analyst can face in terms of the number of compounds involved. In many cases, minor components are of interest as they can impart a distinctive fragrance character to the oil. Because of the closely related structures and molecular weights among terpenes, positive identification of individual compounds is very difficult with a single chromatographic technique. Further, most of the analytical information is lost when a single technique is used because of the limited peak capacity and the resulting peak overlap. For many years, gas chromatography coupled to mass spectrometry (GC-MS) has been the benchmark technique for qualitative and quantitative analysis of essential oils. Retention indices and mass spectra have to be used in combination for confirmation of the identity of components in an essential oil. Other multidimensional or hyphenated techniques also offer advantages that aid in the identification of essential oil components. This thesis demonstrates the application of a comprehensively coupled supercritical fluid and fast temperature programmed gas chromatograph (SFCxGC) to the analysis of essential oils. An SFCxGC instrument was used to analyse the essential oils of Cymbopogon (lemongrass), Artemisia afra (wilde als), Tagetes minuta (kakiebos) and Pelargonium (geranium) species. The unique application of a porous layer open-tubular (PLOT) column, used in conjunction with supercritical carbon dioxide is demonstrated to effect group separation of polar, oxygenated compounds. This separation and elution of very polar compounds from a silica gel column is believed to occur due to the reduced phase ratio (ƒÒ) of the system obtained by increasing the volume available to the mobile phase compared to that of a packed column. This separation obtained in the SFC is used to separate essential oils into different chemical classes such as non-polars, ethers, alcohols. Separated chemical classes are re-injected on-line by use of a modulator into a fast, second dimension, temperature programmed GC to effect separation of individual compounds based on their volatility. The entire sample is analysed by both the SFC and GC in such a way that the resolution obtained in the first dimension is conserved by the GC analyses. By using a range of standards, some of the peaks in these oils could be assigned. The identification of compounds was greatly aided by the combination of the two separation dimensions. The comprehensive two-dimensional technique arranges component peaks in a plane from which chemical class and volatility information of each component is readily obtained. The elution pattern within the two-dimensional chromatograms may also be used for direct comparison of oils without identification of the components in the essential oils. / Dissertation (MSc (Chemistry))--University of Pretoria, 2007. / Chemistry / unrestricted