Thesis (Ph.D.)--University of Melbourne, The School of Chemistry, 2010. / Typescript. Includes bibliographical references.

Thesis (Ph.D.) -- McMaster University, 2001. / Includes bibliographical references. Also available via World Wide Web.

Orientador: Fenelon Martinho Lima Pontes / Co-orientador: James Venturini / Banca: Alejandra Hortencia Miranda González / Banca: Aroldo Geraldo Magdalena / Banca: Vinicius Carvalho Porto / Banca: Willian Zambuzzi / Resumo: O aumento de doenças infecciosas vem perturbando as economias mundiais e a saúde pública. As bactérias que contribuem para essa preocupação são as Escherichia coli, Gram-negativa e a Staphyloccocus aureus, Gram-positiva. Essas bactérias podem provocar infecções graves, principalmente quando presentes em água, alimentos e ambientes hospitalares. Nanopartículas estão sendo desenvolvidas para o tratamento e prevenção dessas estirpes biológicas. Nanoestruturas de ZrO2 apresentam propriedades, ópticas, fungicidas e bactericidas. Quando os metais são suportados nas estruturas, como, Ag, suas propriedades bactericidas são potencializadas. Os materiais foram produzidos por síntese hidrotermal e caracterizados por DRX, UV-Vis, FTIR, MEV, TEM e TG. Para avaliar as nanopartículas sintetizadas, foram realizados testes de atividade antimicrobiana com as bactérias Escherichia coli e Staphylococcus aureus (cepas sensíveis e resistentes à meticilina). A eficiência da avaliação antimicrobiana foi mensurada por cinética de crescimento e estatística, por ensaio colorimétrico de viabilidade e MEV. Os resultados das caracterizações mostraram a metodologia de produção de nanopartículas por rota hidrotermal que foram eficientes na produção de nanomateriais cristalinos com morfologia esférica para a zircônia tetragonal, com tamanhos entre 7 e 10 nm e prata cúbica, com tamanho médio entre 40 e 50 nm. As técnicas de TG e FTIR indicaram e permitiram quantificar e identificar a presença de matéria orgâ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The increase in infectious diseases is disrupting the world's economies and public health. The bacteria that contribute to this concern are Escherichia coli, one Gram-negative bacilli and Staphylococcus aureus, Gram-positive. These bacteria can cause serious infections, especially when present in water, food and hospital environments. Nanoparticles are being developed for the treatment and prevention of these biological strains. ZrO2 nanostructures have properties such as optical, fungicides and bactericides. When metals are supported in the compound, such as, Ag, its bactericidal properties are enhanced. The materials were produced by hydrothermal synthesis and characterized by XRD, UV-Vis, FTIR, SEM, TEM and TG. To evaluate the synthesized nanoparticles Antimicrobial activity tests were performed using Escherichia coli and strains of methicillin-resistant and methicillin-sensitive Staphylococcus aureus. Evaluation of antimicrobial activity was determined by kinetic of growth, vaibility assay and SEM. The results of the characterization showed the nanoparticles production methodology by hydrothermal route that were efficient in the production of crystalline nanomaterials with sherical morphology for tetragonal zirconia with sizes between 7 and 10 nm and cubic silver, with an average size between 40 and 50 nm. TG techniques and FTIR indicated and allowed to quantify and identify the presence of residual organic matter in the synthesis process / Doutor

Made available in DSpace on 2016-01-13T13:26:53Z (GMT). No. of bitstreams: 0 Previous issue date: 2015-07-07. Added 1 bitstream(s) on 2016-01-13T13:32:12Z : No. of bitstreams: 1 000854863.pdf: 5368324 bytes, checksum: f60f5de47f46c51ce3e51ec3e6e81da4 (MD5) / Com aumento do número de veículos automotores em circulação, a quantidade de poluentes lançados no nosso planeta é muito significativa, sendo um risco real ao nosso meio ambiente. Vários avanços tecnológicos têm sido apreentados nos últimos anos, objetivando a redução destas emissões. As cerâmicas têm desempenhado um papel primordial neste cenário. Dentre estas, encontra-se o sensor de oxigênio que utiliza a zircônia (ZrO2) como eletrólito sólido, componente do sistema de gerencialmento eletrônico do motor do ciclo Otto, e elemento primordial na estratégia de reduzir as emissões e o consumo de combustível. Neste trabalho analisou-se o desempenho de quatro sensores de marcas líderes no mercado, com países de origem diferentes, originalmente desenvolvidos para operar com gasolina pura se comportam com combustível de uso alternativo, com composição química e fases distintas, Etanol (líquida) e GNV (gasosa). Instalados em um motor do ciclo Otto de 4 tempos, dotado de sistema de gerencialmento eletrônico multicombustível (Tetrafuel) original de fábrica, funcionando de forma autônoma ao veículo, operando em duas rotações predefinidas. Foram coletados e registrados os seguintes dados operacionais: sinal elétrico, tempo de resposta, temperatura de operação, e emissões de gases. Os valores obtidos nas etapas estipuladas foram tabulados e posteriormente analisados. Quando utilizado o Etanol como combustível, as tensões médias nas duas rotações foram menores que as observadas utilizando-se o GNV, a temperatura na região do sensor também se apresentou superior para o Etanol. O tempo médio de resposta para o Etanol foi superior ao GNV. Analisando as emissões geradas, concluímos que as mesmas estão de acordo com o preconizado na legislação vigente, indicando que o sistema de gerenciamento eletrônico do motor e consequentemente os sensores de oxigênio avaliados, cumprem plenamente e de forma adequada... / With the increasing number of motor vehicles in circulation, the amount of pollutantos released in the atmospheric air is very significant, being a real disk to our planet. People concerned about the consequences resulting from his problem have charged effective actions in order to minimize the impact of polluent generated and the preservaton of the life quality on our planet. Significant technological advances have been made in recent years, both in the forms of propulsion, when on reducing emissions by engines. The development and adoption of new materials, both in construction, or in the control of the several systems, is one of the bases of this major development. Among these materials, the ceramics have played a very important role in this scene, whose applications are enabling the achievement of the proposed objectives. This work focuses primarilly about the oxygen sensor using zirconia (ZrO2) as basic element. Also known as lambda sensor, it is used in automobiles to control along with the electronic management system of the engine, of air-fuel ratio, in orderto reduce the emissions and the fuel comsumption in internal combustion engines of Otto and Diesel cycles. It is installed in the exhaust gas system and aims to measure the residual oxygen content in gases produced by the engine. In this work we analyzed the performance of these sensors in measuring the concentration of residual oxygen content in the exhaust gases when installed on an Otto cycle engine, 4 stroke, endowed with electronic multi fuel management system (Tetrafuel), installed independently to the vehicle on a test bench, operating distinctly with liquid fuel (ethanol) and gas (CNG), in two predefined speeds. In this work, we will present is composition, construction, operating principles and performance in a real operating situation, of four sensors of different manufacturers allowing the understanding of its interaction with the electronic management system and the...

Orientador: Cesar R. Foschini / Banca: Délson Luiz Módolo / Banca: Carlos Alberto Fortulan / Resumo: Com aumento do número de veículos automotores em circulação, a quantidade de poluentes lançados no nosso planeta é muito significativa, sendo um risco real ao nosso meio ambiente. Vários avanços tecnológicos têm sido apreentados nos últimos anos, objetivando a redução destas emissões. As cerâmicas têm desempenhado um papel primordial neste cenário. Dentre estas, encontra-se o sensor de oxigênio que utiliza a zircônia (ZrO2) como eletrólito sólido, componente do sistema de gerencialmento eletrônico do motor do ciclo Otto, e elemento primordial na estratégia de reduzir as emissões e o consumo de combustível. Neste trabalho analisou-se o desempenho de quatro sensores de marcas líderes no mercado, com países de origem diferentes, originalmente desenvolvidos para operar com gasolina pura se comportam com combustível de uso alternativo, com composição química e fases distintas, Etanol (líquida) e GNV (gasosa). Instalados em um motor do ciclo Otto de 4 tempos, dotado de sistema de gerencialmento eletrônico multicombustível (Tetrafuel) original de fábrica, funcionando de forma autônoma ao veículo, operando em duas rotações predefinidas. Foram coletados e registrados os seguintes dados operacionais: sinal elétrico, tempo de resposta, temperatura de operação, e emissões de gases. Os valores obtidos nas etapas estipuladas foram tabulados e posteriormente analisados. Quando utilizado o Etanol como combustível, as tensões médias nas duas rotações foram menores que as observadas utilizando-se o GNV, a temperatura na região do sensor também se apresentou superior para o Etanol. O tempo médio de resposta para o Etanol foi superior ao GNV. Analisando as emissões geradas, concluímos que as mesmas estão de acordo com o preconizado na legislação vigente, indicando que o sistema de gerenciamento eletrônico do motor e consequentemente os sensores de oxigênio avaliados, cumprem plenamente e de forma adequada... / Abstract: With the increasing number of motor vehicles in circulation, the amount of pollutantos released in the atmospheric air is very significant, being a real disk to our planet. People concerned about the consequences resulting from his problem have charged effective actions in order to minimize the impact of polluent generated and the preservaton of the life quality on our planet. Significant technological advances have been made in recent years, both in the forms of propulsion, when on reducing emissions by engines. The development and adoption of new materials, both in construction, or in the control of the several systems, is one of the bases of this major development. Among these materials, the ceramics have played a very important role in this scene, whose applications are enabling the achievement of the proposed objectives. This work focuses primarilly about the oxygen sensor using zirconia (ZrO2) as basic element. Also known as lambda sensor, it is used in automobiles to control along with the electronic management system of the engine, of air-fuel ratio, in orderto reduce the emissions and the fuel comsumption in internal combustion engines of Otto and Diesel cycles. It is installed in the exhaust gas system and aims to measure the residual oxygen content in gases produced by the engine. In this work we analyzed the performance of these sensors in measuring the concentration of residual oxygen content in the exhaust gases when installed on an Otto cycle engine, 4 stroke, endowed with electronic multi fuel management system (Tetrafuel), installed independently to the vehicle on a test bench, operating distinctly with liquid fuel (ethanol) and gas (CNG), in two predefined speeds. In this work, we will present is composition, construction, operating principles and performance in a real operating situation, of four sensors of different manufacturers allowing the understanding of its interaction with the electronic management system and the... / Mestre

Atualmente o ramo industrial tem voltado grande parte de suas atenções para situações ambientais. Um dos grandes problemas mundiais encontra-se no uso de cromo hexavalente, prejudicial à saúde humana, além de contaminar leitos e rios por ser solúvel em água e a fosfatização que é responsável pela eutrofização das águas. Novos processos sustentáveis têm sido estudados para reduzir os impactos ambientais causados por esses tratamentos, dentre os quais podemos citar os revestimentos chamados de nanocerâmicos, por formarem camadas nanoestruturadas de óxido de zircônio na superfície do substrato. Vários parâmetros influenciam na formação da camada (substrato, pH, concentração, tempo). O trabalho teve como objetivo o estudo da influência dos parâmetros no desempenho contra a corrosão do revestimento formado por camadas de conversão obtidas a base de ácido hexafluorzircônio em aço galvanizado. O comportamento eletroquímico foi analisado através dos ensaios de potencial de circuito aberto, espectroscopia de impedância eletroquímica e polarização potenciodinâmica. Também foram realizados ensaios de avaliação anticorrosiva com adição de um revestimento final (tinta comercial) sobre a camada de conversão para avaliar o comportamento como revestimento. A partir dos ensaios realizados chega-se a parâmetros que foram considerados ideais e com melhor desempenho. Com isso obtém-se um pré-tratamento capaz de fazer frente a processos convencionais de cromatização e fosfatização. / Currently, the industrial sector has turned much of their attention to environmental situations. One of the great global problems is the use of hexavalent chromium, harmful to human health and pollute rivers and beds being soluble in water and phosphate which is responsible for water eutrophication. New sustainable processes have been studied to reduce the environmental impacts caused by these treatments, among which we can mention the nanoceramic coatings called for forming nanostructured layers of zirconium oxide on the substrate surface. Several parameters influence the layer formation (substrate, pH, concentration, time). The work aims to study the influence of parameters on the performance against corrosion coating formed by conversion layers obtained acid based hexafluorzirconic on galvanized steel. The electrochemical behavior was analyzed through the trials of open circuit potential data, electrochemical impedance spectroscopy and polarization. Also evaluation trials were performed with addition of an anti-corrosive top coat (commercial ink) on the layer of conversion coating painted as to evaluate the corrosion resistance. From the tests to parameters that were considered ideal and best performance. Thus is obtained a pretreatment able to cope with the conventional processes chromate and phosphate.

Atualmente o ramo industrial tem voltado grande parte de suas atenções para situações ambientais. Um dos grandes problemas mundiais encontra-se no uso de cromo hexavalente, prejudicial à saúde humana, além de contaminar leitos e rios por ser solúvel em água e a fosfatização que é responsável pela eutrofização das águas. Novos processos sustentáveis têm sido estudados para reduzir os impactos ambientais causados por esses tratamentos, dentre os quais podemos citar os revestimentos chamados de nanocerâmicos, por formarem camadas nanoestruturadas de óxido de zircônio na superfície do substrato. Vários parâmetros influenciam na formação da camada (substrato, pH, concentração, tempo). O trabalho teve como objetivo o estudo da influência dos parâmetros no desempenho contra a corrosão do revestimento formado por camadas de conversão obtidas a base de ácido hexafluorzircônio em aço galvanizado. O comportamento eletroquímico foi analisado através dos ensaios de potencial de circuito aberto, espectroscopia de impedância eletroquímica e polarização potenciodinâmica. Também foram realizados ensaios de avaliação anticorrosiva com adição de um revestimento final (tinta comercial) sobre a camada de conversão para avaliar o comportamento como revestimento. A partir dos ensaios realizados chega-se a parâmetros que foram considerados ideais e com melhor desempenho. Com isso obtém-se um pré-tratamento capaz de fazer frente a processos convencionais de cromatização e fosfatização. / Currently, the industrial sector has turned much of their attention to environmental situations. One of the great global problems is the use of hexavalent chromium, harmful to human health and pollute rivers and beds being soluble in water and phosphate which is responsible for water eutrophication. New sustainable processes have been studied to reduce the environmental impacts caused by these treatments, among which we can mention the nanoceramic coatings called for forming nanostructured layers of zirconium oxide on the substrate surface. Several parameters influence the layer formation (substrate, pH, concentration, time). The work aims to study the influence of parameters on the performance against corrosion coating formed by conversion layers obtained acid based hexafluorzirconic on galvanized steel. The electrochemical behavior was analyzed through the trials of open circuit potential data, electrochemical impedance spectroscopy and polarization. Also evaluation trials were performed with addition of an anti-corrosive top coat (commercial ink) on the layer of conversion coating painted as to evaluate the corrosion resistance. From the tests to parameters that were considered ideal and best performance. Thus is obtained a pretreatment able to cope with the conventional processes chromate and phosphate.

There are two industrial sources of zirconia: zircon and baddeleyite [1-5]. The baddeleyite reserves in Phalaborwa (the world’s major baddeleyite source) are expected to be depleted by the year 2005 [1-3]. This leaves the Russian Baddleyite (Kola Peninsula) and zircon as the only industrial sources of zirconia. The major drawback to zircon use is the large amounts of impurities it is found concentrated with, especially radioactive impurities (Uranium and Thorium) [2-3]. Acid leaching of zircon does not remove these impurities [4-5]. The impurities are usually included in the zircon lattice. The tetragonal structure of zircon with the high coordinated bisdisphenoids ZrO8 and low coordinated tetrahedra SiO4 create a safe (inaccessible and stable) habitat for these impurities [7]. Processes for the recovery of zirconia and zirconium chemicals rely heavily on precipitation or cyrstallisation techniques for purification [8-16]. Precipitation techniques need to be repeated to obtain the required purity. The purity of products from such methods is still suspect, as there still remains a high radioactivity content after purification [2]. The long process time is another disadvantage of these precipitation processes. These factors together are the reason for the high cost of zirconia and zirconium chemicals. Zirconium and its compounds are regarded to be of low toxicity [1-6]. This implies that they have a great potential of replacing numerous high toxic chemicals. Prominent examples are seen in leather tanning and paints. In leather tanning chromium chemicals can be replaced. In paints lead driers and chromium chemicals for corrosion resistance can be replaced. The objective of this study was to characterise and optimise the De Wet’s zirconium extraction processes for the beneficiation of zircon sand into high purity zirconia and zirconium chemicals. However, at each process step some factors were varied e.g. fusion temperature, reactant mole ratios and composition of leach solutions. Attention was also paid to reducing the total number of process steps. The products produced at each step were analysed. Particular attention was given to the fate of the radioactive impurities. Characterisation of the decomposition step, showed that within the zircon tetragonal structure, the SiO4 bisdisphenoids linkages. This was shown by the preference of sodium for the SiO4 tetrahedra. Fusion for 336 hours with periodic intermediate milling proved the preference of sodium for attacking the SiO4 tetrahedra linkages. This selectivity was clearly demonstrated when decomposing zircon in sodium poor(<4 moles NaOH per mol of zircon) and low temperature (e.g. 650°C) reaction conditions. The advantage of fusing at 650°C with a mole (or even two moles) of sodium hydroxide is that it leads to minimal (<5% m/m Na2O) sodium in the insoluble solids after the removal of soluble silicates. This is a solution to alkali fusion processes, as high amounts of water are usually required to wash out the neutralised sodium salt e.g. 50g of NAC1 usually requires a litre of distilled water to reach levels below 600 ppm NA2O. This reaction condition can be employed when synthesising products where low amounts of sodium are required in the final products e.g. when synthesising zirconia for the ceramic industry. When fusing for two hours without the intermediate milling step the following results were observed. The reaction at 850°C when fusing a mole of zircon with two moles of sodium hydroxide, was the most efficient in consuming sodium hydroxide. Near complete zircon decomposition was at 850°C when fusing a mole of zircon with six moles of sodium hydroxide. Characterisation with XRD, Raman and IR spectroscopy was misleading as complex spectra were measured, indicating many different phases present. The inconsistency was partly attributed to non-homogeneity in the samples due to NaOH migration. When fusing for 336 hours with the intermediate milling step the following results were observed. The reaction at 850°C when fusing a mole of zircon with a mole of sodium hydroxide was the most efficient in consuming sodium hydroxide. This reaction condition was able to liberate 0.58 moles of zirconia per mole of sodium hydroxide. The highly improved efficiency was attributed to the formation of phases Na2ZrSiO5, Na4Zr2Si3O12 and SrO2. The process is pseudo-catalytic as it liberates zirconium while showing minimal sodium consumption. Decomposition at 650°C also showed improved efficiency but not as efficient as the 850°C sub-stoichiometric fusion. The improved decomposition was attributed to the polymerisation of the orthosilicate monomers Na4SiO4 to the metasilicate chains Na2SiO3. / Dissertation (MSc (Chemical Technology))--University of Pretoria, 2007. / Chemical Engineering / unrestricted

This work was performed as part of the MUZIC-2 (Mechanical Understanding of Zirconium Corrosion) collaboration, established with the goal of understanding the mechanism of hydrogen pickup in zirconium alloys. Hydrogen pickup is one of the least understood and most significant degradation mechanisms affecting zirconium alloys in nuclear reactors. These alloys are used as cladding and structural materials in the reactor core, mainly due to their low thermal neutron absorption cross section and excellent corrosion resistance. This project aims to investigate the effect of oxide texture (i.e. the degree of preferred orientation) on the corrosion performance of zirconium alloys. The texture of the oxide is expected to affect the microstructural development of the oxide, the grain boundary distribution and the stress state. It is therefore considered to be one of the most important factors in determining how the corrosion process occurs, and why different alloys exhibit significantly different corrosion performance. It is hoped that this project will add to the current knowledge of the corrosion process, and in particular hydrogen pickup, so that the route of hydrogen through the protective oxide can be identified. This will lead to the development of a new generation of alloys that provide improved oxidation and hydrogen pickup performance, whilst maintaining the required mechanical properties. This work focuses on four zirconium alloys; Zircaloy-4, ZIRLO™, low-Sn ZIRLO™ and Zr-1.0Nb-0.1Fe. The alloys all have different chemical compositions and therefore exhibit different corrosion performance. The macrotexture of the oxide formed on different alloys was measured by glancing angle X-ray diffraction (XRD) and Electron Backscatter Diffraction (EBSD). A fibre texture was formed in all cases, with the (10-3) to (10-5) planes oriented parallel to the metal-oxide interface for the monoclinic phase. The major orientation was found to be independent of alloy chemistry, substrate orientation and oxidation conditions. The monoclinic texture strength was found to be weakened with increasing oxidation temperature, The major orientation of the tetragonal phase was also found to be a fibre texture, with the (001) planes oriented approximately parallel with the interface. Although significant variation from this texture component was observed. It is suggested that the main driving force for oxide texture development is the transformation stress induced by the Zr-ZrO2 transformation. The microtexture of the oxides was measured using two novel techniques, Transmission Kikuchi Diffraction (TKD) and automated crystal orientation mapping with transmission electron microscopy (TEM). The techniques revealed an oxide microstructure consisting of an outer layer of equiaxed grains with a large range of orientations and an inner layer consisting of well-aligned columnar monoclinic grains. This layer of equiaxed grains was observed to form again after the transition in corrosion kinetics. A large fraction of transformation twin boundaries were observed throughout the oxides. Some of these boundaries were observed to surround large monoclinic grains, providing evidence that the tetragonal grains from which they transformed had grown considerably larger than the critical grain size for stabilisation. Without the presence of Sn, larger monoclinic grains were observed to form with a greater degree of preferred orientation, and with a lower fraction of transformation twin boundaries than Sn-containing alloys. In addition, an increased number of well-oriented tetragonal grains was correlated with the presence of Sn. It is therefore concluded that a reduction in Sn will lead to the formation of an oxide microstructure that is more resistant to both oxidation and hydrogen pickup. An analysis of the crystallography and morphology of a ZrO phase present at the metal-oxide interface was also performed. Finally, the observations have been used to construct a model of the corrosion process.

Anodic films have been produced on zirconium and zirconium alloys potentiostatically (at either 20 or 40 V) in 0.35 M ammonium fluoride in glycerol, with interest in the addition of small amounts of water (up to 5 vol.%) to the electrolyte on their growth, morphologies and compositions. Scanning and transmission electron microscopies have been employed to analyse morphologies of the films, which appeared to be porous under all the investigated conditions.Rutherford backscattering spectroscopy and nuclear reaction analysis, used as techniques to investigate film compositions, disclosed the presence of zirconium, oxygen, fluorine, carbon and nitrogen in the films. The contents of fluorine and oxygen in the films were found to increase and decrease respectively by decreasing the amount of water added to the electrolyte from 5 to 0 vol.%. Moreover, the content of fluorine increased by decreasing the applied formation voltage, from 40 to 20 V, for films formed in electrolytes containing similar amounts of added water.In order to get information on the distribution of the species in the films, cross-sections of selected specimens were produced by focused ion beam and analysed by analytical transmission electron microscopy. Oxide-rich nanotubes were revealed embedded in a fluoride-rich matrix, suggesting that the mechanism of growth of the anodic films is governed by different migration rates of the anionic species in the film base, with F- ions, being the fastest anions. The relative amounts of the oxide-rich and fluoride-rich materials were related to the composition of the electrolyte, with the fluoride regions being less extensive and the oxide-rich nanotubes being thicker-walled by adding small amounts of water. Moreover, nanotubes are constituted of two shells (an outer one surrounding the pores and an inner one located between the outer shell and the matrix), suggesting differences in the composition in these two regions, presumed to be due to the incorporation of carbon species, being the slowest migrating species, in the outer shell. The fluoride-rich matrix chemically dissolved following 1 h immersion of the specimens in the formation electrolytes, promoting the transition from porous to nanotubular morphologies. Ageing of the specimens in deionized water for similar times did not significantly influence the morphologies and compositions of the anodic films.