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Made available in DSpace on 2014-10-09T12:49:28Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:01:16Z (GMT). No. of bitstreams: 0 / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares, IPEN/CNEN-SP

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Made available in DSpace on 2014-10-09T12:49:28Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:01:16Z (GMT). No. of bitstreams: 0 / Quando um país se torna auto-suficiente em uma parte do ciclo nuclear, quanto à produção de combustível que será usado em suas centrais nucleares para a geração de energia, precisa voltar sua atenção para a melhor forma de armazenar este combustível após a sua utilização. A armazenagem do combustível nuclear queimado é uma prática necessária e utilizada nos dias atuais em todo o mundo como temporária, tanto por países que não têm definido o plano de destinação final, isto é, o repositório definitivo, como também por aqueles que já o possuem. Existem dois aspectos principais que envolvem os combustíveis queimados: um referente à armazenagem do combustível nuclear queimado destinado ao reprocessamento e o outro ao que será enviado para deposição final quando o sítio de deposição definitiva estiver definido, corretamente localizado, adequadamente caracterizado quanto aos diversos aspectos técnicos, e licenciado. Este último aspecto pode envolver décadas de estudos por causa das definições técnicas e normativas em um dado país. No Brasil, o interesse está voltado para a armazenagem dos combustíveis queimados que não serão reprocessados. Este trabalho analisa os tipos possíveis de armazenagem, o panorama internacional e a possível proposta para a futura construção de um sítio de armazenagem temporária no país. / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares, IPEN/CNEN-SP

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Current state-of-the-art fuel cells depend on relatively high quantities of platinum metal to function. For fuel cells to become economically feasible as a replacement for the internal combustion engine there needs to be a drastic reduction in the quantity of platinum used within them. ACAL Energy has developed a fuel cell that allows for an 80 % reduction in the quantity of platinum required. This is achieved by replacing the solid supported cathode with an aqueous catholyte solution that contains within it a non-precious metal catalyst. The work contained in this thesis explores a library of non-heme metal complexes as potential candidates for use as catalysts for the 4 electron oxygen reduction reaction at the cathode of the FlowCath® fuel cell. The catalysts chosen, Fe(II) TPEN, Fe(II) TRILEN and Fe(II) TPTCN, are super oxidise dismutase mimics and are known to effectively reduce oxygen in a homogeneous solution. These catalysts were studied in fuel cell-like conditions to gain an understanding of their effectiveness in reducing oxygen. Attempts to decorate the complexes with sulfonate groups led to the evolution of the isoquinoline-based complexes. The change from pyridine-based complexes to isoquinoline-based complexes led to the formation of six alternative complexes, Fe(II) 1-miq TQEN, Fe(II) 3-miq TQEN, Fe(II) 1-miq TRILEN, Fe(II) 3-miq TRILEN, Fe(II) 1-miq TQTCN and Fe(II) 3-miq TQTCN, four of which (1-/3-miq TRILEN and 1-/3-TQTCN) are new to the academic literature. These complexes were analysed for their use as catalysts in the oxygen reduction reaction. In addition to the synthetic and analytical work carried out, computational models of the complexes were created. This theoretical data gave a deeper insight into the molecular structure of the complexes studied and the spin states of the Fe(II) and Fe(III) species.

A model for motor gasoline demand in Canada is developed by household. The model identifies and separates effects of several responses by the household to a change in gasoline prices such as driving fewer miles, purchasing fewer cars, and buying more fuel efficient cars. It also estimates the manufacturers' response of improving the technology of new automobiles. The size and the composition of the fleet according to the interior volume of four classes of automobiles rather than their natural weight is used. Furthermore, two components of the average fuel efficiency of new cars were identified and estimated. The first is the technical fuel efficiency set by the car manufacturers and the second is the sales ratio of four classes of new automobiles. The use of household expenditure survey data make it possible to experiment with some socio-economic variables such as the percentage of households living in urban areas, number of cars per household and the number of persons in the household who can drive. The relatively new technique of cointegration is also utilized. The results indicate that there are certain advantages associated with the elaborate treatment of the stock adjustment and the fuel economy of the fleet. In general, the estimated coefficients suggest that most of the adjustment after a gasoline price increase comes from miles driven in the short run and from miles per gallon, hence fuel efficiency improvements in the long run. The model gave the total short run (one year) price elasticity of gasoline consumption between 0.312 - 0.313 for the different provinces which is relatively small range. One of the more interesting results is that approximately 10 percent of the household response to a price change in the first year was due to a change in the composition of the fleet to a more fuel efficient vehicle. Approximately 75 percent was due to driving fewer miles while the remaining 15 percent was attributed to a change in the size of the fleet. The intermediate run (five year) price elasticities range from 0.689 to 0.7 09 and the long run price elasticities (ten year) range from 0.97 5 to 1.059. The long run price elasticities exceed unity which does not lend support to the belief that long run gasoline price elasticities are also inelastic. The short term household income elasticities range from 0.301 to 0.306, the intermediate term range from 0.655 to 0.679, and the long term range from 0.868 - 0.949.

Magister Scientiae - MSc / Characterization of nanophase electrocatalysts, which are an essential part in the direct methanol fuel cell (DMFC) and solid-polymer electrolyte (SPE) electrolyser, have been studied in this work. Their nanoparticulate size raises significant challenges in the analytical techniques used in their structural and chemical characterization. Hence, the applicability of analytical protocols for the qualitative and quantitative characterization of structural and chemical properties of nanophase platinum and platinum-ruthenium electrocatalysts was investigated. Also, fabricated carbon-supported platinum, platinum-ruthenium, iridium oxide, and mesoporous silica-templated platinum electrocatalysts were screened on the basis of their electrocatalytic activity. A set of structural and chemical parameters influencing the performance of nanophase electrocatalysts was identified. Parameters included crystallinity, particle size, particle size distribution, agglomeration, aggregation, surface area, thermal stability, chemical speciation, electrocatalytic activity, and electrochemically-active surface area. A large range of analytical tools were employed in characterizing the electrocatalysts of interest. High accuracy and precision in the quantitative and qualitative structural characterization of nanophase electrocatalysts, collected by x-ray diffractometry and transmission electron microscopy, was demonstrated. Selected-area electron diffraction was limited to a rapid qualitative evaluation of electrocatalyst polycrystallinity and crystal symmetry. Scanning electron microscopy was limited to the qualitative evaluation of the agglomeration state of supported electrocatalysts. High-performance particle sizing was unable to resolve the particle size of the electrocatalyst from that of the support and was therefore employed in the quantitative investigation of aggregate size and size distribution in supported electrocatalysts. The technique produced high precision data illustrating the reproducibility of the aggregate size data. N2-physisorption produced surface area and pore size distribution data of high quality, but was unable to determine surface areas specific to the metal phase in supported electrocatalysts. The technique was deemed inconsistent in the accurate determination of average pore size. The resolution of scanning electrochemical microscopy and proton-induced x-ray emission spectroscopy (SECM) did not allow for an investigation of characteristics at the nanoscale. Quantitative chemical information was difficult to extract from SECM maps and the technique was limited to the qualitative characterization of surface topography. Thermogravimetry was suitable for the qualitative investigation of the thermal stability of the nanophase electrocatalysts of interest. In this study, temperature-programmed reduction was able to qualitatively speciate the surface chemical state and investigate the strength of the metal-support interaction in supported nanophase electrocatalysts. Cyclic voltammetry and linear-sweep voltammetry were employed in the electrochemical characterization of nanophase electrocatalysts and both qualitative and quantitative information were obtained. The techniques were able to discriminate between various commercial and fabricated electrocatalysts and identify new highly-active materials. Preparation variables could be critically evaluated for the fabrication of cost-effective highly-active nanophase electrocatalysts. Certain techniques were deemed to be highly applicable in discriminating between high and low activity nanophase electrocatalysts based on their structural and chemical properties. The electrocatalyst characterization strategy and methodology was developed and will be implemented for future characterization of nanophase electrocatalysts. / South Africa

Magister Scientiae - MSc / The main objective of this work it to produce membrane electrode assemblies (MEAs) that have improved performance over MEAs produced by the conventional manner, by producing highly efficient, electroactive, uniform catalyst layers with lower quantities of platinum electrocatalyst. The catalyst coated membrane (CCM) method was used to prepare the MEAs for the PEM fuel cell as it has been reported that this method of MEA fabrication can improve the performance of PEM fuel cells. The MEAs performances were evaluated using polarisation studies on a single cell. A comparison of polarisation curves between CCM MEAs and MEAs produced in the conventional manner illustrated that CCM MEAs have improved performance at high current densities (>800 mA/cm2). / South Africa