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En esta tesis se estudian la electrocatálisis de algunas reacciones involucradas en las pilas de combustible. Se utilizan electrodos monocristalinos de oro y platino para analizar, a nivel fundamental, los procesos que tienen lugar en la interfase entre electrodo y la disolución. En una primera parte se analiza la oxidación de ácido fórmico e hidracina que son dos combustibles empleados en las celdas de combustible. Posteriormente se estudian reacciones secundarias a las mismas como es la oxidación de CO o la oxidación y reducción de peróxido de hidrógeno.

Biofuel additives have been designed to reduce vehicular emissions to the atmosphere to limit the effects of greenhouse gases on global climate change. The chemical properties of common biofuel additives exhibit ideal characteristics for use in gasoline and diesel, while limiting emissions from exhaust. As biofuel additives begin to be administered regularly to gasoline and fuel sources, the compounds will appear in spill sites, posing a risk to groundwater sources. The interactions that occur between common biofuel additives and trapped gases below the water table were analyzed in this work to further understand the potential consequences on quasi-saturated groundwater zones. The behaviour of trapped gases contaminated with different biofuel additives were analyzed in laboratory experiments conducted in a two-dimensional flow cell to demonstrate the mechanisms of gas flow through a capillary barrier resulting from modified interfacial properties in the presence of a chemical surfactant. Contamination of gas-fluid interfaces by applied biofuel additives at the pore scale resulted in the breakthrough of gas through the capillary barrier. Gas migration terminated at a critical pool height proportional to the reduction in interfacial tension induced by the administered biofuel additives. To further demonstrate the relationship between interfacial tension and critical gas pool height, an interfacial tension-macroscopic invasion percolation model was developed to simulate the transport mechanisms and behaviours of gas flow when an immobile pool is contaminated with 1-Butanol. The findings in this study provide a fundamental understanding of the mechanisms and behaviours of gas mobilization in the presence of common biofuel additives. / Thesis / Master of Science (MSc) / The use of biofuel additives in gasoline and diesel fuels has become an attractive alternative to fully petroleum-based fuels to reduce the release of vehicular greenhouse gases to the atmosphere. As fuel spills and storage tank leaks continue to be a primary source of groundwater contamination, the appearance of biofuel additives in contaminated systems will appear below the subsurface as they continue to be administered to modern gasoline and diesel fuels. This work investigated the consequences of biofuel contamination of groundwater systems containing gas trapped within pore spaces through the use of laboratory experiments and numerical modelling. Contamination of these systems with different biofuel additives displayed a similar response, in which gas had mobilized from within pore spaces and released to the atmosphere. Mobilization of trapped gas in groundwater can alter the primary hydraulic properties that characterize a particular hydrogeologic system.

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Membrane processes have received growing attention due to their low energy consumption and ease of operation. Thin-film composite reverse osmosis membranes based on polyamides are the most widely applied commercial membranes, because of their high flux and selectivity. However, their application for gas separation processes is still limited. This is the due to the presence of defects in the membrane when in the dry state. Traditionally, thin-film composite membranes are made by interfacial polymerization between a polar (aqueous) phase and a non-polar (organic) phase. The most commonly applied thin-film composite membranes are made by dissolving m-phenylene diamine in the aqueous phase and trimesoyl chloride in the organic phase. This work investigated the possibility of fabricating thin-film composite membranes when an aliphatic alcohol (methanol, ethanol or isopropanol) is used as the polar phase. This is further extended to examining the ability of a PDMS coating to plug the defects in such layers. The effects of temperature and support type on the membrane performance were also studied. Solubility tests were conducted to determine the solubility limit of commercial and in-house fabricated amine monomers in water, methanol, ethanol and isopropanol. Water-insoluble monomers were found to be soluble in ethanol and methanol. Gas permeation tests were conducted on membranes made using water, methanol, ethanol and isopropanol as the polar phase. The results showed that the membranes produced by aliphatic alcohols had higher selectivities. The highest H2/CO2 selectivity of ~ 26 was observed in the ethanol-based membranes when they were coated with PDMS and tested at 80 C. It was confirmed that PDMS is able to plug the defects in the membrane. Membranes made on the polysulfone support were found to have higher permeance and comparable selectivity relative to the membranes made on the polyacrylonitrile supports. It was also found that a change in the polar phase solvent is able to alter the morphology of the membranes. SEM micrographs showed clear differences in the surface structure of each membrane. The average thickness values obtained from ellipsometry measurements showed a correlation with the interface miscibility. The thickest membrane corresponded to the most miscible interface (IPA/Isopar).

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24443号 / 理博第4942号 / 新制||理||1706(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 若宮 淳志, 教授 依光 英樹, 教授 畠山 琢次 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Fiber sizings are used to improve the performance of fiber-reinforced polymer composites made from low-cost fiber and matrix materials. Evaluation of three sizings, poly(vinylpyrrolidone) (PVP), a carboxyl modified polyhydroxyether (PHE), and a standard industrial sizing (G'), have revealed tremendous improvements in static mechanical and enviro-mechanical properties. The focus of this work is to determine if these improvements in performance can be ascertained from a micromechanical test for interfacial shear strength (IFSS) on as-processed materials. The accomplishment of this goal would create more information with fewer experiments and a need for less experimental materials. In this study, a nanoindenter uniquely outfitted with a blunt tip is effectively used to obtain microindentation results where the debond load is extracted directly from the experimental load-deflection curve. Shear lag and finite element analyses are used to evaluate the mechanics of the system, but both methods show limitations with regard to determining interfacial stresses in an experimental system. In the results obtained, the PHE and Gâ materials outperform the PVP in IFSS, but the bulk properties for PVP and PHE outperform the Gâ material, suggesting the presence of another dominant mechanism. Despite better retention of bulk properties after hygrothermal exposure, PHE experiences degradation in IFSS that PVP does not. The PHE loses 10% of its original IFSS after 576 hours of 65ºC moisture exposure, while PVP improves by 25%. The tensile strengths for PHE and PVP decrease 7% and 10% respectively at 576 hours exposure. Finite element modeling shows that matrix swelling due to moisture absorption increases interfacial shear stresses, a finding supported by a comparison of wet and dry specimens subjected to equivalent aging times. Matrix swelling is not, however, responsible for the increase in IFSS of the PVP material. The relationship between tensile strength and IFSS proves to be small as predicted by a tensile strength model, but processing defects and other failure processes that are not included in the tensile strength model appear to have strong influences over the experimental results. IFSS is important in composite materials, but in the case of the G', PHE and PVP materials, other factors dominate fiber direction tensile performance. Therefore, this one simple micromechanical test provides significant insight into the composite material behavior, but it does not provide the same magnitude of information as from bulk composite experiments. / Master of Science