Corrosion is an unstoppable process that occurs spontaneously in many areas of industry, specially, oil and gas industries. Therefore, the need of developing protective coating to lower the cost of corrosion is very consistent. Among different methods, electrodeposition has been a popular method since it offer many advantages such as low cost, ability to control the surface and thickness of the coating, ability to perform at low temperature and pressure, and very convenience. Ceramic nanoparticles have been widely incorporated into metal coating and used as a protective layer to improve both corrosion and hardness properties. Diazonium synthesis was used to modify cerium oxide nanoparticles by grafting with ferrocene for use in nickel nanocomposite coating. Citric acid and citrate salt were used as stabilizing ligands for yttrium oxide and praseodymium oxide nanoparticles in nickel plating solution to prevent the formation of hydroxide, thus, higher amount of nanoparticles was able to incorporate into nanocomposite coatings. These fabricated coatings were evaluate for the corrosion and mechanical properties using many different instruments and electrochemical techniques. As modified cerium oxide, stabilized yttrium oxide or praseodymium oxide added into nickel coatings. The results showed an increase in hardness and corrosion resistance leading to the overall improvement compare to pure nickel coating.

Accelerated soil erosion and the subsequent decline in soil depth has negative environmental, and consequently financial, impacts that have implications across all land cover classifications and scales of land management. Ironically, although attempts to quantify soil erosion nationally have illustrated that soil erosion can occur in the UK, understanding whether or not the UK has a soil erosion problem still remains a question to be answered. Accurately quantifying rates of soil erosion requires capturing both the volumetric nature of the visible, fluvial pathways and the subtle nature of the less-visible, diffuse pathways, across varying spatial and temporal scales. Accordingly, as we move towards a national-scale understanding of soil erosion in the UK, this thesis aims to explore some of the multiple techniques available for developing an understanding of soil erosion in the UK. The thesis first explored the information content of existing UK-based soil erosion studies, ascertaining the extent to which these existing data and methodological approaches can be used to develop an empirically derived understanding of soil erosion in the UK. The second research chapter then assessed which of two proximal sensing technologies, Terrestrial Laser Scanning and Structure-from-Motion Multi-view Stereo (SfM-MVS), is best suited to a cost-effective, replicable and robust assessment of soil erosion within a laboratory environment. The final research chapter built on these findings, using both Rare Earth Oxide tracers and SfM-MVS to elucidate retrospective information about sediment sources under changing soil erosion conditions, also within a laboratory environment Given the biased nature of the soil erosion story presented within the existing soil erosion research in the UK, it is impossible to ascertain if the frequency and magnitude of soil erosion events in the UK are problematic. However, this study has also identified that without ‘true’ observations of soil loss i.e. collection of sediment leaving known plot areas, proxies, such as the novel techniques presented in the experimental work herein and the methods used in the existing landscape scale assessments of soil erosion as included in the database chapter, are not capable of providing a complete assessment of soil erosion rates. However, this work has indicated that despite this limitation, each technique can present valuable information on the complex and spatially variable nature of soil erosion and associated processes, across different observational environments and scales.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第18983号 / 工博第4025号 / 新制||工||1620 / 31934 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 田中 功, 教授 宇田 哲也, 教授 白井 泰治 / 学位規則第4条第1項該当

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18983号 / 工博第4025号 / 新制||工||1620(附属図書館) / 31934 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 田中 功, 教授 宇田 哲也, 教授 白井 泰治 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20389号 / 工博第4326号 / 新制||工||1670(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 江口 浩一, 教授 陰山 洋, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

A obtenção de cerâmicas de SiC pela sinterização com a presença de aditivos que promovam a formação de uma fase líquida (SFL) durante o processo tem sido uma forma adequada para garantir a menor temperatura de sinterização. Pelo fato de o SiC ser frágil, a busca por melhores propriedades mecânicas e avaliação correta das mesmas, para ser aplicado em ambientes agressivos, é contínua. Com base nisso, na primeira etapa, foram estudados, quanto à molhabilidade sobre o SiC, os sistemas AlN/Re2O3 (Re = Dy, Yb) para serem utilizados como aditivos. Os ângulos de contato medidos foram menores que 10° e considerados adequados para a SFL. O SiC sinterizado com esses aditivos permitiu produzir microestruturas diferentes com o aumento da temperatura. Na segunda etapa, foram sinterizadas amostras na forma de pastilhas em várias temperaturas, cujas condições que apresentaram os melhores resultados de massa específica real e densidade relativa foram tomadas como referência para a sinterização na forma de barras prismáticas. Na terceira etapa, essas amostras foram avaliadas quanto à sua tenacidade à fratura (KIC) pelo método da barra entalhada em V, dureza e resistência à flexão. O comportamento de KIC foi avaliado em função da profundidade e raio de curvatura dos entalhes. Os valores variaram entre 2,59 e 3,64 MPam1/2. Verificou-se que os valores de KIC confiáveis foram aqueles encontrados com pequeno raio de curvatura na ponta do entalhe. Quando o raio foi grande, o mesmo não manteve a singularidade da raiz quadrada da ponta do entalhe, e forneceu valores de KIC superestimados. Foram realizados testes para determinar KIC em ar atmosférico e em água, cujos resultados foram menores em água que em ar, com queda entre 2,56 e 11,26%. A maior resistência sob flexão determinada em 4 pontos foi de 482 MPa. Observou-se correlação direta do tamanho dos grãos nos valores de KIC, dureza e módulo de ruptura das cerâmicas de SiC. / Obtaining SiC ceramics by sintering in the presence of additives that promote a liquid phase formation (LPS) during the process has been a proper manner to ensure the lowest sintering temperature. Because SiC is brittle, an ongoing search for better mechanical properties and proper evaluation of these properties for application in aggressive environments maintained. Thus, in the first stage we studied AlN/Re2O3 systems (Re = Dy, Yb), as to their wettability on SiC, for use as additives. The measured contact angles were smaller than 10° and considered suitable for the LPS. The sintered SiC with these additives allowed the production of different microstructures with the increase in temperature. In the second stage, pellet-shaped samples were sintered at various temperatures, and the conditions showing the best density results were taken as reference for sintering prism-shaped bars. In the third stage, these samples were evaluated for toughness (KIC) by single edge V-notched beam method, hardness, and flexural strength. The behavior of KIC was assessed for notch depth and notch radius of curvature. Values ranged between 2.59 and 3.64 MPa/m1/2. The reliable values of KIC were those found with small radius of curvature at the notch tip. When the radius was large, it did not maintain the singularity of the square root of notch tip and provided overestimated KIC values. Tests were performed to determine KIC in atmospheric air and water, and results were lower in water than in air, dropping between 2.56 and 11.26%. The greatest strength under the 4-point bending test was 482 MPa. We observed a direct correlation of grains size in KIC values, hardness and bending strength of SiC ceramics.

A obtenção de cerâmicas de SiC pela sinterização com a presença de aditivos que promovam a formação de uma fase líquida (SFL) durante o processo tem sido uma forma adequada para garantir a menor temperatura de sinterização. Pelo fato de o SiC ser frágil, a busca por melhores propriedades mecânicas e avaliação correta das mesmas, para ser aplicado em ambientes agressivos, é contínua. Com base nisso, na primeira etapa, foram estudados, quanto à molhabilidade sobre o SiC, os sistemas AlN/Re2O3 (Re = Dy, Yb) para serem utilizados como aditivos. Os ângulos de contato medidos foram menores que 10° e considerados adequados para a SFL. O SiC sinterizado com esses aditivos permitiu produzir microestruturas diferentes com o aumento da temperatura. Na segunda etapa, foram sinterizadas amostras na forma de pastilhas em várias temperaturas, cujas condições que apresentaram os melhores resultados de massa específica real e densidade relativa foram tomadas como referência para a sinterização na forma de barras prismáticas. Na terceira etapa, essas amostras foram avaliadas quanto à sua tenacidade à fratura (KIC) pelo método da barra entalhada em V, dureza e resistência à flexão. O comportamento de KIC foi avaliado em função da profundidade e raio de curvatura dos entalhes. Os valores variaram entre 2,59 e 3,64 MPam1/2. Verificou-se que os valores de KIC confiáveis foram aqueles encontrados com pequeno raio de curvatura na ponta do entalhe. Quando o raio foi grande, o mesmo não manteve a singularidade da raiz quadrada da ponta do entalhe, e forneceu valores de KIC superestimados. Foram realizados testes para determinar KIC em ar atmosférico e em água, cujos resultados foram menores em água que em ar, com queda entre 2,56 e 11,26%. A maior resistência sob flexão determinada em 4 pontos foi de 482 MPa. Observou-se correlação direta do tamanho dos grãos nos valores de KIC, dureza e módulo de ruptura das cerâmicas de SiC. / Obtaining SiC ceramics by sintering in the presence of additives that promote a liquid phase formation (LPS) during the process has been a proper manner to ensure the lowest sintering temperature. Because SiC is brittle, an ongoing search for better mechanical properties and proper evaluation of these properties for application in aggressive environments maintained. Thus, in the first stage we studied AlN/Re2O3 systems (Re = Dy, Yb), as to their wettability on SiC, for use as additives. The measured contact angles were smaller than 10° and considered suitable for the LPS. The sintered SiC with these additives allowed the production of different microstructures with the increase in temperature. In the second stage, pellet-shaped samples were sintered at various temperatures, and the conditions showing the best density results were taken as reference for sintering prism-shaped bars. In the third stage, these samples were evaluated for toughness (KIC) by single edge V-notched beam method, hardness, and flexural strength. The behavior of KIC was assessed for notch depth and notch radius of curvature. Values ranged between 2.59 and 3.64 MPa/m1/2. The reliable values of KIC were those found with small radius of curvature at the notch tip. When the radius was large, it did not maintain the singularity of the square root of notch tip and provided overestimated KIC values. Tests were performed to determine KIC in atmospheric air and water, and results were lower in water than in air, dropping between 2.56 and 11.26%. The greatest strength under the 4-point bending test was 482 MPa. We observed a direct correlation of grains size in KIC values, hardness and bending strength of SiC ceramics.

No description available.

Dans le contexte général lié aux économies d’énergie, l’amélioration sensible du rendement des turbines à gaz (aéronautiques ou terrestres), nécessitera d’augmenter notablement la température des gaz de combustion. Cela implique l’emploi de matériaux stables au-delà de 1 500°C. Les céramiques eutectiques préparées par solidification dirigée, à partir des systèmes Al2O3 - Ln2O3 (où Ln représente un élément lanthanide ou l’yttrium) sont une solution envisageable. En effet, leur microstructure, constituée d’un réseau interpénétré 3D de deux phases monocristallines, et exempte de pores, de colonies et de joints de grains, confère à ces systèmes eutectiques des propriétés mécaniques d’un bon niveau, et quasi-constantes jusqu’à des températures proches de leur température eutectique (> 1 700°C). Nos travaux ont consisté à élaborer plusieurs systèmes eutectiques binaires et ternaires, par ajout d’une phase ZrO2 renforçante. Les six systèmes présentant les microstructures les plus prometteuses (3 binaires : Al2O3 - Y3Al5O12, Al2O3 - Er3Al5O12, Al2O3 - GdAlO3, et 3 ternaires : Al2O3 - Y3Al5O12 - ZrO2, Al2O3 - Er3Al5O12 - ZrO2, Al2O3 - GdAlO3 - ZrO2) ont été retenus pour étudier certaines de leurs propriétés mécaniques. Plusieurs modes de fissuration, allant dans le sens de l’augmentation de ténacité détectée dans ces systèmes, ont été décelés après des essais de flexion biaxiale. Ces modes de fissuration ont été corrélés aux caractéristiques microstructurales et à la distribution des contraintes résiduelles, déterminées par le calcul et mesurées par une méthode piézo-spectroscopique. Enfin, l’étude du comportement en fluage à haute température a permis de mettre en évidence une évolution des mécanismes de déformation en fonction des conditions de sollicitation. L’étude MET post mortem a également souligné l’influence marquée du caractère interconnecté de la microstructure sur le comportement en fluage. / In the general context of energy savings at a global scale, the improvement of the thermal efficiency of both terrestrial and aeronautical gas turbines will require to increase the turbine inlet gas temperature. The development of new materials, stable up to 1 500°C, is thus necessary. In this context, Directionally Solidified Eutectic Ceramics (DSEC), prepared from Al2O3 and Ln2O3-based systems, could be a potential solution. Their microstructure consists of two single-crystal phases continuously entangled in a threedimensional interpenetrating network without grain boundaries, pores or colonies. The outstanding stability of these microstructures gives rise to a high strength and creep resistance at high temperature. Our research consisted first in obtaining, by directional solidification, several eutectic systems, either binary or ternary (with addition of a toughening third ZrO2 phase). The six most promising DSEC (3 binary systems: Al2O3 - Y3Al5O12, Al2O3 - Er3Al5O12, Al2O3 - GdAlO3, and 3 ternary systems: Al2O3 - Y3Al5O12 - ZrO2, Al2O3 - Er3Al5O12 - ZrO2, Al2O3 - GdAlO3 - ZrO2) have then been selected to study some of their mechanical properties. Several crack propagation patterns have been detected after biaxial flexure testing, and partially explain the toughening which has been proven for DSEC. Attention has been paid to the possibility of crack deflection in the various phases and in the phase boundaries, a phenomenon which may markedly improve the toughness of these eutectic ceramics. These observations have been correlated to internal stress calculations and piezo-spectroscopic measurements. Finally, the study of the creep behavior showed that the deformation mechanisms evolve with the macroscopic solicitation (temperature and stress). microstructure. Moreover, post mortem TEM observations exhibited that creep mechanisms are strongly dependant on the entangled microstructure.

Made available in DSpace on 2017-07-21T19:26:07Z (GMT). No. of bitstreams: 1 Simoneapa.pdf: 1470043 bytes, checksum: b380a790ad5236069470caa27e038eed (MD5) Previous issue date: 2007-03-02 / In this work, it was accomplished an experimental study about the substitution of the yttrium atom (Y) in the YBa2Cu3O7-x superconductor system for a rare earth oxide (RE2O3), gotten from the xenotime ore. Chemically, this substitution is possible due to the equality of the oxidation state between the Y3+ ions and the earth rare ions, which form the oxide. This way, this substitution should not modify the properties of the superconductor system significantly. The xenotime in its natural form is composed of a rare earth phosphate, zirconita and other heavy elements. The zirconita and the heavy elements can be separated by magnet or gravimetric process. The rare earth phosphate is chemically treated by the acid or the alkaline leaching process, resulting in a rare earth oxide (RE2O3). The xenotime ore used in this work was extracted from the Pitinga mine (AM, Brazil). Four polycrystalline samples were processed through the solid-state reaction, from the precursors: rare earth oxide (RE2O3), barium carbonate (BaCO3) and copper oxide (CuO), forming the REBa2Cu3O7-x superconducting oxide. The chracterization of the samples crystalline structures was studied by x-ray diffraction. The analysis of the samples superficial morphology was studied by optical microscopy and scanning electron microscopy (SEM). The properties of electronic transportation were analyzed by measurements of electric resistivity. Among the analyzed samples, one did not present null state of electric resistance. The measurements of electric resistivity for the other samples revealed superconductor behavior and showed that the critical temperature of the REBa2Cu3O7-x system is around 90 K, as in the YBa2Cu3O7-x system. Such values were confirmed by the measurement of magnetic susceptibility. The analyses of the Xray diffractograms of the samples revealed that the cell parameters of both systems are equal. These results indicate that the substitution of the Y for the rare earth oxide is possible, which may have important implications both from the point of view of basic research and the applied research. / Neste trabalho foi realizado um estudo experimental da substituição do átomo de ítrio (Y) no sistema supercondutor YBa2Cu3O7-x, por um óxido de terras-raras (RE2O3), obtido a partir do minério xenotima. Quimicamente essa substituição é possível devido à igualdade do estado de oxidação entre os íons Y3+ e os íons de terras-raras que formam o óxido. Dessa forma, essa substituição não deve alterar de forma significativa as propriedades supercondutoras do sistema. A xenotima em sua forma natural é constituída por um fosfato de terras-raras, zirconita e outros elementos pesados. A zirconita e os elementos pesados podem ser separados por processos magnéticos ou gravimétricos. O fosfato de terras-raras é tratado quimicamente pelo processo de lixiviação ácida ou alcalina, resultando em um óxido de terras-raras (RE2O3). O minério xenotima utilizado neste trabalho foi extraído da mina do Pitinga (AM, Brasil). Foram processadas quatro amostras policristalinas através da reação de estado sólido, a partir dos precursores: óxido de terras raras (RE2O3), carbonato de bário (BaCO3) e óxido de cobre (CuO), formando o óxido supercondutor REBa2Cu3O7-x. A caracterização das estruturas cristalinas das amostras foi estudada por difração de raios X. A análise da morfologia superficial das amostras foram estudadas por microscopia óptica e microscopia eletrônica de varredura (MEV). As propriedades de transporte eletrônico foram analisadas através de medidas de resistividade elétrica. Das amostras processadas, uma não apresentou estado de resistência elétrica nula. As medidas de resistividade elétrica para as demais amostras revelaram comportamento supercondutor e mostraram que a temperatura crítica do sistema REBa2Cu3O7-x, está em torno de 90 K, como no sistema YBa2Cu3O7-x. Esses valores foram confirmados pelas medidas de susceptibilidade magnética. As análises dos difratogramas de raios X das amostras revelaram que os parâmetros de cela dos dois sistemas são iguais. Esses resultados indicam que substituição do Y pelo óxido de terras-raras é possível, podendo ter importantes implicações tanto do ponto de vista de pesquisa básica como da pesquisa aplicada.