[pt] Uma das atividades relacionadas à recuperação de barragens envolve o alteamento de barragens existentes, normalmente com o objetivo de aumentar a capacidade de armazenamento dos reservatórios, melhorar o fator de segurança dos taludes ou a proteção da estrutura contra possíveis cheias. O alteamento pode estar previsto no projeto original da barragem, mas na maioria dos casos trata-se de um novo estudo, com a barragem em operação, devendo-se verificar as novas condições de fluxo, efeitos na estabilidade de taludes e na resposta da barragem a carregamentos estáticos e sísmicos, estes principalmente em regiões de alta sismicidade, como no sul do Peru, onde se enontram a barragem de terra de Viña Blanca, aqui considerada. Nesta dissertação o método dos elementos finitos e o método de equilíbrio limite, isolada ou conjuntamente, são empregados para análise estática e dinâmica destas barragens de terra considerando diversas opções de alteamento, como a construção de muros parapeito, muros de gabião, solo compactado, solo reforçado com geotêxteis e solo reforçado com revestimento de concreto. De estudos de perigo sísmico efetuados no local das barragens, selecionou-se o valor de aceleração horizontal máximo para ser utilizado nos registros de aceleração ocorridos nos terremotos de Lima (1974) e de Moquegua (2001). As análises numéricas efetuadas mostram que as opções de alteamento consideradas não alteram significativamente as condições de segurança das barragens existentes, tanto do ponto de vista hidráulico como da estabilidade de taludes e resposta dinâmica durante a incidência de terremotos. / [en] One of the activities related to dam constructions involves the raising of the existent structure, normally done with the objective of increasing the water storage capacity of the reservoirs, improving the safety factor of the embankment slopes or to ensure a better protection against possible water flooding. The raising of an earth dam can be predicted in the original dam plan, but in mostly situations consists of a new design, with the dam fully operational, where the effects of a new dam height and reservoir level should be assessed with respect to flow conditions, stability of the embankment soil slopes and the response of the revised structure under static and seismic loads, mainly in highly seismic regions, as in the South of Peru where the earth dam of Viña Blanca, herein studied, was constructed. In this dissertation, the finite element method and the limit equilibrium method were used for the static and dynamic analyses of these earth dams, in their original geometry as well after dam raising with reinforced soil, compacted soil and concrete or gabion structures, among other options. From studies of seismic risk analyses carried out at the dam sites, the value of maximum horizontal acceleration equal to 0.4g was chosen to be used as the peak acceleration in the Lima (1974) and Moquegua (2001) acceleration time histories. The numerical results indicate that all dam raising options investigated in this work do not affect the safety conditions of the dams significantly, either under the point of view of the hydraulic behavior as well as soil slope stabilities or the dynamic response of the earth dams to seismic loads.

[pt] Este trabalho tem como objetivo efetuar um estudo arqueometalúrgico de objetos ferrosos e não-ferrosos resgatados de sítios históricos do Rio de janeiro. A pesquisa experimental desenvolveu uma metodologia de análise utilizando-se de técnicas destrutivas como Microscopia Ótica (MO), Microscopia Eletrônica de Varredura (MEV), Microscopia Eletrônica de Transmissão e não destrutivas como Fluorescência de Raio X (FRX) e Emissão de Raios-X por Indução de Partículas (PIXE). Os objetos foram analisados com o intuito de caracterizar sua composição, estrutura e método de elaboração. Estes correspondem a seis artefatos de natureza metálica não-ferrosa e um de natureza metálica ferrosa. O objeto metálico ferroso corresponde a uma enxada. As características microestruturais dos objetos estão correlacionadas com a função que esses desempenhavam na época e indicativa de que a enxada possa ter sido feita no Brasil por escravos africanos. A análise da enxada permite concluir que é constituída de um ferro pudlado e que foi processada por fundição e forjamento. Quanto aos objetos não-ferrosos, o rosário é constituído de um latão monofásico mais rico em cobre. Com relação à fabricação do rosário pode-se concluir de que seja de origem européia, sendo decorrente de um minério pirítico. As medalhas são de procedência européia constituídas de latão. Historicamente, pode-se deduzir que são referentes ao século XVIII. Conclui-se que as duas moedas do Sítio Rochedo sejam originárias de fontes diferentes, constatado pelas análises químicas. Porém, as concentrações químicas da moeda de 1821 são próximas a uma das moedas de 40 réis. A presente tese permitiu evidenciar a importância da sistemática de trabalho experimental de caracterização, a partir de técnicas destrutivas e nãodestrutivas de materiais, de objetos arqueológicos para estabelecer seu contexto histórico. / [en] This work undertakes an archeometallurgical study of ferrous and non-ferrous artifacts recovered from historical sites of Rio de Janeiro. The experimental research developed an analytical methodology based on destructive techniques, such as Optical Microscopy (OM), Scanning Electronic Microscopy (SEM) and Transmission Electronic Microscopy (TEM); as well as non- destructive techniques, namely X-Ray Fluorescence (XRF) and Particle Induction X-Ray Emission (PIXE). These artifacts were analyzed in order to characterize their composition, structure and elaboration/processing methods. There are six artifacts with a non-ferrous metallic nature and one with a ferrous metallic nature. The ferrous metallic artifact was a hoe. The microstructure characteristics is related to the usage of this object at that time, and indicates that the hoe could have been made in Brazil by African slaves. The analysis of the hoe indicates that it was elaborated from puddle iron and that it had been processed by foundry and forging. The rosary, one of the non-ferrous artifacts, is formed by singlephase brass riche in copper; and according to historical research it is of European origin, deriving from pyrite ore. The medals are also of European origin and are based on brass. Historically one can deduce that they are dated from the 18th century. The two coins from the Rochedo site most probably came from distinct sources, as validated by the chemical analysis. However, the chemical composition of the 1821 coin is close to that of the 40 réis coin. The present thesis has shown the importance of a systematic methodology to characterize ancient objects combining both destructive and non- destructive techniques.

[pt] Em problemas geotécnicos podem ocorrer grandes deformações devido a chuvas prolongadas, sismos, deslizamentos de encostas, etc. Material point method (MPM) é um método de solução baseado no Método dos Elementos Finitos (MEF) que oferece vantagens para o cálculo estático e dinâmico que envolve deformações desse tipo. O objetivo desta dissertação é utilizar o MPM em problemas geotécnicos em condições estáticas e dinâmicas. Esta pesquisa mostra o procedimento de analises do MPM para a condição não acoplada (só solido sem presença de água) e depois acoplada. Para a revisão matemática de MPM se faz antes um resumo da teoria do MEF na metodologia de conservação de quantidade de movimento. Nestas duas formas de resolver os problemas geotécnicos foram expostos três exemplos simples. O primeiro é uma coluna de solo simulado sob os fundamentos da elasticidade, com o objetivo de verificar o deslocamento vertical pelo peso próprio. Isto foi resolvido mediante quatro diferentes métodos: analítica, MEF por resíduos ponderados, MEF por conservação de quantidade de movimento, e MPM. Todos eles consideram somente a fase solida. No segundo exemplo, tem-se solo na geometria de quadrado de lado 1 metro, onde busca-se obter as poropressões quando atingir a condição permanente enquanto os deslocamentos ocorrem ao longo do tempo; ou seja, a análise é acoplada e é resolvida pelo método MPM. Para uma aplicação mais realista, foi feita a análise (não acoplada) da barragem Palo Redondo, pertencente ao projeto Chavimochic, localizada na região de La Libertad, Perú. Nesta análise dinâmica considerou-se dois modelos constitutivos: Elástico e Mohr Coulomb, além de um sismo. / [en] In geotechnical problems can happen large strains because of prolonged rains, earthquake, slide slope, etc. Material point method is a solution method based on the finite element method (FEM) which offers advantages for static and dynamic calculation that involve that kind of strains. The objective in this dissertation is to use the MPM in geotechnical problems in statics and dynamics conditions. This research shows the analysis procedure of MPM for uncoupled condition (only solids, without water) and then coupled. Before the mathematical theory of MPM, a review of the theory of FEM in the conservation of quantidade de movimento is done. In this two methodology were raised three examples. The first one is a soil column that was modeled elastically, in which the main objective in to analyze the vertical displacement because of own weight. This was solved by four different methods: analytically, FEM weighted residual, FEM conservation of momentum, and MPM. All of them consider only the solid phase. The second example is a square of soil with side 1 meter, where the objective is to know the pore-pressure in the permanent condition and at the same time the vertical displacement were generated, it means that the analysis is coupled and were solved by MPM. In order to make a more realistic application, Palo Redondo dam is analyzed (uncoupled condition), which belongs to the Chavimochic project located in La Libertad, region of Perú. This dynamic analysis was done considering two constitutive models: Elastic and Mohr Coulomb, additionally seismic forces.

The pressure on clean and sustainable energy supplies is increasing. In this regard energy conversion by electrochemical processes plays a major role, for both fuel cell reactions and electrolysis reactions. The sulphur dioxide oxidation reaction (SOR) is a common reaction found in the Hybrid Sulphur Cycle (HyS) and the HyS is a way to produce large-scale hydrogen (H2). The problem with the use of the HyS and fuel cells is the cost involved as large amounts of Pt are required for effective operation. The aim of the study was to determine whether there was an alternative catalyst which was more efficient and cost-effective than Pt. The oxygen reduction reaction (ORR), the ethanol oxidation reaction (EOR) and SOR were studied by means of different electrochemical techniques (cyclovoltammetry (CV), linear polarization (LP) and rotating disk electrode (RDE)) on polycrystalline platinum (Pt) and palladium (Pd). The SRR and EOR are common reactions occurring at the cathode and anode, respectively, in fuel cells and these reactions have been investigated extensively. The reason for studying the reactions was as a preparation for the SOR. This study compared polycrystalline Pt and Pd for the different reactions, with the main focus on the SOR as Pd is considerably cheaper than Pt, and for the SOR polycrystalline Pd has by no means been investigated intensively. Polycrystalline Pt and Pd were compared by different electrochemical techniques and analyses. The Koutecky-Levich and Levich analyses were used to (i) calculate the number of e- involved in the relevant reaction, (ii) to determine whether the reaction was mass transfer controlled at high overpotentials and (iii) whether the reaction mechanism changed with potential. Next the kinetic current density ( k) was calculated from Koutecky-Levich analyses, which was further used for Tafel slope analyses. If it was not possible to carry out the analyses, the activation energy (Ea) was used to determine the electrocatalytic activity of the catalyst. The electrocatalytic activity was also determined by comparing onset potentials (Es), peak potentials (Ep) and limited/maximum current density ( b/ p) of each catalyst. This study was only a preliminary study for the SOR and therefore, further studies are certainly required. It seemed Pd shows better electrocatalytic activity than Pt for the SRR in an alkaline electrolyte because of similar Es, but Pd produced a higher cathodic current density. Pt showed a lower Es than Pd for the SRR in an acid electrolyte, but Pd delivered a higher cathodic current density. This, therefore, means that the SRR in an acid electrolyte is kinetically more favourable on Pd than on Pt. For the EOR better electrocatalytic activity was obtained with Pd than with Pt in an alkaline electrolyte due to higher current densities at lower potentials and Pd showed lower Ea values than Pt in the potential range normally used for fuel cells. Pd was inactive for EOR in an acid electrolyte, while a reaction occurred on Pt. A possible reason for this observation may be due to the H2 absorbing strongly on Pd thus blocking the active positions on the electrode surfaces, preventing further reaction. Pd showed higher electrocatalytic activity for the SOR due to lower Es and higher current densities at low potentials. From the RDE studies it was established that the SRR in an alkaline electrolyte on polycrystalline Pt and Pd was mass transfer controlled at low potentials (high overpotentials), but the SRR in an acid electrolyte was only mass transfer controlled on Pt. The SOR was not mass transfer controlled on polycrystalline Pt and Pd at high potentials (high overpotentials). These assumptions were confirmed by Levich analysis. Using Koutecky-Levich analysis, it was determined that the reaction mechanism on polycrystalline Pt and Pd changed with potential for SRR in an alkaline electrolyte and the SOR. For the SRR in an acid electrolyte the reaction mechanism remained constant with changes in potential on polycrystalline Pd, but the reaction mechanism on polycrystalline Pt changed with potential. These assumptions were confirmed by the number of e-, calculated using Koutecky-Levich analyses. Levich and Koutecky-Levich analyses were not performed for EOR as an increase in rotation speed did not produce an increase in current density. Tafel slope analyses were conducted by making use of overpotentials and k, where possible. As in the case of ethanol, it was not possible to execute Koutecky-Levich analyses and, therefore, it was not possible to perform Tafel slope analyses using k. Tafel slope analyses for the EOR was therefore performed with normal current densities at 0 rotations per minute (rpm). The reaction mechanisms on Pt and Pd for the SRR in alkaline and acidic electrolytes differed due to different Tafel slopes. Pt and Pd displayed similar Tafel slopes for the EOR in alkaline electrolyte, thus suggesting that the reaction mechanisms on Pt and Pd were the same. For the SOR it seemed that the reaction mechanism on Pt and Pd were similar because of similar Tafel slopes. This was only a preliminary and comparative study for polycrystalline Pt and Pd, and the reaction mechanism was not further studied by means of spectroscopic techniques. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

The pressure on clean and sustainable energy supplies is increasing. In this regard energy conversion by electrochemical processes plays a major role, for both fuel cell reactions and electrolysis reactions. The sulphur dioxide oxidation reaction (SOR) is a common reaction found in the Hybrid Sulphur Cycle (HyS) and the HyS is a way to produce large-scale hydrogen (H2). The problem with the use of the HyS and fuel cells is the cost involved as large amounts of Pt are required for effective operation. The aim of the study was to determine whether there was an alternative catalyst which was more efficient and cost-effective than Pt. The oxygen reduction reaction (ORR), the ethanol oxidation reaction (EOR) and SOR were studied by means of different electrochemical techniques (cyclovoltammetry (CV), linear polarization (LP) and rotating disk electrode (RDE)) on polycrystalline platinum (Pt) and palladium (Pd). The SRR and EOR are common reactions occurring at the cathode and anode, respectively, in fuel cells and these reactions have been investigated extensively. The reason for studying the reactions was as a preparation for the SOR. This study compared polycrystalline Pt and Pd for the different reactions, with the main focus on the SOR as Pd is considerably cheaper than Pt, and for the SOR polycrystalline Pd has by no means been investigated intensively. Polycrystalline Pt and Pd were compared by different electrochemical techniques and analyses. The Koutecky-Levich and Levich analyses were used to (i) calculate the number of e- involved in the relevant reaction, (ii) to determine whether the reaction was mass transfer controlled at high overpotentials and (iii) whether the reaction mechanism changed with potential. Next the kinetic current density ( k) was calculated from Koutecky-Levich analyses, which was further used for Tafel slope analyses. If it was not possible to carry out the analyses, the activation energy (Ea) was used to determine the electrocatalytic activity of the catalyst. The electrocatalytic activity was also determined by comparing onset potentials (Es), peak potentials (Ep) and limited/maximum current density ( b/ p) of each catalyst. This study was only a preliminary study for the SOR and therefore, further studies are certainly required. It seemed Pd shows better electrocatalytic activity than Pt for the SRR in an alkaline electrolyte because of similar Es, but Pd produced a higher cathodic current density. Pt showed a lower Es than Pd for the SRR in an acid electrolyte, but Pd delivered a higher cathodic current density. This, therefore, means that the SRR in an acid electrolyte is kinetically more favourable on Pd than on Pt. For the EOR better electrocatalytic activity was obtained with Pd than with Pt in an alkaline electrolyte due to higher current densities at lower potentials and Pd showed lower Ea values than Pt in the potential range normally used for fuel cells. Pd was inactive for EOR in an acid electrolyte, while a reaction occurred on Pt. A possible reason for this observation may be due to the H2 absorbing strongly on Pd thus blocking the active positions on the electrode surfaces, preventing further reaction. Pd showed higher electrocatalytic activity for the SOR due to lower Es and higher current densities at low potentials. From the RDE studies it was established that the SRR in an alkaline electrolyte on polycrystalline Pt and Pd was mass transfer controlled at low potentials (high overpotentials), but the SRR in an acid electrolyte was only mass transfer controlled on Pt. The SOR was not mass transfer controlled on polycrystalline Pt and Pd at high potentials (high overpotentials). These assumptions were confirmed by Levich analysis. Using Koutecky-Levich analysis, it was determined that the reaction mechanism on polycrystalline Pt and Pd changed with potential for SRR in an alkaline electrolyte and the SOR. For the SRR in an acid electrolyte the reaction mechanism remained constant with changes in potential on polycrystalline Pd, but the reaction mechanism on polycrystalline Pt changed with potential. These assumptions were confirmed by the number of e-, calculated using Koutecky-Levich analyses. Levich and Koutecky-Levich analyses were not performed for EOR as an increase in rotation speed did not produce an increase in current density. Tafel slope analyses were conducted by making use of overpotentials and k, where possible. As in the case of ethanol, it was not possible to execute Koutecky-Levich analyses and, therefore, it was not possible to perform Tafel slope analyses using k. Tafel slope analyses for the EOR was therefore performed with normal current densities at 0 rotations per minute (rpm). The reaction mechanisms on Pt and Pd for the SRR in alkaline and acidic electrolytes differed due to different Tafel slopes. Pt and Pd displayed similar Tafel slopes for the EOR in alkaline electrolyte, thus suggesting that the reaction mechanisms on Pt and Pd were the same. For the SOR it seemed that the reaction mechanism on Pt and Pd were similar because of similar Tafel slopes. This was only a preliminary and comparative study for polycrystalline Pt and Pd, and the reaction mechanism was not further studied by means of spectroscopic techniques. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014