Thesis (M.S.)--University of Nevada, Reno, 2008. / "May 2008." Includes bibliographical references (leaves 75-80). Online version available on the World Wide Web.

Thesis (Ph. D.)--University of Nevada, Reno, 2008. / "May, 2008." Includes bibliographical references (leaves 136-142). Online version available on the World Wide Web.

Thesis (M.S.)--Ohio University, March, 2009. / Title from PDF t.p. Includes bibliographical references.

Thesis (Ph. D.)--Ohio State University, 2005. / Available online via OhioLINK's ETD Center; full text release delayed at author's request until 2006 Nov 30

Made available in DSpace on 2014-06-11T19:27:12Z (GMT). No. of bitstreams: 0 Previous issue date: 2013-11-07Bitstream added on 2014-06-13T19:55:30Z : No. of bitstreams: 1 rocha_tl_me_ilha.pdf: 2209567 bytes, checksum: 0779f425359ed3738d8731ce2f0ae1f2 (MD5) / A metodologia de Sinterização Direta de Metais por Laser (DMLS) é uma das novas tecnologias de manufaturas aditivas, utilizada para fabricação de componentes de geometrias complexas. Dada à possibilidade de obtenção de peças com geometrias complexas, este método possui um grande potencial para a manufatura de implantes personalizados de reconstituição óssea. Dentre os materiais utilizados no processo, o titânio e suas ligas se destacam por possuírem uma combinação de elevada resistência mecânica, alta resistência à corrosão eletroquímica e resposta biológica favorável. Este trabalho visou apresentar um estudo da corrosão eletroquímica em implante de liga Ti-6Al-4V obtido por DMLS. Os ensaios de corrosão eletroquímica foram realizados em temperatura ambiente e na presença do oxigênio atmosférico. Os eletrólitos utilizados foram Soro Fisiológico, Ringer Lactato e Solução de Hanks que simulam os meios fisiológicos, bem como os três meios acrescidos de Peróxido de Hidrogênio até atingirem pH~5,02 e pH~4,33 que simulam respectivamente reações de inflamação e infecção. As curvas de polarização potenciodinâmicas das amostras foram obtidas com uma velocidade de varredura de 1 mV/s e o intervalo de potencial varrido de -1 V a + 1,2 V. A área ensaiada das amostras (eletrodo de trabalho) foi de 0,5 cm2. As correntes de corrosão foram calculadas no intercruzamento das curvas anódica e catódica linearizadas, na região do potencial de corrosão. Os parâmetros eletroquímicos de corrosão obtidos foram: o potencial de corrosão, a densidade de corrente e a resistência à polarização. A análise qualitativa dos ensaios de corrosão foram obtidas mediante Microscopia Eletrônica de Varredura (MEV) e Microscopia Óptica, onde foi possível evidenciar aumento dos poros identificados na superfície após os ensaios / The methodology Direct Metal Laser Sintering (DMLS) is a new additive manufacturing technology, used for the manufacture of components of complex geometries. Given the possibility of obtaining parts with complex geometries, this method has a great potential for the manufacture of customized implants for bone reconstruction. Among the materials used in the process, titanium and its alloys are distinguished by possessing a combination of high mechanical strength, high corrosion resistance and electrochemical favorable biological response. This work aims to present a study of electrochemical corrosion in implant alloy Ti-6Al-4V obtained by DMLS. The electrochemical corrosion tests were performed at room temperature and in the presence of atmospheric oxygen. The electrolytes used were saline solution, Ringer Lactato and Hank´s solution simulating the fluids physiological, and added hydrogen peroxide until reaching pH~5,02 and pH~4,33 respectively which simulate the reactions of inflammation and infection . The potentiodynamic polarization curves of the samples were with a scan speed employed 1 mV/s and the sweep potential range of -1 V to + 1.2 V. The area of the samples tested (working electrode) was 0.5 cm2. The corrosion currents were calculated intercrossing the anode and cathode of the linearized curve in the region of potential corrosion. The electrochemical parameters obtained were: the corrosion potential of corrosion current density and polarization resistance. Qualitative analysis of the corrosion tests were performed by scanning electron microscopy (SEM) and optical microscopy, where it was possible to demonstrate increased presence of pores before corrosion tests

Orientador: Ruis Camargo Tokimatsu / Coorientador: Carlos Alberto Picone / Banca: Vicente Afonso Ventrella / Banca: Maria Aparecida Larosa / Resumo: A metodologia de Sinterização Direta de Metais por Laser (DMLS) é uma das novas tecnologias de manufaturas aditivas, utilizada para fabricação de componentes de geometrias complexas. Dada à possibilidade de obtenção de peças com geometrias complexas, este método possui um grande potencial para a manufatura de implantes personalizados de reconstituição óssea. Dentre os materiais utilizados no processo, o titânio e suas ligas se destacam por possuírem uma combinação de elevada resistência mecânica, alta resistência à corrosão eletroquímica e resposta biológica favorável. Este trabalho visou apresentar um estudo da corrosão eletroquímica em implante de liga Ti-6Al-4V obtido por DMLS. Os ensaios de corrosão eletroquímica foram realizados em temperatura ambiente e na presença do oxigênio atmosférico. Os eletrólitos utilizados foram Soro Fisiológico, Ringer Lactato e Solução de Hanks que simulam os meios fisiológicos, bem como os três meios acrescidos de Peróxido de Hidrogênio até atingirem pH~5,02 e pH~4,33 que simulam respectivamente reações de inflamação e infecção. As curvas de polarização potenciodinâmicas das amostras foram obtidas com uma velocidade de varredura de 1 mV/s e o intervalo de potencial varrido de -1 V a + 1,2 V. A área ensaiada das amostras (eletrodo de trabalho) foi de 0,5 cm2. As correntes de corrosão foram calculadas no intercruzamento das curvas anódica e catódica linearizadas, na região do potencial de corrosão. Os parâmetros eletroquímicos de corrosão obtidos foram: o potencial de corrosão, a densidade de corrente e a resistência à polarização. A análise qualitativa dos ensaios de corrosão foram obtidas mediante Microscopia Eletrônica de Varredura (MEV) e Microscopia Óptica, onde foi possível evidenciar aumento dos poros identificados na superfície após os ensaios / Abstract: The methodology Direct Metal Laser Sintering (DMLS) is a new additive manufacturing technology, used for the manufacture of components of complex geometries. Given the possibility of obtaining parts with complex geometries, this method has a great potential for the manufacture of customized implants for bone reconstruction. Among the materials used in the process, titanium and its alloys are distinguished by possessing a combination of high mechanical strength, high corrosion resistance and electrochemical favorable biological response. This work aims to present a study of electrochemical corrosion in implant alloy Ti-6Al-4V obtained by DMLS. The electrochemical corrosion tests were performed at room temperature and in the presence of atmospheric oxygen. The electrolytes used were saline solution, Ringer Lactato and Hank's solution simulating the fluids physiological, and added hydrogen peroxide until reaching pH~5,02 and pH~4,33 respectively which simulate the reactions of inflammation and infection . The potentiodynamic polarization curves of the samples were with a scan speed employed 1 mV/s and the sweep potential range of -1 V to + 1.2 V. The area of the samples tested (working electrode) was 0.5 cm2. The corrosion currents were calculated intercrossing the anode and cathode of the linearized curve in the region of potential corrosion. The electrochemical parameters obtained were: the corrosion potential of corrosion current density and polarization resistance. Qualitative analysis of the corrosion tests were performed by scanning electron microscopy (SEM) and optical microscopy, where it was possible to demonstrate increased presence of pores before corrosion tests / Mestre

Neural networks were applied to the analysis of electrochemical noise data. Electrochemical noise is defined as the fluctuations in either current or potential with time for a metal which is immersed in a conductive solution. This data is of interest because of its relationship to particular corrosion processes. Specifically, a system which is experiencing uniform corrosion will produce a different noise signal than one which is experiencing localized (perforation) corrosion. The economic effects of corrosion are significant and methods which improve the ability to detect, measure and predict corrosion would be extremely valuable.Two series of experiments were conducted. The data for both series were collected from aluminum samples immersed in various aqueous solutions. The series differed from each other in the configuration and programming of the potentiostat which collected the data. The first series only dealt with potential noise while the second series dealt with both potential and current noise. Auxiliary parameters, such as the pH and chloride concentration of the solutions were used in the second series. The first series studied data from only two solutions, while the second series included six solutions.It was possible for neural networks to correctly categorize systems in Series 1 according to the class of corrosion being observed (uniform or perforating). Appropriate data transformation steps were required to effect these classifications and it was also observed that many of these data transformations would lead directly to categorization without the use of a neural network.The additional data collected in Series 2 allowed a more complex analysis. Neural networks were able to simultaneously predict both the propensity towards localized corrosion and the metal dissolution rate. This application demonstrated the power of neural networks.Several types of neural networks and learning algorithms were included in this study. The two systems used most were a backpropagation (multi-layer perceptron) and a radial basis system. Comparisons of the various network systems with regard to speed and accuracy were made. / Department of Mathematical Sciences

Currently the development of ferritic alloys Cr-Mo more resistant to corrosion at high temperatures has been much in demand. An alloy widely used in the petrochemical industry is the 9Cr-1Mo alloy. The objective of this work is to study the effect of molybdenum content in the formation of deleterious phases and corrosion resistance alloys model Fe-Cr-Mo making a comparison with the commercial alloy 9Cr-1Mo. We used a program to determine the thermodynamic solubilization temperatures and banding of deleterious phases at temperatures 450-650  C. It was found that the condition solubilized in the model alloys had a ferritic structure. The addition of molybdenum promotes the emergence of intermetallic phases, increasing the presence of the same temperature range. The analysis by different techniques show that the precipitates formed in 9Cr-1Mo alloy are the type M23C6. We observed the formation of a harmful phase rich in molybdenum, the alloys model from the temperature of 450  C. The phase found was characterized as the μ phase. The studied alloys tend to form a passivation film, but which are not stable. The 9Cr-1Mo alloy showed the worst corrosion resistance condition in relation to the model alloys. Molybdenum contents of more than 5% by weight, enable increased formation of deleterious phases and does not promote improvements in corrosion resistance. Key words: Molybdenum, potentiodynamic polarization, P9, μ phase / Atualmente o desenvolvimento de ligas ferrÃticas Cr-Mo mais resistentes à corrosÃo em altas temperaturas tem sido muito solicitado. Uma liga muito utilizada na indÃstria petroquÃmica à a liga 9Cr-1Mo. O objetivo deste trabalho à estudar o efeito do teor de molibdÃnio na formaÃÃo de fases deletÃrias e na resistÃncia à corrosÃo em ligas modelo Fe-Cr-Mo fazendo um comparativo com a liga comercial 9Cr-1Mo. Utilizou-se um programa termodinÃmico para determinar as temperaturas de solubilizaÃÃo e as faixas de formaÃÃo das fases deletÃrias nas temperaturas de 450 a 650 ÂC. Constatou-se que na condiÃÃo solubilizada as ligas modelo apresentavam uma estrutura ferrÃtica. A adiÃÃo de molibdÃnio favorece ao surgimento de fases intermetÃlicas, elevando a faixa de temperatura de existÃncia das mesmas. As anÃlises de por diferentes tÃcnicas mostram que a os precipitados formados na liga 9Cr-1Mo sÃo do tipo M23C6. Observou-se a formaÃÃo de uma fase deletÃria, rica em molibdÃnio, nas ligas modelo a partir da temperatura de 450 ÂC. A fase encontrada foi caracterizada como sendo a fase Â. As ligas estudadas tendem a formar um filme de passivaÃÃo, mas que nÃo sÃo estÃveis. A liga 9Cr-1Mo apresentou a pior condiÃÃo de resistÃncia à corrosÃo em relaÃÃo Ãs ligas modelo. Teores de molibdÃnio superiores a 5%, em massa, possibilitam uma maior formaÃÃo de fases deletÃrias e nÃo promove melhorias na resistÃncia a corrosÃo. Palavras chaves: MolibdÃnio, PolarizaÃÃo potenciodinÃmica, P9, fase Â.

Les alliages de titane sont utilisés dans de nombreux domaines tels que l’aéronautique et l’aérospatial, l’industrie automobile, les plateformes offshore et d’autres applications telles que le biomédical et l’environnement marin. Le choix d’utiliser des alliages de titane repose sur le fait que ces alliages disposent d’un excellent ratio entre la résistance mécanique et la densité ainsi qu’une excellente résistance à la corrosion. Afin d’être employés pour une application marine telle que celle d’un winch innovant, nous avons choisi de travailler sur trois nuances d’alliages de titane β-métastables que sont les alliages Ti-6.8Mo-4.5Fe- 1.5Al, Ti-15Mo-2.7Nb-3Al-0.2Si et Ti-5Al-5Mo-5V-3Cr. Le milieu marin est une atmosphère qui expose les matériaux à des conditions telles qu’elles peuvent générer leur destruction. Divers moyens de dégradation existent. Il était donc intéressant d’évaluer la résistance à la corrosion de ces alliages et de chercher à les protéger contre la corrosion. Le coeur de cette étude repose sur la sélection des alliages de titane susceptibles de répondre au cahier des charges du winch innovant. Des traitements thermomécaniques ont d’abord été définis, puis les alliages ont été caractérisés métallurgiquement et mécaniquement. Ces caractérisations ont permis de connaître les propriétés mécaniques des alliages et de sélectionner les alliages potentiellement employables au sein du winch. Puis des essais de corrosion galvaniques ont été menés via la mesure de différences de potentiel entre les alliages de titane traités et d’autres matériaux susceptibles d’être employé au sein du winch tels que des aciers inoxydables, des alliages d’aluminium et des laitons au plomb. Puis, afin d’évaluer le comportement en corrosion marine du film passif des alliages de titane, des essais de corrosion électrochimiques ont été faits à l’aide d’un dispositif à trois électrodes dans des électrolytes de type chlorure de sodium et eau de mer naturelle. Ainsi des mesures de potentiel libre et de voltammétrie cyclique ont été menées. Le point faible des alliages de titane est le comportement en frottement. Dans ce cas, afin de réduire le coefficient de frottement de ces alliages, il est souvent nécessaire d’effectuer un traitement de surface. Dans cette étude, un traitement thermochimique de nitruration gazeuse a donc été fait sur l’alliage de titane le plus récemment développé parmi les nuances étudiées à savoir le Ti-5Al-5Mo-5V-3Cr. Cet alliage ainsi traité a été caractérisé de façon identique aux alliages traités thermomécaniquement. L’ensemble des essais menés au cours de cette thèse ont permis de déterminer quels alliages de titane parmi ceux étudiés seraient les plus susceptibles d’être employés au sein du winch innovant. / Titanium alloys are used in numerous fields as aerospace industry, automotive industry, off-shore industry, and, in several applications such as medical and marine applications. This is due to their good properties like high mechanical strength, low density and excellent corrosion resistance. In order to be used for an innovating winch and so in a marine environment, we have chosen to study three β-metastable titanium alloys which are Ti-6.8Mo-4.5Fe-1.5Al, Ti-15Mo-2.7Nb-3Al-0.2Si and Ti-5Al-5Mo-5V-3Cr. In marine environment, materials are exposed to tough conditions which can generate their destruction. Several modes of degradation exist. It is so interesting to evaluate the corrosion resistance of these alloys and to search their best corrosion protection. So, the heart of the study is to select titanium alloys to meet the specifications of the innovating winch. At first, we defined thermomechanical treatments for those titanium alloys and then these materials were characterized to know their mechanical and metallurgical properties. These tests allowed us to have a well knowledge of mechanical properties of these alloys and to choose which alloys can be employed in a winch. Then, galvanic corrosion tests were made in nitric acid, sodium chloride and sodium hydroxide. We measured potential differences between our treated titanium alloys and other materials which may be used in a winch such as stainless steels, aluminum alloys and leaded brass. Then, in order to evaluate the behavior of the passive film in marine environment of titanium alloys, electrochemical corrosion tests were conducted using a three-electrode method in sodium chloride and natural seawater electrolytes. So, free potential and cyclic voltammetry measurements were conducted. The flaw of titanium alloys is their low friction coefficient. So in order to improve the coefficient of friction of titanium alloys it is useful to do a surface treatment. In this study, a gaseous nitriding thermochemical treatment was done for the most recent developed alloy among the three studied nuances, which is Ti-5Al-5Mo-5V-3Cr. Then this treated alloy was characterized too similarly to the three thermomechanical treated titanium alloys. All of tests we led allowed us to know which titanium alloys with which thermomechanical and surface treatments may be used for the innovating winch.

Filmes de benzotriazol (BTAH) formados sobre aços carbono e inoxidável 316L foram estudados em meios de ácido sulfúrico, ácido clorídrico e cloreto de sódio a 25°C. Os seguintes aspectos foram considerados: as condições de formação do filme, sua eficiência, sua resistência em meios não contendo o inibidor,a presença de aditivos e o efeito do transporte de massa sobre o mecanismo da reação. Foram empregadas como técnicas: transitórios de potencial de circuito aberto, ensaios gravimétricos, curvas de polarização potenciostáticas e potenciodinâmicas com eletrodo parado e de disco rotativo, cronoamperometria, espectroscopia de impedância eletroquímica, microscopia ótica, microscopia eletrônica de varredura e análise da superfície por dispersão de energia. O BTAH se mostrou inibidor na grande maioria dos meios para os dois materiais estudados. A resistência dos filmes formados não existe ou é parcial quando as superfícies metálicas revestidas com o filme são imersas nos meios estudados sem inibidor. A adição de Cu(II) aumenta a resistência dos filmes, para determinadas relações [BTAH]/[Cu(II)] que estabilizem o intermediário Cu(I). A presença de íons provenientes da dissolução do aço inoxidável 304 em H2SO4 0,50 mol.L-1 contendo BTAH, eleva significativamente a resistência dos filmes formados, quando estes são expostos aos meios sem inibidor. O cloreto de trimetildodecil amônio exerce sinergismo sobre a ação do BTAH como inibidor de corrosão do aço carbono 1010 em meios ácidos. Superfícies de aço carbono previamente reduzidas são mais eficientes na formação de filmes resistentes aos meios sem inibidor. O transporte de massa do BTAH é uma etapa cinética importante no mecanismo de formação do filme sobre aço inoxidável 316L em meio de HCI 2,0 mol.L-1. O BTAH se mostrou inibidor para a corrosão do aço quando revestido pelo \"primer\" da tinta epóxi, quando adicionado à tinta ou quando o filme é formado antes da aplicação do \"primer\". / Benzotriazole (BTAH) films formed on carbon steel and 316L stainless steel have been studied in sulfuric and chloridric acids and in sodium choride solutionsat 25°C. Different aspects were considered: the film formation conditions, its efficiency, its resistance, the presence of additives and the effect of mass transport on the reaction mechanism. Open circuit potential measurements, weight loss experiments, potenciostatic and potentiadynamic polarization curves using stationary and rotating disc electrode, chronoamperometry, electrochemical impedance spectroscopy, optical and scanning electron microscopies and energy dispersive surface analysis have been used as techniques. BTAH have shown inhibitive effect over the majority of the systems studied. The film resistance depends on the presence of the inhibitor in the solution but the result is different if the film is formed in solution containing additives as copper (II) ions or cations obtained from 304 SS dissolution in H2SO4 media; in this case the films resist to chloridric acid media without BTAH. Dodecyltrimetilammonium chloride presents synergism on the inhibitive BTAH action forcarbon steel in acid solution. The BTAH mass transport represents an important step on the film formation mechanism. BTAH is also an effective inhibitor for carbon steel covered by epoxy primer when it is added to the primer or when the film is formed on the carbon steel surface from a H2SO4 solution containing BTAH.