Neste trabalho, a resistência à corrosão in vitro da liga de titânio Ti-13Nb-13Zr, fabricada em laboratório nacional, e destinada a aplicações ortopédicas, foi investigada em soluções que simulam os fluidos corpóreos. Os eletrólitos usados foram solução 0,9 % (massa) de NaCl, solução de Hanks, meio de cultura (MEM), neste dois últimos meios, sem e com adição de peróxido de hidrogênio. A adição de peróxido visou simular condições existentes em caso de processos inflamatórios resultantes de procedimentos cirúrgicos. A resistência à corrosão de ligas já comercialmente consagradas para uso como biomateriais, Ti-6Al-7Nb e Ti-6Al-4V, bem como do titânio puro (Ti-cp), foi também estudada por razões de comparação com a liga Ti-13Nb-13Zr. Foram utilizadas técnicas eletroquímicas e de análise de superfície. As técnicas eletroquímicas consistiram de: (a) medidas da variação do potencial a circuito aberto em função do tempo, (b) polarização potenciodinâmica e (c) espectroscopia de impedância eletroquímica (EIE). Os diagramas experimentais de impedância foram interpretados utilizando circuitos elétricos equivalentes que simulam modelos de filme óxido de estrutura dupla composta de uma camada interna compacta, tipo barreira, e uma camada porosa mais externa. Os resultados mostraram que a resistência à corrosão deve-se principalmente à camada barreira, e indicaram alta resistência à corrosão de todas as ligas e do Ti-cp em todos os meios estudados. O óxido formado na superfície da liga Ti-13Nb-13Zr, seja naturalmente ou em meios fisiológicos, foi caracterizado utilizando espectroscopia de fotoelétrons excitados por raios-X (XPS) e microscopia eletrônica de varredura (MEV). Os resultados mostraram que a presença de peróxido de hidrogênio em MEM promove o crescimento da camada porosa e incorporação de íons minerais, além de favorecer a formação de hidroxiapatita. A citotoxicidade da liga Ti-13Nb-13Zr foi também avaliada e esta se mostrou ser não tóxica. / In this work, the in vitro corrosion resistance of the Ti-13Nb-13Zr alloy, manufactured at a national laboratory, and used for orthopedic applications, has been investigated in solutions that simulate the body fluids. The electrolytes used were 0.9 % (mass) NaCl, Hanks\' solution, a culture medium (MEM), and the two last electrolytes, without and with addition of hydrogen peroxide. The aim of peroxide addition was to simulate the conditions found when inflammatory reactions occur due to surgical procedures. The corrosion resistance of alloys commercially in use as biomaterials, Ti-6Al-7Nb and Ti-6Al-4V, as well as of the pure titanium (Ti-cp), was also studied for comparison with the Ti-13Nb-13Zr alloy. The corrosion resistance characterization was carried out by electrochemical and surface analysis techniques. The electrochemical tests used were: (a) open circuit potential measurements as a function of time, (b) potentiodynamic polarization and (c) electrochemical impedance spectroscopy (EIE). The impedance experimental diagrams were interpreted using equivalent electric circuits that simulate an oxide film with a duplex structure composed of an internal and compact, barrier type layer, and an external porous layer. The results showed that the corrosion resistance is due mainly to the barrier type layer. The titanium alloys and the Ti-cp showed high corrosion resistance in all electrolytes used. The oxides formed on the Ti-13Nb-13Zr, either naturally or during immersion in MEM or Hanks’ solution was characterized by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (MEV). The results showed that the presence of hydrogen peroxide in MEM promotes the growth of the porous layer and incorporation of mineral ions, besides favouring hydroxyapatite formation. The citotoxicity of the Ti-13Nb-13Zr alloy was also evaluated and it was shown to be non-toxic.

Thesis (M.Sc. in Applied Science(Metallurgical Engineering))--University of Pretoria, 2008. / Abstract in English. Includes bibliographical references (leaves 67-69).

Neste trabalho, a resistência à corrosão in vitro da liga de titânio Ti-13Nb-13Zr, fabricada em laboratório nacional, e destinada a aplicações ortopédicas, foi investigada em soluções que simulam os fluidos corpóreos. Os eletrólitos usados foram solução 0,9 % (massa) de NaCl, solução de Hanks, meio de cultura (MEM), neste dois últimos meios, sem e com adição de peróxido de hidrogênio. A adição de peróxido visou simular condições existentes em caso de processos inflamatórios resultantes de procedimentos cirúrgicos. A resistência à corrosão de ligas já comercialmente consagradas para uso como biomateriais, Ti-6Al-7Nb e Ti-6Al-4V, bem como do titânio puro (Ti-cp), foi também estudada por razões de comparação com a liga Ti-13Nb-13Zr. Foram utilizadas técnicas eletroquímicas e de análise de superfície. As técnicas eletroquímicas consistiram de: (a) medidas da variação do potencial a circuito aberto em função do tempo, (b) polarização potenciodinâmica e (c) espectroscopia de impedância eletroquímica (EIE). Os diagramas experimentais de impedância foram interpretados utilizando circuitos elétricos equivalentes que simulam modelos de filme óxido de estrutura dupla composta de uma camada interna compacta, tipo barreira, e uma camada porosa mais externa. Os resultados mostraram que a resistência à corrosão deve-se principalmente à camada barreira, e indicaram alta resistência à corrosão de todas as ligas e do Ti-cp em todos os meios estudados. O óxido formado na superfície da liga Ti-13Nb-13Zr, seja naturalmente ou em meios fisiológicos, foi caracterizado utilizando espectroscopia de fotoelétrons excitados por raios-X (XPS) e microscopia eletrônica de varredura (MEV). Os resultados mostraram que a presença de peróxido de hidrogênio em MEM promove o crescimento da camada porosa e incorporação de íons minerais, além de favorecer a formação de hidroxiapatita. A citotoxicidade da liga Ti-13Nb-13Zr foi também avaliada e esta se mostrou ser não tóxica. / In this work, the in vitro corrosion resistance of the Ti-13Nb-13Zr alloy, manufactured at a national laboratory, and used for orthopedic applications, has been investigated in solutions that simulate the body fluids. The electrolytes used were 0.9 % (mass) NaCl, Hanks\' solution, a culture medium (MEM), and the two last electrolytes, without and with addition of hydrogen peroxide. The aim of peroxide addition was to simulate the conditions found when inflammatory reactions occur due to surgical procedures. The corrosion resistance of alloys commercially in use as biomaterials, Ti-6Al-7Nb and Ti-6Al-4V, as well as of the pure titanium (Ti-cp), was also studied for comparison with the Ti-13Nb-13Zr alloy. The corrosion resistance characterization was carried out by electrochemical and surface analysis techniques. The electrochemical tests used were: (a) open circuit potential measurements as a function of time, (b) potentiodynamic polarization and (c) electrochemical impedance spectroscopy (EIE). The impedance experimental diagrams were interpreted using equivalent electric circuits that simulate an oxide film with a duplex structure composed of an internal and compact, barrier type layer, and an external porous layer. The results showed that the corrosion resistance is due mainly to the barrier type layer. The titanium alloys and the Ti-cp showed high corrosion resistance in all electrolytes used. The oxides formed on the Ti-13Nb-13Zr, either naturally or during immersion in MEM or Hanks’ solution was characterized by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (MEV). The results showed that the presence of hydrogen peroxide in MEM promotes the growth of the porous layer and incorporation of mineral ions, besides favouring hydroxyapatite formation. The citotoxicity of the Ti-13Nb-13Zr alloy was also evaluated and it was shown to be non-toxic.

The corrosion resistance of chemically modified β-eucryptite (Li_0.41Mg_0.035AlP_0.52Si_0.480₄) having low expansion anisotropy and a near zero coefficient of thennal expansion was evaluated. Samples were exposed to aqueous hydrochloride acid at temperatures up to 100°C and environments containing sodium sulfate up to l000°C. The corrosion resistance was characterized by dilatometry, scanning electron microscopy, X-ray diffraction, energy dispersive x-ray analysis, weight variations, and mechanical properties variations. The results show that modified β-eucryptite is more severely corroded than commercial lithium-alumina-silicate glass-ceramics when exposed to these environments. Aqueous HCI removes AIP04 from modified β-eucryptite leaving a very porous structure. Molten salt corrodes modified β-eucryptite by penetration of sodium and sulfur which form an alkali melt under the surface. The modulus of rupture and the Young's modulus are reduced by both types of corrosion. / Master of Science

The corrosion resistance of two commercially available SiC filter materials coated with Mg-doped Al₂ TiO₅ and (Ca _0.6.6' Mg_0.52) Zr₄P₆O₂₄ (CMZP) was investigated in high-temperature high pressure (HTHP) alkali-steam environments. Coated specimen properties, including cold and hot compressive strengths, bulk density, apparent porosity, permeability, and weight change, detected after exposure to 92% air-S% steam 10 ppm Na at 8OO°C and 1.8 MPs for 500 h were compared with those of uncoated specimens. Procedures for applying homogeneous coatings of Mg-doped Al₂ TiO₅ and CMZP to porous SiC filters were established and coating of the materials was successfully accomplished. Efforts to stabilize the Al₂ TiO₅ coating composition at elevated temperature were successful. Coatings show promise for providing improved corrosion resistance of the materials in pressurized fluidized bed combustion (PFBC) environments as evidenced by higher compressive strengths exhibited by coated SiC specimens than by uncoated SiC specimens following HTHP alkali-steam exposure. / Master of Science

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.

Industrial and power generation processes employ units like boilers and gasifiers to burn sulfur containing fuels to produce steam and syn gas (H2 and CO), which can generate electricity using turbines and fuel cells. These units often operate under environments containing gases such as H2S, SO2, O2 etc, which can attack the metallic structure and impose serious problems of corrosion. Corrosion control in high temperature sulfur bearing environments is a challenging problem requiring information on local gaseous species at the surface of alloy and mechanisms of degradation in these environments. Coatings have proved to be a better alternative for improving corrosion resistance without compromising the bulk mechanical properties. Changes in process conditions may result in thermal and/or environment cycling between oxidizing and sulfidizing environments at the alloy surface, which can damage the protective scale formed on the alloy surface, leading to increase in corrosion rates. Objective of this study was to understand the effect of fluctuating environments on corrosion kinetics of carbon steels and develop diffusion based coatings to mitigate the high temperatures corrosion under these conditions. More specifically, the focus was : (1) to characterize the local gaseous environments at the surface of alloys in boilers; (2) optimizing diffusion coatings parameters for carbon steel; (3)understand the underlying failure mechanisms in cyclic environments; (4) to improve aluminide coating behavior by co-deposition of reactive elements such as Yttrium and Hafnium; (5) to formulate a plausible mechanism of coating growth and effects of alloying elements on corrosion; and (6) to understand the spallation behavior of scale by measuring stresses in the scales. The understanding of coating mechanism and effects of fluctuating gaseous environments provides information for designing materials with more reliable performance. The study also investigates the mechanism behind the effect of REs on scale adhesion and sulfidation behavior. Thus, the present work will have a broad impact on the field of materials and coatings selection for high temperature industrial environments such as boilers and gasifiers, and provides information on RE-modified aluminized coatings on carbon steel as an alternative for the use of bulk superalloys under high temperature sulfur bearing environments.

The use of stainless steel alloys in reinforced concrete structures has shown great success in mitigating corrosion in even the most severe of exposures. However, the use of high-strength stainless steels (HSSSs) for corrosion mitigation in prestressed concrete (PSC) structures has received limited attention. To address these deficiencies in knowledge, an experimental study was conducted to investigate the feasibility of using HSSSs for corrosion mitigation in PSC. The study examined mechanical behavior, corrosion resistance, and techniques for the production of HSSS prestressing strands. Stainless steel grades 304, 316, 2101, 2205, 2304, and 17-7 along with a 1080 prestressing steel control were included in the study. Tensile strengths of 1250 to 1550 MPa (181 to 225 ksi) were achieved in the cold-drawn HSSSs. 1000 hr stress relaxation of all candidate HSSSs was predicted to be between 6 and 8 % based on the results of 200 hr tests conducted at 70 % of the ultimate tensile strength. Residual stresses due to the cold drawing had a significant influence on stress vs. strain behavior and stress relaxation. Electrochemical corrosion testing found that in solutions simulating alkaline concrete, all HSSSs showed exceptional corrosion resistance at chloride (Cl-) concentrations from zero to 0.25 M. However, when exposed to solutions simulating carbonated concrete, corrosion resistance was reduced and the only HSSSs with acceptable corrosion resistance were duplex grades 2205 and 2304, with 2205 resistant to corrosion initiation at Cl- concentrations up to 1.0 M (twice that in seawater). Based on these results, duplex grades 2205 and 2304 were identified as optimal HSSSs and were included in additional studies which found that: (1) 2304 is susceptible to corrosion when tested in a stranded geometry, (2) 2205 and 2304 are not susceptible to stress corrosion cracking, and (3) 2205 and 2304 are susceptible to hydrogen embrittlement. Efforts focused on the production of 2205 and 2304 prestressing strands showed that they could be produced as strands using existing ASTM A416 prestressing strand production facilities. Due to the ferromagnetic properties of 2205 and 2304, a low-relaxation heat treatment was found to be a viable option to reduce stress relaxation and improve mechanical properties. The overall conclusion of the study was that HSSSs, especially duplex grades 2205 and 2304, show excellent promise to mitigate corrosion if utilized as prestressing reinforcement in PSC structures exposed to severe marine environments.

Thesis (Ph. D.)--Mississippi State University. Department of Agricultural and Biological Engineering. / Title from title screen. Includes bibliographical references.

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.