ABSTRACT This article aimed to analyze the effect of the thermal oxidation in the corrosion resistance and the hardness properties of TiO2 nanostructures obtained by the anodizing process in the HF/H3PO4 solution TiO2 nanostructures on Ti6Al4V obtained by anodizing processes were subjected to thermal oxidation (TO) treatments over a temperature range from 500 °C to 620 °C for 2 hours. Surface morphology was evaluated by using scanning electron microscopy; the hardness properties of TiO2 nanostructures were obtained by Nanoindentation measurements using a Berkovich probe with a tip radius of 150 mm. The corrosion behavior of the samples was studied using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results showed that TiO2 nanostructures, modified by thermal oxidation, increased the surface properties of hardness and corrosion resistance, compared to the substrate, maintaining its mixed or tubular structure. On the other hand, a transformation of nanotubes to nanopores after 600°C was evidenced, generating significant changes in the mechanical properties of these structures.

RESUMEN El objetivo de este artículo es analizar el efecto de oxidación térmica en la resistencia a la corrosión y las propiedades de dureza de nanoestructuras de TiO2 obtenidas por procesos de anodizado en solución de HF/ H3PO4. Las nanoestructuras de TiO2 sobre Ti6Al4V por procesos de anodizado fueron sometidas a tratamiento de oxidación térmica (OT)en un rango de 500 °C a 620 °Cpor dos (2) horas. La morfología superficial fue evaluada mediante microscopia electrónica de barrido; las propiedades de dureza de nanoestructuras de TiO2 fueron obtenidas por medidas de nanoindentación usando una probeta Berkovich de radio 150 mm. El comportamiento a la corrosión de las muestras fue estudiado usando polarización potenciodinámica y espectroscopia de impedancia electroquímica (EIS). Los resultados mostraron que la nanoestructuras de TiO2, modificadas por oxidación térmica, incrementaron las propiedades superficiales de dureza y resistencia a la corrosión, comparadas a las del substrato, manteniendo su estructura mixta o tubular. Además, se evidenció una transformación de nanotubos a nanoporos después de 600 °C generando cambios significativos en las propiedades mecánicas de estas estructuras.

Abstract Pitting corrosion resistance of two austenitic stainless steels, 18Cr8Ni (Type 304L or UNS S30403 stainless steel) and 17Cr6Mn5Ni, was evaluated in three electrolytic solutions containing a fixed concentration of 0.6M sodium chloride and different additions of sodium sulfate, 0.06M, 0.15M or 0.6M. Cyclic potentiodynamic polarization tests were performed on as-received samples and on specimens annealed at 1010°C, 1040°C, 1070°C or 1100°C. The best pitting corrosion resistance was presented by the 17Cr6Mn5Ni steel annealed at 1070°C or 1100°C, with lower delta ferrite contents, in the electrolyte with the highest sulfate concentration. It can be found that the addition of sodium sulfate inhibits pitting corrosion and has a better inhibitor effect in the high manganese steel.

The effect of aging temperature on mechanical and pitting corrosion properties of UNS S46500 was investigated. Tensile and Hardness tests were carried out and the microstructure was analyzed by optical microscopy, scanning electron microscopy and X-ray diffraction; Thermo-Calc simulations helped in the phase identification. Pitting corrosion properties were investigated in 0.6M NaCl electrolyte with sulfate additions by Potentiodynamic Polarization (PP). Hardness, tensile and yield strength of the UNS S46500 steel after lower aging temperature, 510ºC (H950), are higher than the ones found in the 538ºC (H1000) aged steel.This result is explained by microstructure, X-ray diffraction and Thermo-Calc analysis, which indicated the presence of austenite, chi phase and probably Ni3Ti precipitates finely and uniform distributed throughout the martensite matrix. Pitting corrosion resistance is equivalent in both aging temperatures. The sulfate inhibitor effect on UNS S46500 steel was enhanced for 538ºC condition when the electrolyte reaches 1Cl-:1SO4 2- ratio, which is explained by Ni sulfate adsorption and the amount of interfaces in the microstructure resulting in smaller amount of adsorption sites, such as coarsened Ni3Ti precipitates, smaller fraction of chi phase and recovery of dislocations in martensite structure.

Este documento presenta los resultados de una investigación sobre la influencia del Mn en solución sólida sobre la resistencia a la corrosión por picadura de dos aceros inoxidables austeníticos, uno denominado 17Cr6Mn5Ni y un acero comercial UNS S304L utilizado como material de referencia. Fueron usadas soluciones electrolíticas de 0,6M NaCl en tres diferentes condiciones de concentración de oxígeno (solución desaireada, naturalmente aireada y aireada artificialmente). El desempeño de cada condición fue medido a través de ensayos de polarización potenciodinámica y mediante exámenes metalográficos. Se determinaron los potenciales de corrosión (Ecorr) y de picadura (Ep). La concentración de oxígeno en la solución electrolítica influenció el parámetro Ecorr, pero no el Ep. El manganeso en solución sólida beneficia la absorción de iones Cl- en aceros inoxidables austeníticos, ejerciendo por tanto un efecto negativo en cuanto a resistencia a corrosión por picadura. A través de datos experimentales de energía libre de Gibbs de formación de compuestos (ΔG°) y de la teoría de absorción competitiva, fue propuesto un mecanismo para explicar este fenómeno.

In this research are shown the results about the study of the influence of manganese in solid solution on the pitting corrosión resistance of austenitic stainless steels, a steel is referred to as 17Cr6Mn5Ni and the UNS S304L steel as benchmarking material. Electrolytic solution containing 0.6M NaCl in three different oxygen concentration were used (aerated, non aerated and naturally aerated). The behavior of each condition was measured through potentiodynamic polarization tests and metallographic examinations. The values of corrosion potential (Ecorr) and pitting potential (Ep) were determined. The oxygen concentration of the electrolytic solution influenced the Ecorr but not the Ep parameter. Manganese in solid solution benefits the Cl- ions absorption in austenitic stainless steels. Therefore, causes negative effect on pitting corrosion resistance. A mechanism was proposed through the standard Gibbs free energy of formation of compounds (ΔG°) data, and through the competitive absorption theory.

Este documento apresenta os resultados de uma pesquisa sobre a influencia do Mn em solução sólida sobre a resistência à corrosão por pite de aços inoxidáveis austeníticos, um denominado 17Cr6Mn5Ni e um aço comercial UNS S304L utilizado como material de referencia. Foram usadas soluções electrolíticas de 0,6M NaCl em três diferentes condições de concentração de oxigênio (solução desaerada, naturalmente aerada e aerada artificialmente). O desempenho de cada condição foi medido a través de testes de polarização potenciodinâmica e mediante exames metalográficos. Determinaram-se os potencias de corrosão (Ecorr) e de pite (Ep). A concentração de oxigênio na solução eletrolítica influenciou o parâmetro Ecorr, mas não o Ep. O manganês em solução sólida beneficia a absorção de íons Cl- em aços inoxidáveis austeníticos, exercendo, portanto um efeito negativo quanto à resistência à corrosão por pite. Através de dados experimentais de energia livre de Gibbs de formação de compostos (ΔG°) e da teoria de absorção competitiva, foi proposto um mecanismo para explicar este fenômeno.