This project was focused on the generation of porous and nanotubular anodic films on titanium and Ti-6wt.%Al alloy, and investigation of the key factors responsible for a transition between porous and nanotubular morphologies. Advanced analytical techniques were employed for characterisation of the anodic films, in particular scanning and transmission electron microscopies, including analytical transmission electron microscopy, Raman spectroscopy, nuclear reaction analysis, Rutherford backscattering spectroscopy and atomic force microscopy. Preparation of electron transparent sections for analysis by analytical transmission electron microscopy was undertaken using the focused ion beam technique. Initially, the influence of a post-anodizing rinsing treatment, using various media, on the morphology, structure and composition of anodic films generated on titanium in 0.2 M ammonium fluoride in glycerol, containing 0 and 5 vol.% added water, was investigated. Porous anodic films were formed in an electrolyte without added water followed by rinsing with ethanol. It was revealed that the oxide-rich nanotubes are embedded in a fluoride-rich matrix, with fluoride-rich material being more extensive and oxide-rich nanotubes being thinner-walled for the anodic films generated in the electrolyte with no added water followed by rinsing with ethanol compared with those for the films formed with added water to the electrolyte and rinsed similarly. However, post-anodizing rinsing of the former films transforms the porous morphology of the films to a tubular one. The contents of titanium and fluorine were reduced in the case of anodic films with the nanotubular morphology. It was suggested that dissolution of the fluoride-rich matrix occurs during rinsing of the specimens with water, leading to the transition from porous to nanotubular morphologies and subsequent loss of titanium and fluorine. Further work was undertaken to study the effect of ageing in deionised water on the morphology, structure and composition of the anodic films. It was revealed that loss of titanium and fluorine is greater for the films generated in the electrolyte with no added water followed by rinsing with water and ethanol and ageing compared with that for the films formed in the electrolyte with 5 vol.% added water followed by rinsing with water and ethanol and ageing. Finally, the anodic films generated on the Ti-6wt.%Al alloy were investigated. Porous anodic films were formed in the electrolyte without added water followed by rinsing with ethanol whereas the films treated with water disclosed nanotubular morphology. Porous anodic films contained greater amount of fluorine than nanotubular ones. Compositional analysis revealed an increased amount of fluorine for the anodic films generated on the alloy compared with those for the films formed on titanium under all investigated conditions. The difference in film compositions may be related to the difference in composition of the substrates used for anodizing, in particular, to the presence of aluminium as alloying element in the Ti-6wt.%Al alloy.

Orientador: Prof. Dr. Renato Altobelli Antunes / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2016. / O fenômeno da corrosão é uma das maiores ameaças à integridadedos aços de alta resistência e baixa liga (ARBL) utilizados para transporte de petróleo e gás.No presente trabalho, investigou-sea estabilidade de filmes anódicos formados sobre o aço API 5L X80 em eletrólitos utilizados para testes de inibidores de corrosão, variando o pH da solução, o potencial de formação na técnica de voltametria cíclica, e a formação espontânea dos filmes por ensaios de imersão. Explorando outro objetivo, foram produzidos filmes anódicos por polarização potenciostática com o intuito de formar uma camada de proteção contra a corrosão do aço API 5L X80. Estes experimentos foram conduzidos em solução de metassilicato de sódio.Neste caso otempo de exposição da amostra aumpotencial fixode formaçãofoi variadoe, como forma de estabelecer um comparativo, foram formados filmes espontaneamente sobre o eletrodo por ensaios de imersão.A caracterização do comportamento eletroquímico foi investigadausando espectroscopia de impedância eletroquímica(EIE)epolarização potenciodinâmica. As propriedades eletrônicas dos filmes anódicos foram analisadas pela abordagem de Mott-Schottky. A morfologia dos produtos de corrosão foi observada com auxílio de microscopia confocal a laser e microscopia eletrônica de varredura (MEV). A composição das camadas de óxido foi identificada com auxílio de espectroscopia Raman. Os resultadosmostraramque os filmesformados em solução alcalina foram mais resistentes àdissolução,menos defeituosos e mais estáveis do que aqueles formados em solução ácida.O produto de corrosão formado por voltametria cíclica tanto emeletrólitode caráter ácido quanto em eletrólitode caráter básico foi identificado como sendo hematita,enquanto a composição doproduto de corrosão formadopor imersãoem eletrólito de caráter básico indicouumadiversidade de compostos, especialmente quando o tempo de imersão foi maior, sendo possível identificar outros compostos além de hematita.A caracterização do comportamento eletroquímico dos filmes obtidos em solução de metassilicato de sódiomostrou que tanto apolarização potenciostáticaquanto a produçãoespontâneados filmes(ensaios de imersão)apresentaram poucos defeitos,alta estabilidade superficiale um aumentosignificativoda resistência à corrosão.A respeito da sua composição química, os filmes formados por cronoamperometria em solução de metassilicato de sódio apresentaram compostos à base de óxidos e oxihidróxidosde ferro, embora a análise de EDS sugerisse a presença de silíciona composição dosfilmes. Por sua vez, a composição dos filmes formados por imersão, em especial o espectro do filme imerso pelo maior período detempo, não foi possível deser identificada com precisão por espectroscopia Raman. / Corrosion is a major threat to the integrity ofhigh strength low alloy (HSLA) steels usedaspipelinesfor oil and gas transportation. In this study, we investigated the stability of the formed anodic films on API 5L X80 steel in electrolytes used for testing corrosion inhibitors, varying the pH of the solution, the formation potential in cyclic voltammetry technique and the spontaneous formation of films by immersion tests. Exploring another objective,anodic films were produced by potentiostatic polarization in order to form a protective layer against corrosion of the API 5L X80 steel. These experiments were conducted in a sodium metasilicate solution. In this case,the exposure time of the sample at a fixed formation potential was varied and, in order to establish a comparison, films were formed spontaneously on the electrode by immersion tests. The characterization of the electrochemical behavior was carried outusing electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. The electronic properties of anodic films were assessedbytheMott-Schottky approach. The morphology of corrosion products was observed with the aid of confocal laser scanning microscopy and scanning electron microscopy (SEM). The composition of the oxide layers was identified with the aid of Raman spectroscopy. The results showed that the films formed in alkaline solutions were more resistant to dissolution, less defective and more stable than those formed in acidicsolution. The corrosion product formed by cyclic voltammetry in both the acidic and alkaline solutionswas identified as hematite, while the corrosion product composition formed by immersion in the alkaline solutionindicated a diversity of compounds.Especially whenthe immersiontime was longer, it waspossible to identify other compounds in addition to hematite. The characterization of the electrochemical behavior of the films obtained in the sodium metasilicate solution showed that both the potentiostatic polarizationandthe spontaneous production of films (immersion test) produced layers withfew defects, high surface stability and significantlyincreased corrosion resistance. Regarding its chemical composition, the films formed by chronoamperometry insodium metasilicate solution presented iron oxides and oxyhydroxides, althoughEDS analysis suggested the presence of silicon in the composition of the films. In turn, the composition of thefilms formed upon immersion, in particular the spectrum of the film immersed forthe longest time, could not be reliably determined using Raman spectroscopy.