Dissertations / Theses on the topic 'Surface pitting'

The use of XPS and AFS technique has been explored in the stLrly of the surface chemistry of a whole electrode surface (XPS) and the surface chemistry of natural pits (AFS). EDXA and to a snall extend SIMS were also used in the investigation of the individual pits. A high resolution Auger electron microscope which has an analytical resolution as snall as 0.1 .un enables a nevly formed pit of less than 2 .un in diameter to be investigated. By using a Cl/Mg ratio an attempt had been made to correlate the surface chemistry of whole electrodes exposed at different potentials in 1M MgCl2 solution to the surface chemistry of individual pits naturally produced qy means of a simulated metal to metal crevice made of cammercial stainless steels (SS316 and SS304) immersed in 1M MgCl2 solution. '!he correlation was fomd to be good and within the expected limit of the data produced by XPS and AFS. The estimated val ue of potentials of the surface of pit and its immediate vicinity was based on a theoretical model of variation of potential aromd a pit by Melville and also on the potential-current curve of the steel sample in the test sol ution. The Q/Mg ratio was shown to be useful in determining the activity of pits. In repassivated pits in the crevice mouth zone magnesiun was a dominant species relative to chlorine, this is in contrast to the pits in the central part of the crevice which were (ii) engulfed in general corrosion. Active pits in the area between the two regions have higher value of Cl./Mg ratio in their surface than that in the surface in their immediate vicinity. The role of chraniun in pitting corrosion is suggested to counter the pitting attack by the fonnation of chramiun oxide and oxy-chloride on the surface of pit. Molybdenun when present, also concentrates on the surface of pit. The type of corrosion attacks on sulphide inclusions in stainless steel depend on the copper content of the inclusions. Pitting will be likely to take place on pure MnS incl usions but not on copper enriched-MnS inclusions. The fonnation of copper sulphide is suggested to be important in reducing the amount of active species of sulphur on the corroded inclusions.

The surface structures associated with the very early stages of pitting corrosion on stainless steels have been studied using a set of such surface analytical techniques as XPS, ToF-SIMS and SAM combined simultaneously with EDXA. Two types of 316 stainless steel, having minor variation in chemical composition were prepared for this work and passivated chemically in a solution of 0.5 M H2SO4 + 0.5 M NaCI + 0.08% H2O2. Survey and narrow scan XP spectra were acquired from the samples using a V. G. Scientific ESCALAB (II) in Angular XPS format. The survey scans were examined with emphasis on the essentials of the background slope caused by electron energy losses. The narrow scans of the peaks of significance, i.e., C1s, 01s, Cr2p and Fe2p were used for quantitative analysis in which the compositions of the surface species were determined. An angular and a depth profile were constructed as a basis for obtaining a layer sequence of the surface structures. ToF-SIMS analysis of the passive film was undertaken to validate the Angular XPS data. The program GOOGLY has been employed in fitting the oxide and metallic components of chromium and iron as well as oxygen and carbon, using the intrinsic shape parameter, k. The use of peaks of identical shape, position and background for each electron take-off angle facilitates the dependency of the residual extrinsic background on angle. The use of a polynomial function, that approximates the Tougaard background, has been included in the fitting routine. This function has been utilised in defining a background slope parameter that assigns different background tails to the components in a multiple peak. The rationale behind the use of the extrinsic background is to enable surface structures to be placed in depth-wise order with only a minor extension to the conventional peak-fitting routine. The work has shown also that it is possible to extract information from the background close to the peak, which can be used to develop a useful approach for the estimation of overlayer thickness. Pitting initiation at non-metallic inclusions on the steel surface, i.e., sulphide and mixed oxide particles have been examined by employing the high spatial resolution afforded by SAM in conjunction with the depth analysis offered by EDXA. Many of the multi-oxide inclusions, composed of silicates, remained inert to the solution. A small number that contained calcium silicate and oxide, however, showed evidence of attack. Inference was therefore made that the corrosion pathway, involving insoluble silicate inclusions, is largely dependent on soluble calcium containing phases within the inclusions. Scanning Auger microscopy has been utilised in demonstrating that the relatively high susceptibility of sulphide inclusions to pitting attack in corrosive media stems from the alloy distribution. The data obtained supports the proposal that depletion of chromium, exclusively in the immediate neighbourhood of the sulphide inclusions, leads to favourable ingress of aggressive ions. The GOOGLY program has been used to extend the intrinsic shape and background slope consideration to fit the FeLMM Auger peaks of both air-formed and passive films on stainless steel. Quantification of the peaks was complicated but the fits showed a reasonable correlation with those from Angular XPS. The much-reduced spot size obtainable on a high resolution (V. G. Scientific Sigma Probe) XPS instrument has been utilised in a localised characterisation of the passive film on stainless steel. The spectra acquired from different points on the steel surface have displayed a high degree of similarity to each other. The results obtained have been reasonably satisfactory.

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Dissertação (Mestrado)
IPEN/D
Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

A resistência à corrosão das ligas de alumínio está relacionada ao meio de exposição, composição química, presença de intermetálicos e microestrutura do metal, entre outras. Neste trabalho investigou-se a corrosão nas ligas de alumínio 3105 H16 e 5052 H34, comumente utilizadas na indústria de carrocerias de ônibus, em meio aquoso continham íons agressivos, tais como cloretos, sulfatos e hidroxilas. Avaliou-se comparativamente o comportamento destas ligas com os revestimentos de proteção de Nanocerâmico, Cromo VI, Cromo III e Sistema de Pintura em exposição atmosférica acelerada e imersão em diferentes meios agressivos. Estudos mais aprofundados restringiram-se às ligas sem tratamento, para as quais foram realizados ensaios de exposição acelerada em névoa salina neutra, névoa salina acética, câmara de umidade e exposição atmosférica natural. Microscopia eletrônica de varredura por emissão de campo foi empregada para caracterizar a superfície das ligas antes e após os ensaios de névoa salina neutra e acética. O comportamento eletroquímico das ligas sem tratamento foi determinado através do monitoramento do potencial de circuito aberto, curvas de polarização potenciodinâmica anódicas e espectroscopia de impedância eletroquímica. Os resultados mostraram que o tratamento de Cromo VI foi o que obteve melhor desempenho na proteção de ligas de alumínio, particularmente para a liga 5052. De um modo geral, a liga 5052 apresentou maior resistência à corrosão nos meios testados em presença ou não de tratamentos superficiais. Na exposição à névoa salina, a corrosão manifestou-se principalmente na forma de pites. Ficou comprovado que o efeito do íon Cl- é importante, porém o fator preponderante do comportamento à corrosão das ligas de alumínio está relacionado ao pH do meio de exposição, sendo este recomendado para avaliar revestimentos protetores. Além das condições do meio ao qual o metal será exposto, na seleção de tratamentos anticorrosivos é importante considerar as particularidades de cada liga, uma vez que suas características composicionais e microestruturais exercem relevante influência no desempenho à corrosão.
The corrosion resistance of aluminum alloys is related to the exposure medium, chemical composition, presence of intermetallic particles and metallic microstructure, among others. This work investigated corrosion of 3105 H16 and 5052 H34 aluminum alloys commonly used in the bus body industry in aqueous media containing aggressive ions, such as chlorides, sulfates and hydroxyls. The behavior of these alloys with the protective coatings of Nanoceramic, Chromium VI, Chromium III and Paint System in accelerated atmospheric exposure and immersion in different aggressive media was evaluated comparatively. Further studies were restricted to untreated alloys for which accelerated exposure tests were performed on neutral salt spray, acetic salt spray, moisture chamber and natural atmospheric exposure. Field scanning electron microscopy was used to characterize the alloys surface before and after neutral and acetic salt spray tests. The electrochemical statement of the untreated alloys was determined by monitoring the open circuit potential, anodic potentiodynamic polarization curves and electrochemical impedance spectroscopy. Results have shown that the treatment with Chromium VI was the one that obtained better performance in the protection of the aluminum alloys, particularly for 5052 alloy. In general, 5052 aluminum alloy presented greater resistance to corrosion in all tested media, with or without surface treatments. Under salt spray exposure, the corrosion attack appeared mainly in the form of pitting. It has been proven that the effect of Cl- ion is important, but the predominant factor on the corrosion behavior of aluminum alloys is related to the pH of the exposure medium, which is recommended to evaluate protective coatings. Besides the conditions of the medium to which the metal will be exposed, in the selection of anticorrosive treatments it is important to consider the particularities of each alloy, since its compositional and microstructural characteristics exert a relevant influence on the corrosion performance.

Les aciers inoxydables duplex (DSS) sont caractérisés par une structure biphasée comprenant un mélange de ferrite et d’austénite. La proportion entre les deux phases est d'habitude environ 50 %. Ils sont de plus en plus employés dans les industries chimiques, pétrochimiques, nucléaires, marines et de papier, principalement en raison de leurs excellentes propriétés mécaniques couplées à une bonne résistance à la corrosion par piqûre (basse teneur en nickel et molybdène). L’austénite ayant une composition chimique différente de celle de la ferrite, un film hétérogène se forme à la surface des aciers inoxydable duplex. Par ailleurs, les deux phases métalliques ayant des propriétés mécaniques différentes, un champ de contrainte hétérogène est généré dans les grains. Sous certaines conditions, l’existence de gradients de contraintes peut conduire à des hétérogénéités du film passif. Dans ce travail , on étudie l’effet des éléments d’alliages sur les propriétés physico-chimiques du film passif et le comportement en corrosion par piqures avant et après vieillissement en milieu chlorurés, pour une surface de référence respectant certains critères à savoir une surface lisse exempt de tout défauts (pas de couche écrouie, rugosité faible..). Les propriétés physico- chimiques du film sont étudiés à l’aide des analyses Auger et XPS à l’échelle locale et globale. Le comportement en corrosion des alliages duplex a été ensuite déterminé à partir d’essais TCP (détermination de la température critique de piqûration). Les résultats avant vieillissement ont montré que le film passif est homogène à l’échelle macroscopique et que l’amorçage des piqûres semblent être liée à la taille des grains et à la texture cristallographique décrit par le GOS. Après vieillissement de longue durée en milieu représentatif, les analyses de surface montrent un renforcement de la passivité par un épaississement du film passif, une augmentation significative du rapport Cr/Fe ce qui ont pour effet d’améliorer le comportement en corrosion par piqures des alliages. Des critères métallurgiques ont été proposés pour expliquer l’amorçage de piqûres pour ces alliages
Duplex stainless steels (DSS) are characterized by a two-phase structure comprising a mixture of ferrite and austenite. The proportion between the two phases is usually about 50%. They are increasingly used in the chemical, petrochemical, nuclear, marine and paper, mainly because of their excellent mechanical properties coupled with good resistance to pitting corrosion (low grade nickel and molybdenum). The austenite having a different chemical composition than the ferrite, a heterogeneous film is formed on the surface of duplex stainless steels. Furthermore, the two metallic phases having different mechanical properties, a field of heterogeneous stress is generated in the grains. Under certain conditions, these differences may also yield formation of a heterogeneous passive film. In this work, we study the effect of alloying elements on the physico-chemical properties of the passive film and behavior pitting corrosion before and after ageing in chloride media for a reference surface that meet certain criteria ie a smooth surface free from any defects (no hardened layer .. low roughness). The physicochemical properties of the film are studied using Auger and XPS analysis at the microscale. The corrosion behavior of duplex alloys was then determined from CPT tests (determination of the Critical Pitting Temperature). The results before ageing have shown that the passive film is homogeneous on a macroscopic scale and that pitting corrosion appear to be related to the grain size and crystallographic texture described by GOS. After ageing, surface analysis shows a strengthening of passivity by thickening of the passive film and the ratio Cr/Fe are significantly increased which has the effect of improving behavior pitting alloys. Metallurgical criteria for pitting were proposed

En raison de leurs excellentes propriétés mécaniques, couplées à une bonne résistance à la corrosion par piqûres et à un coût modéré (basse teneur en nickel et en molybdène), les aciers inoxydables austéno-ferritiques (dits aciers inoxydables duplex) sont largement utilisés dans de nombreux secteurs industriels. Les aciers inoxydables duplex ont une microstructure complexe composée à proportion équivalente d’austénite et de ferrite. L’austénite ayant une composition chimique différente de celle de la ferrite, un film hétérogène se forme à la surface des aciers inoxydable duplex. Par ailleurs, les deux phases métalliques ayant des propriétés mécaniques différentes, un champ de contraintes hétérogènes est généré dans les grains. Sous certaines conditions, l’existence de gradients de contraintes peut conduire à des hétérogénéités du film passif. Dans cette étude, l’effet d’un vieillissement de longue durée dans un milieu contenant des chlorures sur la composition chimique du film passif a été tout d’abord étudié. Le comportement en corrosion de certains alliages duplex a été ensuite déterminé à partir d’essais TCP (détermination de la température critique de piqûration). Les résultats ont été analysés en tenant compte des informations obtenues précédemment. Après vieillissement, l’épaisseur du film passif et le rapport Cr/Fe ont significativement augmenté. La distribution des chlorures dans le film passif est hétérogène. Cette distribution a été reliée à la microstructure du matériau et au champ de contraintes résiduelles. Il a été montré qu’elle influence le comportement électrochimique du matériau. Le comportement en corrosion est ensuite analysé à l’aide des courbes de polarisation locales. Des critères métallurgiques ont été proposés pour l’amorçage de piqûres
Duplex stainless steels (DSS) are highly important engineering materials, due to their generally high corrosion resistance combined with high strength and moderate alloy cost (lower nickel and molybdenum content). They are widely used in various industrial sectors. DSS have a complex microstructure with comparable volume of austenite and ferrite. Due to differences in chemical composition between austenite and ferrite, a heterogeneous passive film is formed on both phases. In addition, due to differences in mechanical properties, a heterogeneous stress field may be generated in metallic grains. Under certain conditions, these differences may also yield formation of a heterogeneous passive film. In this work, the influence of long-term ageing in chloride-containing media by on the chemical composition of the passive film was first studied by means of XPS and Auger at the microscale. The corrosion behaviour of some duplex stainless steels was then determined from CPT tests (determination of the critical pitting temperature). Results were analysed taking into account information obtained previously. After ageing, the thickness and the ratio Cr/Fe are significantly increased. The chloride distribution in the passive film was heterogeneous. It was related to the microstructure and the residual strain field. It was shown that this distribution modifies the electrochemical behaviour of samples. The corrosion behaviour was then analysed from local polarization curves and CPT tests. Metallurgical criteria for pitting were proposed

Orientadores: Paulo Roberto Mei, Anselmo Eduardo Diniz
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica
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Resumo: Foram investigados os efeitos das condições de usinagem em operação de torneamento na integridade superficial do aço inoxidável superaustenítico ASTM A744 Gr.CN3MN. A operação de acabamento foi o foco principal, porém também foram realizados estudos com a operação prévia, de desbaste. As principais variáveis no acabamento foram: ângulo de saída da ferramenta, velocidade de corte, profundidade de corte e avanço. No desbaste variou-se somente o ângulo de saída e a velocidade de corte. Os ensaios foram realizados em um torno horizontal CNC, utilizando fluido de corte. Os parâmetros analisados foram: microestrutura por microscopia ótica, rugosidade, encruamento por ensaio de microdureza e tensão residual por difração de raio-X. Para se estudar a resistência à corrosão por pites, superfícies usinadas foram imersas em solução de cloreto de ferro e examinadas no estereoscópio, medindo-se, por área, a densidade de pites e a perda de massa. Os resultados mostraram a presença de tensão residual de tração e de uma camada encruada em todas as superfícies usinadas. A redução da rugosidade elevou a resistência à corrosão por pite. A melhor combinação das condições de corte encontrada para obter os menores valores de rugosidade e de tensão residual de tração, no acabamento, para profundidade de corte de 0,2 ou 0,4 mm, foi a maior velocidade de corte (120 m/min), o menor avanço (0,1 mm/rot) e o maior ângulo de saída (10º), no desbaste; para a profundidade de corte de 2,5 mm e avanço de 0,25 mm/rot., foi a menor velocidade de corte (60 m/min) e o maior ângulo de saída (10º).
Abstract: An investigation was made of the effects of the machining conditions employed in the turning operation on the surface integrity of ASTM A744 Grade CN3MN superaustenitic stainless steel. The main focus was the finishing operation, but studies were also carried out with a prior roughening operation. The main input variables in finishing were: tool rake angle, cutting speed, cutting depth and feed rate. The only input variables in the roughening operation were rake angle and cutting speed. The tests were conducted on a CNC horizontal lathe, using cutting fluid flood. The following parameters were analyzed: microstructure and roughness - examined by optical microscopy; work hardening - determined by microhardness measurements; and residual stress - analyzed by X-ray diffraction. To study the pitting corrosion resistance, machined surfaces were immersed in a ferric chloride solution and examined under a stereoscope, measuring the pits density and mass loss per area. The results revealed the presence of residual tensile stress and a hardened layer on all the machined surfaces. Reducing the roughness caused the pitting corrosion resistance to increase. To obtain the lowest values of roughness and residual tensile stress in finishing at cutting depths of 0.2 or 0.4 mm, the best combination of cutting conditions was the highest cutting speed (120 m/min), the lowest feed rate (0.1 mm/v), and the highest rake angle (10º). In roughening at a cutting depth of 2.5 mm and a feed rate of 0.25 mm/rot., the best combination was the lowest cutting speed (60 m/min) and the highest rake angle (10º).
Mestrado
Materiais e Processos de Fabricação
Mestre em Engenharia Mecânica

Apres leur elaboration et leur caracterisation metallurgique (structure, composition, geometrie, stabilite thermique. . . ), cette etude examine les roles de la composition et de la structure de l'alliage sur les tenues a la corrosion generalisee et a la corrosion localisee d'alliages amorphes inoxydables (fe, ni, cr) (p, b) et (fe, cr) (p, b, si) dans des milieux acides sans chlorure et neutres chlorures. Le comportement en corrosion generalisee et la resistance a la corrosion par piqures des alliages amorphes sont compares aux comportements d'aciers inoxydables rapidement solidifies et de l'acier inoxydable austenitique commercial z6cn18-08

Tubos de cobre fabricados com o material ASTM C12200 (99,9%Cu-0,015-0,040%P) são utilizados mundialmente no transporte de água potável. A maior causa de vazamentos nestas tubulações é a corrosão por pite, que usualmente estão relacionadas com a qualidade da água. Estudos recentes mostraram que vazamentos em tubos de cobre usados para transporte de água de rede pública ocorreram em decorrência da corrosão por pite, o que se deu em virtude da presença do íon cloreto originado do tratamento para a desinfecção da água. Outro parâmetro que pode influenciar a corrosão por pite é a condição de acabamento interno dos tubos. Os óleos lubrificantes usados no processo de fabricação de tubos de cobre contêm carbono e este forma um filme deletério após o recozimento destes tubos. Este filme cria condições na superfície interna para a formação de pilhas de ação local. O objetivo deste trabalho é investigar se o teor de cloreto de sódio no meio aquoso, e o acabamento superficial da superfície interna de tubos de cobre utilizados comercialmente para transporte de água (ABNT/NBR-13206), têm influência na resistência à corrosão destes tubos. A resistência à corrosão foi investigada por meio de ensaios eletroquímicos em soluções naturalmente aeradas com várias concentrações de cloreto de sódio, a 25 oC. A superfície interna dos tubos foi observada, antes e após os ensaios eletroquímicos, por microscopia eletrônica de varredura (MEV). Os tipos de acabamentos superficiais estudados foram: desengraxamento, jateamento e acabamento do processo final de fabricação (sem tratamento). Foi também construído um circuito fechado para estudar o efeito do acabamento superficial na resistência à corrosão sob condições mais próximas das encontradas na prática. O efeito do tratamento de recozimento do tubo em atmosfera inerte, que causa a recristalização da microestrutura e eliminação dos resíduos de óleo lubrificante, também foi avaliado. Os resultados indicaram que o mecanismo de corrosão em soluções com teores de cloreto entre 0,06 mol L-1 e 0,12 mol L-1 correspondeu ao de ataque localizado, enquanto que para a concentração de 0,6 mol L-1 prevaleceu o ataque generalizado. Os resultados do estudo do efeito do acabamento superficial indicaram que os tratamentos que reduzem o teor de carbono na superfície são benéficos à resistência à corrosão, mas este não é o único fator que afeta a resistência à corrosão. Outras características superficiais resultantes do tratamento da superfície também devem ser consideradas. Por exemplo, embora o jateamento cause a diminuição do teor de carbono na superfície dos tubos, o aumento de rugosidade produzido por este acabamento pode resultar em uma menor resistência à corrosão. Os tratamentos superficiais que produziram superfície com maiores resistências à corrosão foram aqueles que também produziram superfícies com menores teores de carbono, a saber, desengraxe e recozimento.
Copper tubes manufactured with C12200 ASTM (99.9% Cu-0015-0040% P) are used worldwide for potable water transport. The largest number of leakages in these tubes is due to pitting, usually related to the water quality, associated to the presence of chloride ions originated from water disinfecting treatment. The literature on the effect of chloride on the corrosion of copper pipelines is controversial. The finishing of the copper tubes inner might also influence pitting corrosion. The lubricating oils used in the manufacture of copper tubes contain carbon and a deleterious film might form during annealing. The objective of this study is to investigate the effect of sodium chloride content and the inner surface finishing of copper tubes used for water transport (ABNT/NBR-13206) on their corrosion resistance. The study was carried out by electrochemical tests in naturally aerated sodium chloride solutions at various concentrations, at 25 °C. The tubes inner surface was observed previous to and after the electrochemical tests by scanning electron microscopy (SEM). The effects of the following surface finishing were investigated: degrease, sand blasting, annealing and the surface without treatment. A loop was built to simulate the operational conditions of the tubes. Results indicated that the corrosion mechanism in chloride solutions with concentrations between 0.06 mol L-1 and 0.12 mol L-1 was localized attack, whereas in the 0.6 mol L-1 solution, generalized attack was the predominant mechanism. The results the surface finishing investigation indicated that the treatments that leads to carbon content reduction are beneficial to corrosion resistance. However, other features must also be considered. For instance, although sand blasting reduces the carbon content on the tubes surface, the increase in roughness due to this treatment decreases the corrosion resistance. The surface treatments that resulted in increased corrosion resistance were those that also resulted in lower carbon levels at the surface, namely degreasing and annealing.

Bien que dits « inoxydables », les aciers inox peuvent être sujets à diverses formes decorrosion localisée telles que la piqûration. La formation de piqûres, nuisible à l’aspect et à l’intégritéstructurelle du matériau, est notamment contrôlée par les propriétés du film passif protecteur qui seforme à la surface des inox. De nombreuses études ont été menées sur les mécanismes de piqûration desurfaces modèles préparées au laboratoire. Cette thèse, au contraire, étudie les relations entre lespropriétés physico-chimiques et électroniques, d’une part, et la résistance à la corrosion par piqûres,d’autre part, de films passifs formés sur des inox par des finis de surfaces industriels.Les propriétés des films passifs ont été caractérisées par des méthodes variées, utiliséesclassiquement ou de façon plus originale : multi-piqûres et transitoires électrochimiques pour lapropriété d’usage, XPS et SDL pour la chimie de surface, spectroscopie d’impédance électrochimique,chrono-ampérométrie et photoélectrochimie pour les propriétés semi-conductrices des films.Il a été montré que la résistance à la piqûration des finis industriels pouvait valablement êtredéterminée par la méthode des transitoires électrochimiques et par la multi-piqûres, utiliséesauparavant pour les seules surfaces modèles. Par ailleurs, l’analyse comparée des résultats depiqûration et de ceux d’XPS et SDL a mis en évidence que la composition chimique des films passifsne suffit pas à rendre compte des différences de résistance à la piqûration des différents finisindustriels testés. En revanche, l’analyse des propriétés semi-conductrices des différents films passifs apermis de proposer des explications à ces écarts de comportements en corrosion localisée, confirmantque structure et taux de défauts du film passif sont deux paramètres clef de la résistance à la corrosionpar piqûres des films passifs.Enfin, une amélioration du comportement en piqûration des surfaces industrielles a pu êtremise en évidence, soit après un traitement court de ces dernières en milieu nitrique acide, soit àl’application aux échantillons d’un balayage en potentiel en milieu sulfate neutre
Stainless steels can suffer localized corrosion like pitting corrosion which can damage thestructural integrity of the material. The pit formation is mainly controlled by properties of theprotective layer formed on the stainless steel surface, which is called passive film. Many studies haveexamined pitting mechanism on model surface prepared in the laboratory. This work is dedicated tostudy the relations between physicochemical and electronic properties of industrially processedpassive films and their pitting corrosion resistance.The properties of passive films have been characterized with several methods which can beconventional or in a more innovative way: multi-pitting statistics and electrochemical noise for the useproperty, XPS and SDL for the surface chemistry, electrochemical impedance spectroscopy,chronoamperometry and photo-electrochemistry for semi-conductive properties of the passive films.Multi-pitting statistics and electrochemical transients which were usually used on modelsurfaces have been shown to be accurate for the evaluation of the pitting resistance of industrialsurface finishing samples. Furthermore, the comparison of the results of pitting resistance and of XPSand SDL analyses has shown that the chemical composition of passive films is not sufficient to explainthe difference of pitting resistance behavior among tested industrial passive films. However, the semiconductiveproperties characterizations are able to explain these differences of localized corrosionresistance. They confirm that structuration and defect level are two key parameters of pitting resistanceproperties of passive films.At last, this study highlighted that the pitting resistance of industrial passive films can beimproved by a short nitric acid treatment or by sweep voltammetry in neutral sulfate medium

SYNOPSIS OF THIS THESIS The aim of this thesis is to more fully understand and explain the binding mechanism of organic molecules to the Au(111) surface and to explore the conduction of such molecules. It consists of five discreet chapters connected to each other by the central theme of “The Single Molecule Device: Conductance and Binding”. There is a deliberate concentration on azine linkers, in particular those with a 1,10-phenanthroline-type bidentate configuration at each end. This linker unit is called a “molecular alligator clip” and is investigated as an alternative to the thiol linker unit more commonly used. Chapter 1 places the work in the broad context of Molecular Electronics and establishes the need for this research. In Chapter 2 the multiple break-junction technique (using a Scanning Tunnelling Microscope or similar device) was used to investigate the conductance of various molecules with azine linkers. A major finding of those experiments is that solvent interactions are a key factor in the conductance signal of particular molecules. Some solvents interfere with the molecule’s interaction with and attachment to the gold electrodes. One indicator of the degree of this interference is the extent of the enhancement or otherwise of the gold quantized conduction peak at 1.0 G0. Below 1.0 G0 a broad range for which the molecule enhances conduction indicates that solvent interactions contribute to a variety of structures which could bridge the electrodes, each with their own specific conductance value. The use of histograms with a Log10 scale for conductance proved useful for observing broad range features. vi Another factor which affects the conductance signal is the geometric alignment of the molecule (or the molecule-solvent structure) to the gold electrode, and the molecular alignment is explored in Chapters 3 for 1,10-phenanthroline (PHEN) and Chapter 4 for thiols. In Chapter 3 STM images, electrochemistry, and Density Functional Theory (DFT) are used to determine 1,10-phenanthroline (PHEN) structures on the Au(111) surface. It is established that PHEN binds in two modes, a physisorbed state and a chemisorbed state. The chemisorbed state is more stable and involves the extraction of gold from the bulk to form adatom-PHEN entities which are highly mobile on the gold surface. Surface pitting is viewed as evidential of the formation of the adatom-molecule entities. DFT calculations in this chapter were performed by Ante Bilic and Jeffery Reimers. The conclusions to Chapter 3 implicate the adatom as a binding mode of thiols to gold and this is explored in Chapter 4 by a timely review of nascent research in the field. The adatom motif is identified as the major binding structure for thiol terminated molecules to gold, using the explanation of surface pitting in Chapter 3 as major evidence and substantiated by emergent literature, both experimental and theoretical. Furthermore, the effect of this binding mode on conductance is explored and structures relevant to the break-junction experiment of Chapter 2 are identified and their conductance values compared. Finally, as a result of researching extensive reports of molecular conductance values, and having attempted the same, a simple method for predicting the conductance of single molecules is presented based upon the tunneling conductance formula.

PhD
SYNOPSIS OF THIS THESIS The aim of this thesis is to more fully understand and explain the binding mechanism of organic molecules to the Au(111) surface and to explore the conduction of such molecules. It consists of five discreet chapters connected to each other by the central theme of “The Single Molecule Device: Conductance and Binding”. There is a deliberate concentration on azine linkers, in particular those with a 1,10-phenanthroline-type bidentate configuration at each end. This linker unit is called a “molecular alligator clip” and is investigated as an alternative to the thiol linker unit more commonly used. Chapter 1 places the work in the broad context of Molecular Electronics and establishes the need for this research. In Chapter 2 the multiple break-junction technique (using a Scanning Tunnelling Microscope or similar device) was used to investigate the conductance of various molecules with azine linkers. A major finding of those experiments is that solvent interactions are a key factor in the conductance signal of particular molecules. Some solvents interfere with the molecule’s interaction with and attachment to the gold electrodes. One indicator of the degree of this interference is the extent of the enhancement or otherwise of the gold quantized conduction peak at 1.0 G0. Below 1.0 G0 a broad range for which the molecule enhances conduction indicates that solvent interactions contribute to a variety of structures which could bridge the electrodes, each with their own specific conductance value. The use of histograms with a Log10 scale for conductance proved useful for observing broad range features. vi Another factor which affects the conductance signal is the geometric alignment of the molecule (or the molecule-solvent structure) to the gold electrode, and the molecular alignment is explored in Chapters 3 for 1,10-phenanthroline (PHEN) and Chapter 4 for thiols. In Chapter 3 STM images, electrochemistry, and Density Functional Theory (DFT) are used to determine 1,10-phenanthroline (PHEN) structures on the Au(111) surface. It is established that PHEN binds in two modes, a physisorbed state and a chemisorbed state. The chemisorbed state is more stable and involves the extraction of gold from the bulk to form adatom-PHEN entities which are highly mobile on the gold surface. Surface pitting is viewed as evidential of the formation of the adatom-molecule entities. DFT calculations in this chapter were performed by Ante Bilic and Jeffery Reimers. The conclusions to Chapter 3 implicate the adatom as a binding mode of thiols to gold and this is explored in Chapter 4 by a timely review of nascent research in the field. The adatom motif is identified as the major binding structure for thiol terminated molecules to gold, using the explanation of surface pitting in Chapter 3 as major evidence and substantiated by emergent literature, both experimental and theoretical. Furthermore, the effect of this binding mode on conductance is explored and structures relevant to the break-junction experiment of Chapter 2 are identified and their conductance values compared. Finally, as a result of researching extensive reports of molecular conductance values, and having attempted the same, a simple method for predicting the conductance of single molecules is presented based upon the tunneling conductance formula.

Lors de l’usinage, les conditions de pression et de température à la surface usinée sont trèsélevées. La microstructure et l’état mécanique du matériau sont impactés, ce qui a desconséquences sur la réactivité chimique de la surface usinée. Dans cette thèse, ons’intéresse au tournage de superfinition de l’acier inoxydable martensitique X4CrNiMo16-5-1traité thermiquement (dénommé APX4 optimisé). Il présente la particularité d’êtremultiphasé à la température ambiante (martensite, ferrite et austénite). L’objectif est dequantifier les relations entre les conditions de coupe, les propriétés d’usage et ladégradation par corrosion des surfaces usinées. Des essais d’usinage en coupe orthogonale(type QST) ont été réalisés afin de comparer directement les résultats expérimentaux auxprédictions numériques 2D des surfaces usinées.Les changements de phase du matériau ont été étudiés par des essais de calorimétriejusqu’à 1200°C. Les cycles thermiques réalisés ont mis en évidence différentestransformations métallurgiques. L’étude bibliographique complémentaire permet deconclure quant aux possibilités de transformation de phase en usinage, qui sont quasiinexistantes du fait des cinétiques de chauffage extrêmement élevées en tournage.Les échantillons usinés ont été caractérisés avec une étude microstructurale parmicrographie optique et par MEB-EBSD. Ces deux techniques mettent en évidence lesdéformations importantes en extrême surface indiquées par l’étirement des îlots de ferriteparallèlement à la surface usinée. Ces résultats microstructuraux ont été mis en relationavec les résultats de microdureté Vickers. Une relation de la dureté superficielle a étéexprimée en fonction des conditions de coupe. La technique EBSD a permis de montrer pourles échantillons usinés dans les conditions les plus sévères la déformation de la ferrite avecapparition de sous-joints de grain, un affinement microstructural de la martensite et uneaccentuation de l’affinement de la matrice martensitique à proximité de la ferrite déformée.Une simulation numérique de prédiction des déformations à l’échelle macroscopiquea été réalisée. Ces résultats numériques ont été comparés aux résultats de déformation etde microdureté issus d’une campagne d’essais. Des essais numériques complémentairesappliqués à l’échelle de la microstructure (matériau considéré biphasé) permettent ded’appréhender la déformation de la phase ferritique et son influence locale sur ladéformation de la matrice martensitique. Ces résultats sont cohérents avec les résultatsexpérimentaux.Les phénomènes de corrosion par piqûres ont été étudiés par le biais d’essais depolarisation à l’aide de la microcellule électrochimique et d’essais spécifiques pulsés. Cesderniers essais ont permis l’analyse des piqûres générées (en diamètre et en densité). Larésistance à la corrosion localisée des surfaces d’acier inoxydable martensitique reste bonneaprès usinage, même améliorée (densité de piqûres plusieurs fois plus faible que l’état deréférence). Ce comportement est corroboré à l’état de compression de la surface.La microdureté de surface, qui est contrôlée majoritairement par l’avance, conditionne lepotentiel de piqûre. L’augmentation du diamètre de piqûre a été reliée à l’affinementmicrostructural (observé à partir d’un certain seuil de microdureté superficielle)
During machining, pressure and temperature conditions at the machined surface are veryintensive. Machined material microstructure and mechanical state are changed, whichimpacts the chemical reactivity of the machined surface. In this PhD study, we focus onsuperfinish turning of heat treated martensitic stainless steel X4CrNiMo16-5-1 (namedoptimized APX4). It has to be mentioned that this material has a multiphased microstructureat ambient temperature (martensite, ferrite and austenite). The aim is then to quantifyrelationships between cutting conditions, properties and the deterioration (corrosion) ofmachined surfaces. Machining trials in orthogonal cutting configuration (QST) have beenrealized in order to compare experimental results directly to 2D numerical forecast ofmachined surfaces.Material phase transformations have been studied by calorimetry tests until 1200°C. Testshave evidenced different metallurgical transformations. The complementary bibliographystudy allows to conclude that phase transformation possibilities during machining are veryquasi nonexistent due to extremely high heating kinetics in turning.Machined samples have been characterized by a microstructural study by opticalmicrography and SEM-EBSD. Both techniques highlight high strains in extreme machinedsurface as indicated by the stretching of ferrite islands in parallel to the machined surface.Microstructural results have been linked to the Vickers microhardness results. Surfacehardness has been expressed as a function of the cutting conditions.EBSD measurements have shown for machined samples in the most severe conditionsstraining of the ferrite with low angle grain boundaries, microstructural refining ofmartensite and heightening of martensitic matrix close to the strained ferrite.A numerical simulation predicting strains at the macroscopic scale has been carried out.These numerical results have been compared to strain and microhardness results arise fromone trials campaign. Further numerical simulations applied at the microstructure level(considered as biphased material) allow understanding of ferritic phase strain and its localinfluence on martensitic matrix strain. These results are consistent with experimentalresults.Pitting corrosion phenomenon has been studied by polarization testing using theelectrochemical microcell and specific pulsed testing. Last used method has been conductedto analyze the generated pits (diameter and density). Localized corrosion resistance ofmachined martensitic stainless steel surfaces remains good, even improved (few times lowerpitting density than the reference state). This behaviour is corroborated to the compressivestate of the surface.Surface microhardness, which is mainly controlled by the feed rate, conditions the criticalpitting potential. Increased pitting diameter has been linked to microstructural refining(observed above a surface microhardness level)

Efficiency of internal combustion engines (ICEs) is far from optimal. Due to the continuously increasing demands on CO2 regulations, automobile industries are forced to improve such efficiency. A crankshaft roller bearing (CSRB) can lead to significant improvements in engine efficiency. However, before this can be implemented into an actual engine, several challenges have to be addressed. One such challenge is the satisfactory performance of CSRB. The current crankshaft limits the service life since it must act as a roller bearing raceway. Therefore, better material properties are required for the use of CSRB in crankshaft applications. In order to select suitable material for the CSRB, development of several characterization methods is required. These methods are based on failure modes that are expected to occur in the actual application. Surface initiated fatigue was shown to be the main failure mode that could lead to complete failure of such a component. The following three characterizations needs are identified: material characterization, lubricant characterization and surface roughness characterization. Two of these methods are partially part of this thesis. Material characterization is required to select the optimal steel candidate for the CSRB component. A method was developed to assess the damage modes on a reference 100Cr6 steel pair under conditions prevalent to CSRB application. However, fully formulated oil was excluded from this investigation and only low-additive oil was employed. Micro-pitting and wear damage modes were identified and were later assessed. Different surface roughness combinations were tested, from where micro-pitting regions were identified. In addition, the effects of surface hardness and sliding on micro-pitting and wear were investigated. It was found that hard steel contacts are more prone to micro-pitting damage compared to soft ones, but less susceptible to mild wear. In addition, higher sliding increases the degree of micro-pitting and wear. Lubricant characterization was performed to optimize the engine oil formulation for rolling contacts. A method to assess different engine oils in terms of micro-pitting and wear damages of rolling contacts was employed. The effect of viscosity, additive chemistry and different mixtures of base oils on aforementioned performance were presented and discussed. In addition, lubricant characterization will provide in-depth knowledge for engine oils’ manufacturers to improve engine oil formulations for satisfactory performances of CSRB design.

Les matériaux métalliques sont utilisés dans des conditions de plus en plus sévères et doivent présenter une parfaite intégrité sur des périodes de plus en plus longues. L'objectif de ce travail de thèse est d'évaluer le potentiel d'un traitement de refusion laser pour améliorer la résistance à la corrosion d'un acier inoxydable de type 304L ; l'utilisation du laser dans le domaine des traitements de surface constituant un procédé en pleine évolution à cause des changements récents dans la technologie des lasers. Dans le cadre de ce travail, le choix du laser s'est porté sur un laser nano-impulsionnel à fibre dopée ytterbium dont les caractéristiques permettent la fusion quasi-instantanée sur quelques microns de la surface traitée, immédiatement suivie d'une solidification ultra-rapide avec des vitesses de refroidissement pouvant atteindre 1011 K/s. La combinaison de ces processus favorise l'élimination des défauts surfaciques, la formation de phases hors équilibre, la ségrégation d'éléments chimiques et la formation d'une nouvelle couche d'oxyde dont les propriétés sont gouvernées par les paramètres laser. Afin de les corréler avec la réactivité électrochimique de la surface, l'influence de deux paramètres laser sur les propriétés physico-chimiques de la surface a été étudiée : la puissance du laser et le taux de recouvrement des impacts laser. Pour clarifier ces relations, la résistance à la corrosion par piqûration des surfaces traitées a été déterminée par des tests électrochimiques. Pour des paramètres laser spécifiques, le potentiel de piqûration d'un acier inoxydable de type 304L augmente de plus de 500 mV traduisant ainsi une meilleure tenue à la corrosion localisée en milieu chloruré. L'interdépendance des différents phénomènes résultant du traitement laser a rendu complexe la hiérarchisation de leur effet sur la sensibilité de l'alliage testé. Cependant, il a été montré que la nature de l'oxyde thermique formé au cours de la refusion laser et ses défauts sont du premier ordre pour l'amorçage des piqûres.

Cylinder liners in heavy-duty truck engines are subjected to intense vibrations and may sustain damage from the cavitation of bubbles in the coolant liquid, with some risks of leakage and engine breakdown. An ultrasonic oscillating probe was used to simulate the pitting rates and behavior of samples extracted from cylinder liners, which are made of grey cast iron, with differences in surface roughness, glycol and inhibitor content in coolant, coolant temperature and graphite flake class; bainitic microstructures were also tested. Measurements consisted of mass losses under set intervals during experiments lasting 2.5 or 4 hours. Affected surfaces were later evaluated with scanning electron microscopy and confocal microscopy. Results indicate higher cavitation damage with: lower concentrations of glycol and absence of corrosion/cavitation inhibitors in the coolant liquid, lower liquid temperatures between 76⁰C and 90⁰C, and presence of B-type graphite class in the microstructure. Results regarding surface roughness were inconclusive. A sequence of surface damage mechanisms has been proposed, with corresponding microscope observations, to explain the mass loss trends and the associated microstructural changes over time.

Les effets d'amelioration des capacites de passivation apportees par le molybdene et les effets de depassivation induits par le soufre adsorbe et en solution solide ont ete etudies en milieu h::(2)so::(4) sur des alliages monocristallins a base de nickel contenant 2% et 6% de molybdene, a l'aide de techniques electrochimiques et radiochimiques (traceur s**(35))

博士
國立中山大學
機械與機電工程學系研究所
91
Abstract The electrical pitting often occurs at the bearing of the ro-tating machinery due to the actions of the shaft voltage and the shaft current resulting in the arcing effect on the lubricated surface and causing the bearing failure. Since the mechanism of the electrical pitting cannot be microscopically observed in process, it is difficult to prevent the bearing damage. Hence, this study uses a static electrical pitting tester with sub -micrometer accuracy to experimentally investigate the effects of supply voltage, supply current, oil film thickness, and ad-ditive on the threshold condition of electrical pitting under the conventional bearing material pairs. Moreover, according to the SEM micrograph and EDS analysis, the mechanism of the pitted surfaces is investigated. According to the experimental results and the surface ob-servations of steel/steel pair using a paraffin base oil, three electrical pitting regimes are found under the influences of shaft voltage and oil film thickness, namely, pitting, transition, and no-pitting regimes. In the electrical pitting regime, the interface voltage, interface impedance, and interface power increases slightly with increasing oil film thickness at a certain supply current. However, the interface voltage and interface power increases with increasing supply current, and the inter-face impedance decreases with increasing supply current at a certain film thickness. Furthermore, the pitting area versus the interface power relationship is a cubic function. According to the experimental results and the surface ob-servations of babbitt alloy/steel pair using a paraffin base oil, two electrical pitting regimes are found under the influences of shaft voltage, oil film thickness, and melting point of material, namely, pitting and no-pitting regimes. The mechanism of electrical pitting on the babbitt alloy surface is significantly influenced by the interface power and the oil film thickness. At the smaller oil film thickness, the eroded surface of babbitt alloy exhibits a concave crater with a few micro-porosity in the vicinity of center region with a plateau on its surrounding, especially at high supply current. The polished track can be observed at the plateau. A large amount of tin element trans-fers to the steel ball surface because the molten tin contacts the ball. At the higher oil film thickness, only a little amount of metal element transfers to each other. The major pitting area of the babbitt alloy is caused at the initial stage of the arc dis-charge. With increasing arc discharge time, the pitting area increases slightly, and finally reaches a saturated value. According to the experimental results and the surface ob-servations of babbitt alloy/steel pair using an additive of MoS2 in a paraffin base oil, two electrical pitting regimes are found under the influences of shaft voltage, oil film thickness, and particle concentration of additive, namely, pitting and no-pitting regimes. The area of pitting regime increases with increasing additive concentration and supply current. Fur-thermore, the ratio of pitting area to the interface power in-creases with increasing additive concentration and supply current at the oil film thickness smaller than 6 mm. However, this ratio increases rapidly to about 10 times with increasing additive concentration and supply current as the oil film thickness increases from 6 mm to 10 mm. This results from the molten plateau that directly connects two specimens, and the interface power is mainly consumed at the heating of the pla-teau and the interfacial materials. According to the above re-sults, the growth model of the plateau on the pitting surface is proposed at the lubricated condition using an additive of MoS2 in paraffin base oil.

博士
國立成功大學
機械工程學系
86
A gear/cam adapter was employed to study various aspects of line-contact lubrication, using oil with extreme-pressure at two different concentrations. The effect of run-in on the tribological performance of rollers with two different surface roughnesses was investigated in terms of friction coefficient, wear loss, oil temperature, specimen roughness and electrical resistanc?蒞he relation between roller wear loss and the time rate of electrical resistance change was established. The run-in effect on roller wear loss in smooth rollers is opposed to that in rough rollers. The asperity height of the smooth rollers was increased by wear testing irrespective of run-in; however, run- in enhanced the increase in surface roughness. The extreme- pressure additive concentration instead of run-in was the decisive factor in electrical resistance. Friction coefficient during testing showed a strong positive relation with composite surface roughness. The pitting behavior of rollers with two different surface roghnesses was investigated in terms of crack length, chemical reaction thin film, pitting area, pitting depth, and specimen''s life. Rollers with a rough contact surface induced a longer life by means of a shallower stress distribution in the subsurface. The presence of extreme-pressure additive in the base oil reduced Weibull slope and promoted the L50 life. The results were confirmed due to the plastic flowing of Beilby layer, which restrained the propagation of cracks.

Digital in-line holographic microscopy (DIHM) has been incorporated as an additional simultaneous in situ optical technique with ellipsomicroscopy for surface imaging and microscopy to study metastable pitting corrosion on stainless steel 316LVM in simulated biological solutions. DIHM adds microscopic volume imaging, allows one to detect local changes of the index of refraction in the vicinity of a pitting event, and allows one to track tracer particles and/or material ejected from the pitting sites. To improve the pitting corrosion resistance of stainless steel 316LVM, a simple surface treatment was tested and the aforementioned imaging techniques were used to verify that pitting occurred only on the wire face. Treatments consisted of polishing the samples to remove the passive layer, then immersing the wires in 90 C nanopure water for several hours. Treated wires show a marked increase in pitting corrosion resistance over untreated wires: the pit initiation potential increases by a minimum of 200 mV. Additional testing with scanning electron microscopy and energy dispersive X-ray spectroscopy indicate that the removal of sulphide inclusions from the surface is the most probable cause of this enhancement. To increase holographic reconstruction performance, Graphics Processing Units (GPUs) have been used; 4 Mpixel holograms are reconstructed using the dot product approximation of the Kirchhoff-Fresnel integral in 60 ms on a Tesla c1060 GPU. Errors in sizes and positions can easily be as large as 5 to 10 % for regions where the dot product approximation is not valid, so algorithms with fewer or no approximations are also required. Reconstructions for arbitrary holographic geometries using the full Kirchhoff-Fresnel integral take approximately 1 hour (compared to 1 week on a quad-core CPU), and reconstructions using convolution methods, in which the results of 256 reconstructions at 4096 x 4096 pixels in one plane are combined, take 17 s. This method is almost exact, with approximations only in the obliquity factor.

碩士
國立中山大學
機械與機電工程學系研究所
91
When the shaft current passes through the bearing under lubrication condition, the arc often occurs and the pitting can be observed on the surface of bearing. Consequently, the life of bearing is shortened. The pitting resulting from discharge is dependent upon the shaft voltage, the oil film thickness, and the insulation of lubricant. To simulate the pitting, the dynamic pitting tester is developed to investigate the effects of the kinematics parameters on the electrical pitting formation mechanism for the common material of bearing by changing the supply voltage current and the oil film thickness. Result show that in the static condition, since the arc action causes the surface melting of two specimens, and the actions of coulomb force and electrostatic force cause the specimens to attract each other, the plateau can be observed on the surfaces of specimens. The plateau is like a bridge to connect two specimens. In this moment the plateau accumulates continuously and causes two specimens to produce the repulsive force. In the dynamic condition, the formation of pitting at the initial stage is quite similar to that in the static condition. Since the effect of sliding speed, the bridge is sheared and the friction force increases. Under the actions of joule heat and friction force, the surfaces of two specimens melt and scratch continuously. When the dynamic pitting occurs, the pitting width of square specimen, the normal force and the friction force increases with increasing supply voltage, supply current, and oil film thickness. When the interface power is larger, the melting phenomenon is more obvious, and the pitting width becomes larger. Because the surface melting and the actions of Coulomb force and electrostatic force cause the material accumulates continuously, the normal force and the friction force increase with increasing the interface power. To investigate all effects of experimental parameters on the pitting width, the empirical formula for the pitting width is established in terms of supply voltage, supply current, and oil film thickness. This formula can be used to predict oil film thickness or the size of pitting width on the bearing surface for diagnosing the lubricant condition of bearing.