M.Sc. (Physics) / Please refer to full text to view abstract

Thesis. 1977. M.S.--Massachusetts Institute of Technology. Dept. of Electrical Engineering and Computer Science. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING. / Includes bibliographical references. / M.S.

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

Doctorat en Sciences / info:eu-repo/semantics/nonPublished

No description available.

This study was intended to provide a fuller understanding of the surface chemical processes which result in the corrosion of ferrous materials.

The focus of this research is to explore the molecular-level interactions between reactive metal surfaces and aqueous environments by combined ultra-high vacuum/electrochemistry (UHV-EC) methodology. The objectives of this work are to understand (1) the effects of sulfate ions on the passivity of metal oxide/hydroxide surface layer, (2) the effects of sulfur-modification on the evolution of metal oxide/hydroxide surface layer, and (3) the effects of sulfur adsorbate on cation adsorption at metal surfaces.

Metal oxide reactions at metal oxide surfaces or at metal-metal oxide interfaces are of exceptional significance in areas such as catalysis, micro- and nanoelectronics, chemical sensors, and catalysis. Such reactions are frequently complicated by the presence of high electric fields and/or H2O-containing environments. The focus of this research was to understand (1) the iron oxide growth mechanism on Fe(111) at 300 K and 500 K together with the effect of high electric fields on these iron oxide films, and (2) the growth of alumina films on two faces of Ni3Al single crystal and the interaction of the resulting films with water vapor under non-UHV conditions. These studies were conducted with AES, LEED, and STM. XPS was also employed in the second study. Oxidation of Fe(111) at 300 K resulted in the formation of Fe2O3 and Fe3O4. The substrate is uniformly covered with an oxide film with relatively small oxide islands, i.e. 5-15 nm in width. At 500 K, Fe3O4 is the predominant oxide phase formed, and the growth of oxide is not uniform, but occurs as large islands (100 - 300 nm in width) interspersed with patches of uncovered substrate. Under the stress of STM induced high electric fields, dielectric breakdown of the iron oxide films formed at 300 K occurs at a critical bias voltage of 3.8 ± 0.5 V at varying field strengths. No reproducible result was obtained from the high field stress studies of the iron oxide formed at 500 K. Ni3Al(110) and Ni3Al(111) were oxidized at 900 K and 300 K, respectively. Annealing at 1100 K was required to order the alumina films in both cases. The results demonstrate that the structure of the 7 Å alumina films on Ni3Al(110) is k-like, which is in good agreement with the DFT calculations. Al2O3/Ni3Al(111) (γ'-phase) and Al2O3/Ni3Al(110) (κ-phase) films undergo drastic reorganization and reconstruction, and the eventual loss of all long-range order upon exposure to H2O pressure > 10-5 Torr. Al2O3/Ni3Al(110) film is significantly more sensitive to H2O vapor than the Al2O3/Ni3Al(111) film, and this may be due to the incommensurate nature of the oxide/Ni3Al(110) interface. STM measurements indicate that this effect is pressure- rather than exposure- dependent, and that the oxide instability is initiated at the oxide surface, rather than at the oxide/metal interface. The effect is not associated with formation of a surface hydroxide, yet is specific to H2O (similar O2 exposures have no effect).

The purpose of this study was to investigate the effects and interactions of lead, frequency, amplitude of slip, humidity, and film thickness of polyvinyl chloride on fretting corrosion. In particular, this study describes the effects of these parameters on the polymer film life and also on the wear of the metal surfaces after metallic contact had occurred. The two levels that were used for each parameter are: load, 15.6 and 31.1 N (3.5 and 7.0 lb); amplitude of slip, 165 and 330 μm (6.5 and 13 mils); frequency of slip, 20 and 40 Hz; humidity of air, 16.6 percent, and 58.4 percent relative humidity; and PVC film thickness, 20 and 37 μm (0.8 and 1.45 mils). The 52100 steel balls were loaded against a 1045 steel disk that was coated with PVC. This configuration was then subjected to a two-level, five-factor experiment comprised of the above levels of conditions. / M.S.

O presente trabalho discute a influência da microestrutura dos ferros fundidos, cinzento (FFC) e vermicular (FFV), na ocorrência de metal dobrado (FM) em superfícies brunidas e no comportamento tribológico em ensaio lubrificado do tipo anel sobre cilindro. As amostras de ferro fundido foram extraídas diretamente de um bloco de motor de combustão interna, em regiões de diferentes espessuras. O anel de pistão utilizado foi de aço inoxidável martensítico nitretado com perfil assimétrico e o óleo lubrificante foi o SAE 30 CF monoviscoso. A quantificação de sulcos e de metal dobrado (FM) foi realizada empregando-se uma metodologia baseada na literatura. Para a execução dos ensaios tribológicos foi projetada e construída uma adaptação para a montagem das amostras e controle de temperatura do óleo lubrificante. Um parâmetro para avaliação do desempenho tribológico foi proposto – índice de mérito tribológico (IMT) – que leva em conta coeficiente de atrito (COF) e alterações de topografia. Os ferros fundidos apresentaram microestruturas típicas. Contudo, observaram-se diferenças de morfologia e distribuição da grafita; com maior número de grafitas e menor fração de grafita para os materiais de parede fina. Observou-se FM nos platôs e nos sulcos das superfícies brunidas em todas as amostras. Quantificações mostraram que as larguras dos sulcos foram estatisticamente iguais e com alto percentual de obstrução. A quantificação de FM dos materiais mostrou maiores valores presentes na região do Spk (FMspk) para os FFC's. Os materiais de parede grossa apresentaram maiores valores de % FM dentro do sulco (%FM/Sulco) e este parâmetro teve forte e positiva correlação estatística com a fração de grafita. Evidências, obtidas em avaliações de seções transversais, corroboraram a relação entre FM e grafita. Constatou-se que o FM pode ser formado diretamente sobre a grafita ou, ainda, de forma indireta devido à extrusão desta fase. Ademais, verificou-se que a morfologia e orientação da grafita têm influência na formação do FM. Realizaram-se ensaios preliminares de curta duração de anel sobre cilindro para a avaliação da repetibilidade dos resultados de COF, os quais indicaram menor dispersão para condições com menores frequências e maiores forças normais. Avaliações da dinâmica do ensaio tribológico permitiram apontar relações de redução de COF durante os semi-ciclos de movimento e associá-las à teoria de lubrificação hidrodinâmica. O COF para ensaios de longa duração apresentou comportamento cíclico com transições. Estas transições foram associadas a mecanismos de formação-remoção-formação de tribofilmes de ZDDP. Os ensaios impuseram alterações nos parâmetros de rugosidade (principalmente com alisamento das superfícies) e redução do parâmetro de filme. O IMT evidenciou pouca influência da espessura do material; e melhor desempenho tribológico para os FFV's. A rotina de quantificação de FM mostrou limitação técnica devido ao alisamento da superfície, o que causa mudança na referência de alturas das superfícies brunidas. Ainda assim, verificou-se redução do %FM/Sulco e tendência de desobstrução do sulco. Contatou-se pouca influência do FM no comportamento do COF devido à similaridade dos parâmetros de FM entre os materiais. Contudo, o FM foi associado a um agente de abrasão à três corpos e apresentou forte correlação positiva do parâmetro de FMspk (no início do ensaio) com o parâmetro do IMT relacionado com a alteração de topografia. / The present work discusses the influence of the microstructure of gray cast iron (GCI) and compacted graphite iron (CGI) on the occurrence of folded metal (FM) on honed surfaces and its tribological behavior in ring-on-cylinder test under lubrication. The cast iron samples were taken directly from an internal combustion engine block in regions of different thicknesses. The piston ring used was a nitrided martensitic stainless steel with asymmetrical profile and the lubricant oil was the SAE 30 CF. The quantification of grooves and folded metal (FM) was carried out using a methodology based on the literature. For the execution of the tribological tests an adaptation was designed and built for assembling the samples and for controlling the oil temperature. One parameter to evaluate the tribological performance was proposed - tribological merit index (TMI) - which considers the coefficient of friction (COF) and changes in topography. Each cast iron presented typical microstructures. However, differences in morphology and graphite distribution were observed; the samples from thinner wall presented higher number of graphite and less fraction of graphite. FM was observed on the plateaus and grooves of the honed surfaces in all samples. Quantification showed that the widths of the grooves were statistically similar and with a high percentage of obstruction. GCIs present a higher amount of FM in the Spk region (FMspk).The thicker wall samples presented a higher amount of FM in the grooves (% FM / Groove) and this parameter had a strong and positive statistical correlation with the graphite fraction. Evidences, obtained in cross section evaluations, corroborated the relationship between FM and graphite. It was verified that FM can be formed directly on graphite or indirectly due to the extrusion of this phase. In addition, its morphology and orientation influenced the occurrence of FM. Preliminary short-term tests were performed to evaluate the repeatability of COF results. These tests indicated less dispersion for conditions with lower frequencies and higher normal forces. Evaluations of the dynamics of the tribological test allowed to point out conditions to reduce the COF during the half-cycles of movement and to associate them to the theory of hydrodynamic lubrication. The COF for long-term tests presented cyclical behavior with transitions. These transitions were associated with formation-removal-formation mechanisms of ZDDP tribofilms. The tribological tests imposed changes on the roughness parameters (mainly with smoothness of the surfaces) and reductions on the film parameter. The thickness of samples affected little the TMI; and a better tribological performance of CGIs was detected. The FM quantification routine showed a technical limitation due to surface smoothing, which causes a change in the reference of heights of honed surfaces. Nevertheless, there was a reduction in %FM/Groove and tendency to clear the grooves. There was little influence of FM in COF behavior due to the similarity of FM parameters among the materials. However, FM was associated as a three-body abrasive agent and a strong positive correlation between the FMspk parameter (at the beginning of the test) and the TMI parameter was described.