Submitted for t he MASTERS OF SCIENCE Chemistry in the Department of Chemistry UNIVERSITY of the Witwatersrand December 1995

Orientador: Assis Vicente Benedetti / Coorientador: Cecílio Sadao Fugivara / Banca: Idalina Vieira Aoki / Banca: Hercílio Gomes de Melo / Banca: Roberto Garcia / Banca: Patricia Hatsue Suegama / Resumo: Nesta tese foi desenvolvida uma metodologia para avaliar a ação corrosiva de biodiesel usando as técnicas de espectroscopia de impedância eletroquímica e análise do ruído eletroquímico com eletrodos de carbono vítreo, aço carbono SAE 1020, cobre puro, latão e zinco puro em meio de biodiesel (B100), produzido a partir de óleo de soja e metanol, sem utilização de eletrólito de suporte. Devido à baixa condutividade ou elevada resistência à passagem de corrente do biodiesel foi necessária a realização de uma série de testes com potenciostato antes da realização das medidas eletroquímicas. Adicionalmente, foram realizados estudos para determinação do intervalo de amplitude de potencial AC mais adequado para a realização de medidas de impedância utilizando células eletroquímicas desenvolvidas para o estudo em meio de biodiesel. Todos os resultados de impedância eletroquímica obedeceram às premissas de causalidade, linearidade e estabilidade. Foram feitas medidas de impedância eletroquímica durante 5 ou 9 dias utilizando biodiesel sem degradação e degradado em diferentes condições, respectivamente. De forma geral, o biodiesel degradado a 110 ºC apresentou maior corrosividade quando comparado ao biodiesel sem degradação e biodiesel degradado a 170 ºC. Essa observação também foi confirmada pelos estudos de microscopia e microanálise feitos nas superfícies dos materiais. Esse comportamento provavelmente se deve a evaporação de espécies agressivas em maior temperatura. Foram feitas medidas de ruído eletroquímico em meio de biodiesel, mas os resultados ainda são pouco conclusivos e até o presente momento não é do conhecimento do grupo a existência de relatos na literatura sobre este tipo de medida neste meio. A espectroscopia na região do infravermelho indicou a formação de óxidos em algumas... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In this thesis we have developed a methodology for the electrochemical study of glassy carbon, SAE 1020 carbon steel, pure copper, brass and pure zinc in biodiesel (B100) medium, produced from soy bean oil and methanol, without the intentional addition of supporting electrolyte, utilizing electrochemical impedance spectroscopy and electrochemical noise analysis. Due to the biodiesel low conductivity or high resistance to current flow, it was needed to perform a series of tests with potentiostat before conducting the electrochemical measurements. Additionally, it was carried out studies in order to determine AC potential amplitude range more adequate to perform the impedance measurements by using electrochemical cells developed for using in biodiesel medium. All electrochemical impedance results obeyed the assumptions of causality, linearity and stability. Electrochemical impedance measurements were conducted during 5 or 9 days using biodiesel without degradation and with different degradation conditions, respectively. In general, the biodiesel degraded at 110 ºC showed higher corrosivity compared to both non-degraded and degraded at 170 ºC. This observation was also confirmed by microscopy and microanalysis studies performed on the materials surface. This behavior is probably due to aggressive species evaporation at higher temperatures. Electrochemical noise analyses were carried out in biodiesel medium, however the results are still inconclusive and as far as our knowledge go, there is no literature reports using this kind of measurement in this medium. Infrared spectroscopy indicated the oxides formation in certain surface regions of copper, brass and zinc in contact with biodiesel. Non-degraded and degraded at 170 ºC biodiesel samples were analyzed by gas chromatography-mass spectrometry and the... (Complete abstract click electronic access below) / Doutor

Este trabalho foi desenvolvido com o intuito principal de adquirir \"know how\" na fabricação de componentes fundidos e usinados de bombas centrífugas, para aplicações em plataformas \"offshore\". Os materiais utilizados para esse destino - aços inoxidáveis super duplex - constituem sistemas termodinamicamente meta estáveis, que buscam o estado de estabilidade termodinâmica quando excitados termicamente. Por outro lado, esses materiais apresentam uma grande instabilidade dimensional, devido às tensões residuais desenvolvidas no resfriamento do tratamento térmico e durante o processo de usinagem, principalmente quando se trabalha com tolerâncias extremamente pequenas (10 m a 15 μm). Nesse contexto, foram realizados tratamentos térmicos a partir de 520°C, variando-se de 20°C em 20°C até a temperatura limite de 1180°C, com o objetivo de verificar-se a influência dessas temperaturas na microestrutura, dureza e tenacidade ao impacto do material. O enfoque principal foi dado na dinâmica de precipitação da fase sigma, que é o intermetálico mais conhecido e estudado nessa categoria de aços. Sua precipitação é inevitável, durante o processo de solidificação, porém, pode ser minimizada controlando-se a composição química e a taxa de resfriamento. Partindo-se de uma estrutura solubilizada, foi possível determinar as temperaturas a partir das quais a fase sigma começa a precipitar e dissolve-se por completo, bem como a influência de sua presença na dureza e na energia absorvida no ensaio de impacto Charpy. Técnicas de microscopias óptica, eletrônica de varredura, eletrônica de transmissão e difração de raios-x foram utilizadas para caracterização microestrutural do material nas várias condições de tratamento térmico. Ensaios eletroquímicos utilizando-se água do mar sintética, aerada e saturada com C02, contendo 20000ppm, 40000ppm e 80000ppm de íons cloreto, a temperaturas de 5OC, 25OC e 60°C foram realizados somente para o material solubilizado a 1130°C, 1160°C e solubilizado a 1130°C, seguido por alívio de tensões a 520°C. Os resultados mostraram que o tratamento térmico de alivio de tensões a 520°C, não promoveu precipitação de fases intermetálicas na microestrutura e tampouco prejudicou a resistência a corrosão do material, indicando a possibilidade prática de seu uso. / The present work was developed to acquire know how in manufacturing of castings and machined components for centrifugal pumps for offshore platform applications. Normally, the materials used to do them are the super duplex stainless steels that are thermodynamically metastable systems which tend to equilibrium when thermally activated. On the other hand, these materials show a great dimensional instability due to the residual stresses developed during the cooling from heat treatment process and also after machining process. This is crucial when working with very small dimensional tolerances, typical for these components. It were made stress relief heat treatments from 520°C, increasing the temperatures in 20°C steps until 1180°C to check the influence of these temperatures on microstructures, hardness and absorbed energy in Charpy test of this materials. The main focus was given on sigma phase precipitation dynamic, because it is the most common and studied intermetalic in this kind of stainless steels. It is impossible to avoid its precipitation during the cooling from solidification process, but it can be minimized by controlling the chemical composition and the cooling rate from solidification. Starting with a solution annealed structure, it was possible to determine the temperature where the sigma phase begins to precipitate and also its dissolution temperature. The influence of sigma phase content on hardness and absorbed energy in impact test was evaluated. Microstructure characterization was made using optical, scanning and transmission electron microscopy, as well as X-ray diffraction analysis for each different temperature. The electrochemical corrosion tests using synthetic sea water with 20000ppm, 40000ppm and 80000ppm of chlorine ions, at 5oC, 25°C and 60°C were made. Samples solution annealed such at 1130°C and at 1160°C and solution annealed at 1130°C followed by aging at 520°C were tested electrochemically. The results showed that the stress relief heat treatment at 520°C did not promote the intermetalic phase precipitation on material\'s microstructure and also, did not diminish the material\'s corrosion resistance.

É grande o uso do alumínio em virtude de sua viabilidade técnica e econômica além da alta proteção frente à corrosão conferida pelo filme de óxido de alumínio formado em sua superfície. Neste trabalho foram realizadas deposições de filme de polianilina (PAni) sobre ligas de alumínio AA-2014, AA-2024 e 7075 O. Os experimentos de eletropolimerização foram realizados por voltametria cíclica e cronoamperometria a partir de soluções aquosas contendo ácido fosfórico, ácido sulfâmico e anilina. Para a caracterização dos filmes obtidos sobre as superfícies das ligas foram utilizadas as técnicas de espectroscopia de infravermelho, microscopia eletrônica de varredura e espectroscopia de impedância eletroquímica. Os ensaios de corrosão foram realizados em meio agressivo ao alumínio, solução aquosa de NaCl 0,6 mol L-1 por medidas de polarização potenciodinâmica. Também foi estudada a nucleação dos filmes de PAni por cronoamperometria sobre as mesmas ligas. A partir da caracterização dos polímeros, os resultados demonstram diferenças estruturais entre os filmes de PAni decorrentes do meio ácido utilizado na eletropolimerização, que influencia na proteção contra corrosão. Estruturalmente os filmes eletropolimerizados em meio de ácido fosfórico são mais porosos em relação ao filme de PAni obtido em meio de ácido sulfâmico. Tanto para os filmes obtidos a partir de soluções aquosas de ácido fosfórico como de ácido sulfâmico ocorreram variações estruturais dos filmes após os ensaios de corrosão. Os parâmetros eletroquímicos extraídos das curvas potenciodinâmicas e das análises de impedância demonstram que os filmes obtidos protegem as ligas estudadas contra corrosão. Considerando-se o filme no estado desdopado, para a liga AA-2014, houve um deslocamento no potencial de corrosão de 61,2 mV para valores mais positivos em relação a liga sem recobrimento. Para as outras ligas esse deslocamento foi de 176,1 mV para a liga AA-2024 e 134,3 mV para a liga 7075, evidenciando assim uma maior proteção contra corrosão. Os estudos de corrosão evidenciam que os filmes de PAni podem ser alternativas viáveis aos outros meios protetores utilizados contra corrosão. / Aluminum is widely used due to its technical and economic advantages, as well as due to its high level of corrosion protection provided by the oxide film formed on the surface of the metal. In the current study deposition of polyaniline (PAni) on three different Al alloys (AA-2014 F, AA-2024 T3 and 7075 O) was studied. The electrodepositions were realized from aqueous solutions of either phosphoric acid or sulphamic acid that contained the aniline monomer, using the techniques of cyclic voltammetry and chronoamperometry. The films were characterized by infrared spectroscopy (IR), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). To evaluate the resistance of the films under conditions aggressive to Al, potentiodynamic polarization curves were performed in 0,6 mol L-1 NaCl. The nucleation of the films on the aluminum alloys was also investigated using chronoamperometry. Characterization of the PAni films obtained demonstrates that the use of different acids results in distinct structural characteristics, which influence their corrosion protection properties. Structurally the electro-deposited PAni films are more porous when phosphoric acid is used compared to sulphamic acid. After the corrosion assays structural differences are observed, independent of the acid used in the electrosynthesis. Data obtained from the potentioidynamic polarization curves and the impedance measurements indicate that the films obtained protect the alloys studied against corrosion. Considering the film in the undoped form for the alloy AA-2014 F, there was a positive shift in the corrosion potential of 61.2 mV. For the AA-2024 T3 and 7075 O alloys the shifts were 176.1 and 134.4 mV, respectively, indicating a greater degree of corrosion protection. The present study demonstrates that PAni films are viable alternatives to other protection methods.

by Ka-Man Mak. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1998. / Includes bibliographical references. / Text in English; abstract also in Chinese. / by Ka-Man Mak. / Acknowledgement --- p.i / Abstract --- p.ii / List of tables --- p.v / List of figures --- p.vi / Table of contents --- p.xi / Chapter Chapter One --- Introduction --- p.1-1 / Chapter 1.1 --- History of intermetallics --- p.1-1 / Chapter 1.2 --- Properties of intermetallic compounds --- p.1-5 / Chapter 1.2.1 --- Magnetic properties --- p.1-5 / Chapter 1.2.2 --- Chemical properties --- p.1-6 / Chapter 1.2.3 --- Semiconducting properties --- p.1-7 / Chapter 1.2.4 --- Superconducting properties --- p.1-7 / Chapter 1.2.5 --- Hydrogen storage --- p.1-8 / References --- p.1-9 / Chapter Chapter Two --- Background --- p.2-1 / Chapter 2.1 --- Some Behaviours of Intermetallics / Chapter 2.1.1 --- Intergranular and cleavage fracture --- p.2-1 / Chapter 2.1.2 --- Corrosion --- p.2-3 / Chapter 2.1.3 --- Oxidation in high-temperature intermetallics --- p.2-5 / Chapter 2.1.4 --- Hot corrosion --- p.2-8 / Chapter 2.2 --- Nickel aluminides --- p.2-9 / Chapter 2.2.1 --- Ni3Al --- p.2-10 / Chapter 2.2.2 --- NiAl --- p.2-12 / References --- p.2-14 / Chapter Chapter Three --- Oxidation --- p.3-1 / Chapter 3.1 --- Introduction --- p.3-1 / Chapter 3.2 --- Specimens preparation --- p.3-1 / Chapter 3.3 --- Experiment process --- p.3-5 / Chapter 3.3.1 --- Instrumentation --- p.3-5 / Chapter 3.3.2 --- Choosing of experimental temperature --- p.3-9 / Chapter 3.3.3 --- Methodology --- p.3-9 / Chapter 3.4 --- Results and Discussions --- p.3-10 / Chapter 3.4.1 --- Dependence of time --- p.3-10 / Chapter 3.4.2 --- Dependence of temperature --- p.3-14 / Chapter 3.4.3 --- Dependence of composition --- p.3-15 / Chapter 3.4.4 --- Activation energy of oxidation --- p.3-15 / Chapter 3.4.5 --- Oxidation morphology and mechanism --- p.3-16 / Chapter 3.5 --- Conclusions --- p.3-20 / References --- p.3-21 / Chapter Chapter Four --- Hot corrosion --- p.4-1 / Chapter 4.1 --- Introduction --- p.4-1 / Chapter 4.2 --- Specimens preparation --- p.4-1 / Chapter 4.3 --- Experiment process --- p.4-3 / Chapter 4.3.1 --- Instrumentation --- p.4-3 / Chapter 4.3.2 --- Choosing of experimental environment and temperature --- p.4-5 / Chapter 4.3.3 --- Methodology --- p.4-6 / Chapter 4.3.3.1 --- Experiment --- p.4-6 / Chapter 4.3.3.2 --- Experimental setup --- p.4-8 / Chapter 4.4 --- Results and discussions --- p.4-9 / Chapter 4.4.1 --- Dependence of time --- p.4-9 / Chapter 4.4.2 --- Dependence of temperature --- p.4-10 / Chapter 4.4.3 --- Comparison between hot corrosion with oxidation --- p.4-11 / Chapter 4.4.4 --- Dependence of composition --- p.4-12 / Chapter 4.4.4.1 --- Comparison between S1 and S2 --- p.4-12 / Chapter 4.4.4.2 --- Comparison between S3- S7 --- p.4-12 / Chapter 4.4.5 --- Results from XRPDS --- p.4-13 / Chapter 4.4.6 --- Study of microstructure --- p.4-13 / Chapter 4.4.6.1 --- Dependence on time --- p.4-14 / Chapter 4.4.6.2 --- Dependence on temperature --- p.4-14 / Chapter 4.4.6.3 --- Dependence on composition --- p.4-14 / Chapter 4.5 --- Corrosion mechanism --- p.4-15 / Chapter 4.5.1 --- Chemical reactions --- p.4-15 / Chapter 4.5.2 --- Corrosion process --- p.4-16 / Chapter 4.5.2.1 --- Temperature effect --- p.4-16 / Chapter 4.5.2.2 --- Composition dependence --- p.4-17 / Chapter 4.6 --- Conclusions --- p.4-18 / References --- p.4-19 / Chapter Chapter Five --- Conclusionsand suggestions for further studies --- p.5-1 / Chapter 5.1 --- Oxidation --- p.5-1 / Chapter 5.2 --- Hot corrosion --- p.5-2 / Chapter 5.3 --- Further development --- p.5-3

Concrete structures can prematurely deteriorate due to the corrosion of reinforcing steel. Corrosion can occur through chloride ingress due to exposure to aggressive media such as seawater and deicing salts. Corrosion causes over $100 billion in damage annually. There are many corrosion mitigation techniques on the market today; these techniques have limited effectiveness as demonstrated by the fact that billions of dollars are still being expended each year due to corrosion-related damage. Therefore, there is a need for innovative approaches to corrosion prevention. This research program used cinnamaldehyde (CA), a bioactive agent derived from cinnamon bark, as a method for corrosion mitigation. Although CA can prevent the corrosion of metals, its hydrophobicity has a negative effect on hydration when incorporated in cementitious systems. In order to avoid these negative consequences while harnessing the anti-corrosive properties, CA was incorporated in a cementitious mixture through the use of lightweight aggregate (LWA). Several tests were carried out to investigate the potential chemical and mechanical effects due to the addition of LWA pre-wet with CA. Promising results were observed, in which the time to corrosion was prolonged by 91 %.

The annual cost of corrosion in the United States Navy and Coast Guard is in excess of $2.7 billion dollars. The salt water environment provides a ripe surrounding for rapid corrosion and deterioration of ship decking, which requires frequent and expensive maintenance. Decks of ships are susceptible to corrosion and wear, but must also maintain a non-slip surface in a constantly wet environment. Few options for non-skid deck materials are currently approved for use by the Navy and require frequent and expensive maintenance or replacement. A new material known as Laser Deposited Non-Skid, currently used in industrial flooring applications, shows potential for serving as a more durable non-skid material with extended service life and greater resistance to corrosion. The purpose of this research is to investigate the feasibility of Laser Deposited Non-Skid in decks of ships and to compare the corrosion, wear and cost data with existing deck materials. Sample plates of A36 and A572 steel and 5086 and 5456 marine grade aluminum alloy were coated with selected non-skid materials and subjected to laboratory salt fog testing and corrosion in environmental conditions in the Caribbean Sea. Wear behavior among non-skid materials was evaluated through wear cycles, measurement of coefficient of friction, and surface characterization. Salt fog testing was more corrosive than the actual operational environment in all cases and the Laser Deposited Non-Skid samples had the best resistance to wear and corrosion. The Peel and Stick Non-Skid demonstrated corrosion by undercutting while the Traditional Non-Skid corroded through the material. The relative area did not correlate well with friction or wear mass loss. Aluminum Laser Deposited Non-Skid appears suitable for use as a deck material on small boats. More research is needed to evaluate maintenance issues and possible stress cracking associated with the Laser Deposited Non-Skid on steel decks.

Epoxy coatings are currently the most popular corrosion protection mechanism for steel reinforcement in structural concrete. However, these coatings are easily damaged on worksites, negating their intended purpose. This study investigates self-healing coatings for steel reinforcement to introduce an autonomous healing mechanism for damaged coatings. Coatings were applied to steel coupons, intentionally damaged, and introduced to a corrosive environment via aerated salt-water tanks. Performance of the experimental coatings was evaluated qualitatively and quantitatively. Adhesion strength and effects of coating thickness were also studied. Results from coated steel coupons subjected to damage and submerged in salt-water aeration tanks exhibited improved corrosion resistance performance with self-healing coatings. However, self-healing coatings have comparable poor adhesion to the substrate as do conventional coatings. This paper shows preliminary results demonstrating the potential benefits of self-healing coatings for steel reinforcement and identifies numerous avenues for future research.

As an important technique for corrosion control in marine environment, Cathodic Protection (CP) should be applied with a full understanding of environmental conditions and a good consideration of current requirements. Early studies on different kinds of steel specimens in the intertidal zone show severe corrosion losses. Nevertheless, there is evidence that CP can work in these regions of a steel structure because electrolyte pathway can remain some time on thin wetted surfaces when tides recede. This research aims to study corrosion activities and their behaviour under the influence of CP in a thin layer of electrolyte as a simulation of the inter-tidal zone. By means of a mechanical vibrating probe, Scanning Vibrating Electrode Technique (SVET) may be used to study local activities at coating defects in a thin electrolyte layer. The effect of CP on the local currents at the defect site was confirmed by SVET and, significantly, the development of calcareous films under these conditions in seawater was also observed. Such films are found to be effective in the absence of cathodic polarisation and only failed after damage. In order to explore the performance of applying CP, a Finite Element (FE) model of electrically connected zinc and steel samples beneath a specific thickness of electrolyte has been created, with full polarisation curves implemented for each metal based on experimental results obtained. The influence of the electrolyte conductivity and the geometry of the electrodes has also been considered. A comparison can then be made between experimental investigation and computational modelling of this corrosion cell. Epoxy-coated and uncoated mild steel samples obtained in the simulated tidal facility were also investigated. The formation of calcareous films was confirmed. Calcareous films were protective under these intermittent wetting conditions. Techniques used to understand the performance include optical observation, Scanning Electron Microscopy (SEM) together with Energy Dispersive X-ray (EDX) and X-ray Diffraction (XRD) analysis.

Orientador: Herman Jacobus Cornelis Voorwald / Banca: Maria Odila Hilário Cioffi / Banca: Mauro Pedro Peres / Banca: Andre Luis Moreira de Carvalho / Banca: Carlos de Moura Neto / Resumo: As ligas de alumínio desempenham papel fundamental na indústria aeronáutica. A liga Al 7050 é usada em diversas partes da estrutura dos aviões e, em particular, na fabricação de componentes do trem-de-pouso. As condições operacionais fazem com que estes componentes trabalhem sob condições ambientais agressivas, tornando necessário aumentar sua resistência à corrosão através de tratamentos superficiais. Para o alumínio e suas ligas, a anodização é um dos tratamentos mais utilizados para esta finalidade. Os processos de anodização melhoram a resistência à corrosão das ligas de alumínio, mas reduzem a resistência à fadiga. Para minimizar ou eliminar os efeitos negativos das anodizações foram realizados estudos com o processo mecânico de shot peening sobre o material base antes das anodizações. Foram realizados ensaios de fadiga por flexão rotativa e por flexão alternada para as condições sem e com shot peening e fadiga axial, sem shot peening para as direções longitudinal e transversal à direção de laminação. Os resultados somente com anodização mostram que, para todos os processos de anodização, há redução na resistência à fadiga do material e que a anodização crômica é a que apresenta os melhores resultados, seguidos da anodização sulfúrica e dura. Os dados com shot peening seguido de anodização mostram que este tratamento neutraliza os efeitos negativos da anodização e promove um aumento na resistência à fadiga, sobre o material-base para a maioria das condições analisadas. Nos ensaios de fadiga por flexão rotativa e flexão alternada não foram observadas tendências de melhor comportamento em fadiga em relação à direção dos corpos-de-prova. Na fadiga axial os melhores resultados foram obtidos para a direção transversal a laminação. / Abstract: Aluminum alloys play a fundamental role in the it elaborates aeronautics. The 7050 aluminum alloy is used in several parts of the structure of the airplanes and in the production of landing year components. The operational conditions like aggressive environment, made necessary to increase corrosion resistance through superficial treatments. For the aluminum alloys, the anodization is one of the treatments used for this purpose. The anodization processes improve the resistance to corrosion of the aluminum alloy, but reduce the resistance to fatigue. To minimize or to eliminate the negative effects of the anodization, studies they were performed with the mechanical process of shot peening on the base material before the anodization. Rotating and reverse bending for the conditions without and with shot peening, for the longitudinal and traverse directions were performed. The results only with anodizing they show that for all processes was reduction in the fatigue strength of the material occurred among them the anodizing chromic was the one that presented the best results, followed by the sulfuric and hard anodizing. The results with shot peening followed by anodizing show that the shot peening neutralized the negative effects of the anodizing and promoted an increase in the fatigue resistance, for most of the analyzed conditions. In the results for rotating and reverse bending tendencies of better behavior were not observed in fatigue with relation to the direction of the samples and in the axial fatigue the best results were obtained for the traverse direction. / Doutor