Nitriding and oxidising treatments of alloys for toolingpurposes have been investigated both experimentally andtheoretically. Specimens prepared by a combination of differentprocessing steps are investigated by light-optical, scanningand transmission electron microscopy and hardness measurments.The bounds of carbon and nitrogen concentration profiles duringnitriding are obtained from simulations using the DICTRA code.As a result, a new processing route to produce oxide-dispersediron-base alloys with large volume fraction of carbides issuggested. On the theoretical side the methods based on the random walktechnique have been investigated and developed further. The newmethods have been applied to study a vide range of phenomenae.g. internal oxidation, diffusion in inhomogeneous media,phase transformations and formation of porosity due to theKirkendall effect in welded joints. Probability distributionsare introduced to replace random number generators in order toincrease computational efficiency. A general method to simulatediffusional phase transformations in multicomponent systems isdeveloped and applied to ternary alloys. / QC 20100506

Os aços semi processados, utilizados para a fabricação de lâminas de rotor e estator, são adquiridos das Siderúrgicas e após serem estampados em sua forma final, devem ser submetidos a um tratamento térmico de recozimento, o qual tem o objetivo de melhorar as propriedades magnéticas desse aço. Se esse tratamento térmico for realizado sob condições impróprias, os elementos dissolvidos na matriz que apresentam certa afinidade com o oxigênio reagirão com o mesmo, favorecendo assim a formação de uma camada de óxidos interna. Essa camada é considerada vilã para esses aços por deteriorar suas propriedades magnéticas, ou seja, diminui a permeabilidade magnética e aumenta a perda magnética. A formação desses óxidos ocorre durante o tratamento térmico devido ao demasiado tempo de exposição do aço e a temperaturas elevadas e elevado potencial de oxigênio, o que influencia diretamente na espessura e na morfologia da camada de óxido formada. Aços semi processados cuja somatória dos teores de Si e Al estão entre 0,5 e 2,0% em peso são particularmente mais susceptíveis a oxidação interna durante essa etapa. Então, identificar a influência do potencial de oxigênio na formação dessa camada, quantificar seus efeitos deletérios nas propriedades magnéticas e buscar melhorias de processo para minimizar os valores de perdas e maximizar a permeabilidade magnética são atualmente, de fundamental importância tecnológica. / Semi processed electrical steels, used for the manufacture of rotor and stator laminations are acquired from Steel Markers and after being punched in its final shape, must undergo an annealing heat treatment, which aims to improve the magnetic properties of the steel. If this heat treatment is carried out under inappropriate conditions, the dissolved elements in the matrix that have a certain affinity with oxygen will react together, thereby forming an oxides subsuperficial layer. This layer is considered villain for these steels for deteriorating their magnetic properties, better saying, it decreases the magnetic permeability and increases the magnetic loss. The formation of these oxides occurs during the heat treatment due to too long steel exposure at high temperatures and high oxygen potential, which directly influences the thickness and morphology of semi processed steel whose sum of the silicium and aluminum components are 0,5 and 2,0% in weight are particularly more susceptible to internal oxidation during this step. Then, identifying the oxygen potential influence in the formation of this layer, quantifying its deleterious effects on magnetic properties and seeking process improvements to minimize the values of losses and maximize the magnetic permeability are nowadays an important technological issue.

Os aços semi processados, utilizados para a fabricação de lâminas de rotor e estator, são adquiridos das Siderúrgicas e após serem estampados em sua forma final, devem ser submetidos a um tratamento térmico de recozimento, o qual tem o objetivo de melhorar as propriedades magnéticas desse aço. Se esse tratamento térmico for realizado sob condições impróprias, os elementos dissolvidos na matriz que apresentam certa afinidade com o oxigênio reagirão com o mesmo, favorecendo assim a formação de uma camada de óxidos interna. Essa camada é considerada vilã para esses aços por deteriorar suas propriedades magnéticas, ou seja, diminui a permeabilidade magnética e aumenta a perda magnética. A formação desses óxidos ocorre durante o tratamento térmico devido ao demasiado tempo de exposição do aço e a temperaturas elevadas e elevado potencial de oxigênio, o que influencia diretamente na espessura e na morfologia da camada de óxido formada. Aços semi processados cuja somatória dos teores de Si e Al estão entre 0,5 e 2,0% em peso são particularmente mais susceptíveis a oxidação interna durante essa etapa. Então, identificar a influência do potencial de oxigênio na formação dessa camada, quantificar seus efeitos deletérios nas propriedades magnéticas e buscar melhorias de processo para minimizar os valores de perdas e maximizar a permeabilidade magnética são atualmente, de fundamental importância tecnológica. / Semi processed electrical steels, used for the manufacture of rotor and stator laminations are acquired from Steel Markers and after being punched in its final shape, must undergo an annealing heat treatment, which aims to improve the magnetic properties of the steel. If this heat treatment is carried out under inappropriate conditions, the dissolved elements in the matrix that have a certain affinity with oxygen will react together, thereby forming an oxides subsuperficial layer. This layer is considered villain for these steels for deteriorating their magnetic properties, better saying, it decreases the magnetic permeability and increases the magnetic loss. The formation of these oxides occurs during the heat treatment due to too long steel exposure at high temperatures and high oxygen potential, which directly influences the thickness and morphology of semi processed steel whose sum of the silicium and aluminum components are 0,5 and 2,0% in weight are particularly more susceptible to internal oxidation during this step. Then, identifying the oxygen potential influence in the formation of this layer, quantifying its deleterious effects on magnetic properties and seeking process improvements to minimize the values of losses and maximize the magnetic permeability are nowadays an important technological issue.

Les matériaux basés sur le système Fe-Ni-Cr utilisés à haute température doivent présenter une bonne résistance à l'oxydation, généralement obtenu par la croissance lente d’une couche d’oxyde de chrome à la surface de ces alliages. Pour prédire la formation d'une couche d’oxyde protectrice la perméabilité de l'oxygène dans l’alliage doit être connue, la perméabilité étant définie comme le produit de la solubilité et du coefficient de diffusion de l’oxygène. L'objectif de nos travaux est de mesurer la perméabilité, la solubilité et la diffusivité de l'oxygène dans des alliages Fe-Ni pour des températures supérieures à 1000°C. Afin d'obtenir les meilleurs résultats,la formation d'une couche externe d'oxyde pendant les expériences doit être évitée. Pour cela, la pression partielle d'oxygène a été fixée à la pression d'équilibre Fe/FeO dans toutes les expériences. En outre, afin d'étudier l'effet de la vapeur d'eau sur la perméabilité, la solubilité et la diffusivité de l’oxygène, deux atmosphères ont été utilisées: l’une considérée comme sèche et l’autre comme humide. L'atmosphère sèche a été obtenue en utilisant la technique du « pack de Rhines »: les échantillons sont oxydés dans des capsules en quartz sous vide qui contiennent un mélange de poudre de fer et de wüstite. L'atmosphère humide a quant à elle été obtenue en utilisant des mélanges gazeux H2/H2O avec un ratio approprié de vapeur d'eau et d’hydrogène afin de fixer la pression partielle d’oxygène à la pression d’équilibre Fe/FeO. Les mesures de solubilité réalisées dans ce travail ont montré que celle-ci atteint son maximum dans le fer pur et diminue avec l’ajout de nickel. Cependant, la dépendance de la solubilité avec la composition de l’alliage Fe-Ni n'est pas idéale et ne peut être prédite à partir de modèles simples. De plus, les résultats obtenus sous atmosphère humide suggèrent que la présence de vapeur d'eau dans l'atmosphère augmente la solubilité de l'oxygène d’un facteur 2 dans les alliages avec une concentration en nickel inférieure ou égale à 60 at.% pour des températures proches de 1000°C,tandis qu'à 1150°C, la solubilité de l'oxygène est indépendante de l'environnement. La perméabilité de l'oxygène a été déterminée en mesurant la cinétique d'oxydation interne d'alliages Fe-Ni-Cr. Les résultats ont montré que la perméabilité de l'oxygène présente les mêmes variations avec la composition de l’alliage que la solubilité de l'oxygène, indépendamment de l'atmosphère.De plus, aucun effet significatif de la vapeur d'eau sur les valeurs de perméabilité de l'oxygène n'a été observé. Le coefficient de diffusion de l'oxygène a également été déterminé en utilisant les résultats précédents, c’est à dire la perméabilité et la solubilité de l’oxygène mesurées dans notre étude. Pour une température supérieure à 1000°C, la variation du coefficient de diffusion de l'oxygène avec la composition de l'alliage est similaire dans tous les environnements testés et un maximum est observé pour les alliages avec une teneur en nickel de 40 at.%. Cependant, la présence de vapeur d'eau dans l'atmosphère diminue les valeurs du coefficient de diffusion de l'oxygène, par un facteur 2-3 à 1000°C, pour les alliages avec une concentration en nickel inférieure ou égal à 60 at.%. De plus, il a été trouvé que la différence entre les coefficients de diffusion mesurés dans l’atmosphère sèche et humide augmente à mesure que la température diminue. En conclusion, il a été constaté que la vapeur d'eau n'a aucun effet sur la manière dont la perméabilité, la solubilité et la diffusivité de l'oxygène varient avec la composition des alliages Fe-Ni. Cependant, la présence de vapeur d'eau dans l'environnement semble augmenter la solubilité de l'oxygène et diminuer sa diffusivité dans les alliages riches en fer. De plus, l’effet de la vapeur d’eau apparaît plus important aux plus basses températures étudiées. / It is a worldwide priority to reduce emissions of greenhouse gases such as CO2. One solution for reducing these emissions is to improve the efficiency of energy production units by increasing their operating temperature. However, in order to increase operating temperature, new austenitic materials based on the Fe-Ni-Cr system have to be designed. In addition, these materials need to exhibit good protection against high temperature oxidation, which is achieved by the formation of a slow growing chromium oxide or alumina scale on the metal. However, to predict the formation of a protective scale, knowledge of the oxygen permeability, the product of oxygen solubility and diffusivity, in the base alloy is required. The objective of this study is to measure the permeability, solubility and diffusivity of oxygen in Fe- Ni alloys at temperatures above 1,000°C. In order to obtain the best results, the formation of an external oxide layer during the experiment has to be avoided. To achieve this, the oxygen partial pressure was fixed at the Fe/FeO equilibrium pressure in all experiments. In addition, two types of atmospheres were used: one dry and one wet, in order to investigate the effect of water vapour on oxygen permeability, solubility and diffusivity. The dry atmosphere was achieved using the Rhines Pack technique. The samples were oxidised in vacuum-sealed quartz capsules, which contained a mixture of powdered iron and wüstite. The humid atmosphere was obtained by using H2/H2O gas mixtures with the appropriate water vapour to hydrogen ratio to fix oxygen partial pressure at the Fe/FeO equilibrium. The maximum oxygen solubility was found in pure iron, and decreased continuously with nickel additions to the alloy. The dependence of solubility on alloy composition is non-ideal, and cannot be predicted from simple models. Moreover, the presence of water vapour in the atmosphere seems to increase the solubility by a factor of 2 in alloys with nickel content lower than 80 at.% at temperatures near 1,000°C. However, at 1,150°C the solubility of the oxygen is independent of the environment. The oxygen permeability was determined by measuring the internal oxidation kinetics of Fe-Ni-Cr alloy. These kinetics were evaluated by measuring the internal oxidation zone depth by optical microscopy, or by continuous and discontinuous thermogravimetry. Results showed that the oxygen permeability exhibits the same variation with alloy composition as the oxygen solubility, independent of the atmosphere. In particular, no significant effect of water vapour on oxygen permeability values was observed. In the present study, the oxygen diffusion coefficient was also determined using permeability, in addition to the independent measurement of the oxygen solubility carried out in the present study. For temperature above 1,000°C, the variation of oxygen diffusion coefficient with the alloy composition is similar in all environments tested, and a maximum is observed for alloys with a nickel content of 40 at.%. However, for a given nickel content up to 60 at.%, the presence of water vapour in the atmosphere decreases the value of the oxygen diffusion coefficient by a factor of 2-3 at 1,000°C. In addition, this difference between diffusion coefficients measured in a dry and wet atmosphere increases as the temperature decreases. Overall, it was found that the water vapour has no effect on the way in which oxygen permeability, solubility and diffusivity vary with the alloy composition. However, the presence of water vapour in the environment appears to increase the oxygen solubility and decrease the oxygen diffusivity in iron-rich alloys, the effect being more significant at low temperatures. These results suggest further research into interactions between O, H and metal vacancies, particularly for temperature around 1,000°C and below, as the latter defect is thought to change the diffusion and solubility properties of interstitial species.

Joints between carbon steel and Alloy 600, containing Alloy 82 weld metal, were exposed to two steam-hydrogen environments considered to simulate exposure to primary water conditions in a Pressurized Water Reactor (PWR) or Canada Deuterium Uranium (CANDU) reactor. The welds were found to have elevated and variable iron contents due to dilution by carbon steel during welding. This gave the Alloy 82 weld, near the inner surface of the component, an iron content approaching that of Alloy 800. A potentially protective external iron oxide film formed on the inner surface of the weld. However, the chromium content throughout the weld is below that which would form an external chromium oxide. The results indicate that low chromium content causes internal oxidation throughout the weld and potentially below the external iron oxide which could lead to Primary Water Stress Corrosion Cracking (PWSCC).

Joints between carbon steel and Alloy 600, containing Alloy 82 weld metal, were exposed to two steam-hydrogen environments considered to simulate exposure to primary water conditions in a Pressurized Water Reactor (PWR) or Canada Deuterium Uranium (CANDU) reactor. The welds were found to have elevated and variable iron contents due to dilution by carbon steel during welding. This gave the Alloy 82 weld, near the inner surface of the component, an iron content approaching that of Alloy 800. A potentially protective external iron oxide film formed on the inner surface of the weld. However, the chromium content throughout the weld is below that which would form an external chromium oxide. The results indicate that low chromium content causes internal oxidation throughout the weld and potentially below the external iron oxide which could lead to Primary Water Stress Corrosion Cracking (PWSCC).

Os tratamentos de cementação, têmpera, revenimento e jateamento por granalhas são muito utilizados na produção seriada de peças da indústria automobilística, como engrenagens e eixos. Variações destes processos podem influenciar a vida em fadiga por flexão dos componentes descritos. O objetivo deste trabalho foi estudar a influência de variações no tempo de jateamento por granalhas, variações na temperatura de revenimento e de diferentes profundidades de oxidação intergranular, no crescimento de trincas curtas por fadiga na camada cementada do aço DIN 20MnCr5. Para isso foram feitos ensaios de fadiga por flexão em quatro pontos, utilizando corpos de prova de seção retangular e sem entalhe. Para o acompanhamento do crescimento de trincas curtas foi utilizado o método de réplicas de acetato. Foram estudados seis níveis de jateamento, quatro níveis de revenimento e dois níveis de oxidação intergranular. Como resultados principais, foram obtidas curvas de comprimento de trinca por número de ciclos e taxa de crescimento de trinca por tamanho médio da trinca. Amostras jateadas entre trinta minutos e uma hora, revenidas à 160&#176C e com oxidação intergranular por volta de dez mícrons, apresentaram os melhores resultados em relação à vida em fadiga. / Carburizing, quenching, tempering and shot peening treatments are often used in mass production of automotive parts, such as gears and shafts. Changes in these treatments can influence the bending fatigue life of these parts. The purpose of this study was to measure the influence of different shot peening times, different tempering temperature and different internal oxidation depths, on the short fatigue crack growth in case carburized DIN 20MnCr5 steel. Four-point-bend fatigue tests were carried out in rectangular section specimens without notch. The surface short crack growth was monitored by means of acetate replication technique. Six levels of shot peening, four levels of tempering temperatures and two levels of internal oxidation were studied in this work. Crack length versus number of cycles and crack growth rate versus mean crack length were obtained as principal results. Shot peening from 30 minutes to one hour, tempering at 160#176C and a lO~m depth of internal oxidation showed the best results in fatigue life.

Os tratamentos de cementação, têmpera, revenimento e jateamento por granalhas são muito utilizados na produção seriada de peças da indústria automobilística, como engrenagens e eixos. Variações destes processos podem influenciar a vida em fadiga por flexão dos componentes descritos. O objetivo deste trabalho foi estudar a influência de variações no tempo de jateamento por granalhas, variações na temperatura de revenimento e de diferentes profundidades de oxidação intergranular, no crescimento de trincas curtas por fadiga na camada cementada do aço DIN 20MnCr5. Para isso foram feitos ensaios de fadiga por flexão em quatro pontos, utilizando corpos de prova de seção retangular e sem entalhe. Para o acompanhamento do crescimento de trincas curtas foi utilizado o método de réplicas de acetato. Foram estudados seis níveis de jateamento, quatro níveis de revenimento e dois níveis de oxidação intergranular. Como resultados principais, foram obtidas curvas de comprimento de trinca por número de ciclos e taxa de crescimento de trinca por tamanho médio da trinca. Amostras jateadas entre trinta minutos e uma hora, revenidas à 160&#176C e com oxidação intergranular por volta de dez mícrons, apresentaram os melhores resultados em relação à vida em fadiga. / Carburizing, quenching, tempering and shot peening treatments are often used in mass production of automotive parts, such as gears and shafts. Changes in these treatments can influence the bending fatigue life of these parts. The purpose of this study was to measure the influence of different shot peening times, different tempering temperature and different internal oxidation depths, on the short fatigue crack growth in case carburized DIN 20MnCr5 steel. Four-point-bend fatigue tests were carried out in rectangular section specimens without notch. The surface short crack growth was monitored by means of acetate replication technique. Six levels of shot peening, four levels of tempering temperatures and two levels of internal oxidation were studied in this work. Crack length versus number of cycles and crack growth rate versus mean crack length were obtained as principal results. Shot peening from 30 minutes to one hour, tempering at 160#176C and a lO~m depth of internal oxidation showed the best results in fatigue life.

Effects of mould flux contaminant on scale-steel adhesion and hydraulic descaling of scale formed on slabs were investigated. In this investigation, stainless steel type 304 (austenitic with 18% Cr and 8% Ni) and specific mould fluxes were used when growing the scale on contaminated samples under simulated industrial reheating conditions, with subsequent high pressure water hydraulic descaling. The basic hypothesis was that the steel-scale adhesion depends on the microstructure of different phases present in the scale, the segregation of specific elements at the interface and the interfacial morphology of the scale after reheating. It was found that mould flux contaminant decreases scale-steel adhesion and therefore improved the descaling effectiveness significantly compared to non contaminated stainless steel. The descaling effectiveness of contaminated and uncontaminated slab was dependent to the presence of metal free paths (chromite layers along the austenite grains boundaries) and the presence of unoxidized metal in the scale due to nickel enrichment at the interface. Compared to the uncontaminated samples, the descaling of contaminated samples was efficient which could be due to the fact that some mechanisms which increase scale– steel adhesion (notably nickel enrichment at the interface) were considerably reduced. For all contaminated samples, the descaling effectiveness after visual observation were close to 100% and it was found that mould flux type 832 ( low basicity) gave a high descaling efficiency with better steel surface quality after descaling compared to mould fluxes type 810 and RF1. / Dissertation (MSc)--University of Pretoria, 2009. / Materials Science and Metallurgical Engineering / unrestricted

In this study, the possibility of using low pressure hydrogenated steam to simulate primary water reactor conditions is examined. The oxides formed on Alloy 600 (WF675) between 350 Celsius and 500 Celsius in low pressure hydrogenated steam (with a ratio of oxygen at the Ni/NiO to oxygen in the system of 20) have been characterised using analytical electron microscopy (AEM) and compared to oxide that formed in a high pressure water in a autoclave at 350 Celsius with 30 cc/kg of hydrogen. Preferential oxidation of grain boundaries and bulk internal oxidation were observed on samples prepared by oxide polishing suspension (OPS). Conversely, samples mechanically ground to 600 grit produced a continuous, protective oxide film which suppressed the preferential and internal oxidation. The surface preparation changed the form of the oxides in both steam and autoclave tests. The preferential oxidation rate has been determined to be K_{oxide} = Aexp{-Q/RT}with A = 2.27×10^(−3) m^(2)s^(−1) and Q = 221 kJ.mol^(−1) (activation energy) for WF675 and A = 5.04 × 10^(−7) m^(2)s^(−1) and Q = 171 kJ.mol^(−1) for 15% cold worked WF675. These values are consistent with the activation energy of primary water stress corrosion cracking (PWSCC) initiation. Bulk oxygen diffusivities were calculated from the internal oxidation after 500 h exposures. At 500 Celsius the oxygen diffusivity was determined to be 1.79×10^(−20) m^(2)s^(−1) for WF675 and 1.21×10^(−20) m^(2)s^(−1) for 15% cold worked WF675, the oxygen diffusivity at 400 Celsius in 15% cold worked WF675 was calculated to be 1.49×10^(−22) m^(2)s^(−1).The Cr-depletion associated with preferential oxidation has been assessed by AEM. The Cr-depletion was asymmetric and it could not be accounted for by local variations in the diffusion rate. Chemically induced grain boundary migration is suggested as a possible explanation. Constant load SCC tests conducted in hydrogenated steam at 400 Celsius have shown a similar trend to the classical dependency of PWSCC as a function of potential. The SCC samples were also prepared with two surface finishes, OPS and 600 grit. In all SCC tests, significantly more cracking was observed on the OPS surface and all failures initiated from this surface.