Spinodal decomposition is a phenomenon which hinders the usage of ferrite containing steels under certain conditions. With a better understanding and knowledge of spinodal decomposition new ferritic and duplex stainless steels could be designed. The project is divided into two parts, an experimental part and a theoretical part. The aim of the theoretical part was to compare simulated values of the amplitude and wavelength of spinodal decomposition, obtained from solving the Cahn-Hilliard equation with other experimental values. The experimental part is performed as to determine the chemical diffusion coefficient and the mobility of Fe and Cr in the binary Fe-Cr system for lower temperatures using the Boltzmann-Matano method from chemical profiles of different samples. Another purpose with the project is to determine if the methods and the approach which are taken is viable and useful for calculating diffusion coefficients and if it can be used in studies to come. The simulations were in good agreement with other data at higher time intervals, but deviates at lower times. The calculated interdiffusion coefficients were in all cases lower than the expected values and as such the conclusion that is drawn is that the methods which are used could need further development. / Spinodalt sönderfall är ett fenomen som hindrar användningen av stål som innehåller ferrit under vissa förutsättningar. Med en större förståelse och mer kunskap om spinodalt sönderfall så kan nya ferritiska och duplexa rostfria stål utformas. Projektet är uppdelat i två delar, en experimentell del och en teoretisk del. Syftet med den teoretiska delen var att jämföra simulerade värden av amplituden och våglängden för spinodalt sönderfall, vilka erhölls från att lösa Cahn-Hilliard ekvationen med andra experimentella värden. Den experimentella delen utförs för att bestämma kemiska diffusionskoefficienter för Fe och Cr i det binära Fe-Cr system för lägre temperaturer med hjälp av Boltzmann-Matano metod från kemiska profiler av olika prover. Ett annat syfte med projektet är att ta reda på om de metoder och tillvägagångssätt som tas är livskraftiga och användbara för beräkning av diffusionskoefficienter och om den kan användas i studier framöver. Simuleringarna var i god överensstämmelse med annan experimentel data vid högre tidsintervall, men avviker vid lägre tider. De beräknade Interdiffusion koefficienterna var i samtliga fall lägre än de förväntade värdena och som sådan, dras slutsatsen att de metoder som används kan förbättras.

The following dissertation is divided into two parts. Part I deals with the modeling of helium trapping at oxide-iron interfaces in nanostructured ferritic alloys (NFAs) using density functional theory (DFT). The modelling that has been performed serves to increase the knowledge and understanding of the theory underlying the prevention of helium embrittlement in materials. Although the focus is for nuclear reactor materials, the theory can be applied to any material that may be in an environment where helium embrittlement is of concern. In addition to an improved theoretical understanding of helium embrittlement, the following DFT models will provide valuable thermodynamic and kinetic information. This information can be utilized in the development of large-scale models (such as kinetic Monte Carlo simulations) of the microstructural evolution of reactor components. Accurate modelling is an essential tool for the development of new reactor materials, as experiments for components can span decades for the lifetime of the reactor. Part II of this dissertation deals with the development, and use of, kinetic Monte Carlo (KMC) simulations for improved efficiency in investigating catalytic chemical reactions on surfaces. An essential technique for the predictive development and discovery of catalysts relies on modelling of large-scale chemical reactions. This requires multi-scale modelling where a common sequence of techniques would require parameterization obtained from DFT, simulation of the chemical reactions for millions of conditions using KMC (requiring millions of separate simulations), and finally simulation of the large scale reactor environment using computational fluid dynamics. The tools that have been developed will aid in the predictive discovery, development and modelling of catalysts through the use of KMC simulations. The algorithms that have been developed are versatile and thus, they can be applied to nearly any KMC simulation that would seek to overcome similar challenges as those posed by investigating catalysis (such as the need for millions of simulations, long simulation time and large discrepancies in transition probabilities). / Ph. D.

Os aços inoxidáveis ferríticos são susceptíveis à corrosão intergranular após resfriamento rápido a partir de 950°C. A teoria de empobrecimento no teor de cromo nas vizinhanças do carboneto e/ou nitreto, precipitados nos contornos de grão, é o mecanismo mais aceito para descrever este fenômeno. O presente trabalho avalia o efeito dos tratamentos isotérmicos na resistência à corrosão intergranular do aço inoxidável ferrítico UNS S43000, utilizando o método de reativação eletroquímica potenciodinâmica na versão ciclo duplo (DL-EPR). As amostras foram solubilizadas a 1200°C e posteriormente tratadas isotermicamente a temperaturas entre 500°C e 700°C, por tempos de 5 minutos a 16 horas. O ensaio DL-EPR foi realizado em solução 0,5M H2SO4 com velocidade de varredura de 1,67 mV/s. As amostras foram examinadas em microscópio óptico e microscópio eletrônico de varredura após ensaio DL-EPR, Práticas W e X da norma ASTM A763 e ataque metalográfico com reagente Vilella. Foram obtidos diferentes valores de grau de sensitização em função do tempo de tratamento isotérmico. Análises por difração de raios X, sobre resíduos extraídos quimicamente identificaram precipitação de nitretos e de carbonetos de cromo, Cr2N e Cr23C6, respectivamente. As temperaturas de 550°C e 600°C mostraram dois máximos de grau de sensitização em função do tempo, por isso este processo de sensitização foi denominado de dupla sensitização. A partir dos resultados obtidos: grau de sensitização DL-EPR, exame microestrutura e difração de raios X, o presente trabalho propõe o seguinte mecanismo para explicar a dupla sensitização: (Etapa 1) no resfriamento da temperatura de solubilização são precipitados nos contornos de grão fases ricas em cromo; (Etapa 2) os tratamentos isotérmicos geram uma fina precipitação de Cr2N nos contornos de grão sobre os precipitados formados na Etapa 1; (Etapa 3) esses precipitados são posteriormente dissolvidos o que permite (Etapa 4) uma nova precipitação de Cr2N e Cr23C6 nos contornos de grão e (Etapa 5) finalmente temse o processo de crescimento, coalescimento e recuperação final. A recuperação total da resistência à corrosão intergranular foi obtida após tratamentos isotérmicos realizados a 650°C por tempos maiores que 20 minutos e a 700°C a partir de 5 minutos. O trabalho confirma que tanto os fenômenos de precipitação, sensitização e recuperação são controlados 5 pela difusão do cromo na ferrita. Tal confirmação foi possível a partir de análises da solução da segunda lei de Fick e gráficos de Arrhenius, construídos a partir do ensaio DL-EPR e dos exames microestruturais, os quais indicaram uma energia de ativação de precipitação com valor de 255 kJ/mol (219 kJ/mol é o valor da energia de ativação para difusão do cromo na ferrita encontrado em literatura (ARAI; TAKEDA; ARATA, 1987; WOLFE; PAXTON, 1964)). / Ferritic stainless steels are prone to intergranular corrosion following quick cooling from 950°C. The explanation based on chromium impoverishment near the carbides and/or nitrides precipitated in the grain boundaries is the most accepted to describe the observations. This work study the effects of heat treatments on the resistance to intergranular corrosion of the UNS S43000 ferritic stainless steel, using the Double Loop Electrochemical Potentiodynamic Reactivation test (DL-EPR). Specimens have been solution annealed at 1200oC followed by isothermical holding at temperatures between 500°C and 700°C, for times of 5min up to 16h. The DL-EPR test was made in a 0,5M H2SO4 solution using scan rate of 1,67 mV/s. The specimens were observed by optical microscope and scanning electron microscope after DLEPR test, Practices W and X (ASTM A763) and metallographic etch with Vilella reagent. Different degrees of sensitization were obtained for different isothermal holding time. X rays diffraction of extracted precipitates identified chromium nitrides and chromium carbides, Cr2N and Cr23C6. The temperatures of 550°C and 600°C produced two maxima in the curves of degree of sensitization as function of time; the process was named double sensitization. From the results of degree of sensitization DL-EPR, microstructural examination and X rays diffraction, this work proposes the following mechanism to explain double sensitization: (1st stage) during cooling from the solution annealing temperature there is grain boundary precipitation of chromium rich phases; (2nd stage) the isothermal treatments produce a fine grain boundary precipitation of Cr2N on the precipitates formed in the 1st stage; (3rd stage) increasing the time, these precipitates are dissolved, allowing for a (4th stage) new grain boundary precipitation of Cr2N e Cr23C6; finally (5th stage) there is growth, coalescence and recovery. Total recovery of intergranular corrosion resistance was achieved, isothermically at 650°C for times longer than 20min and at 700°C for times longer then 5min. Precipitation, sensitization and recovery are controlled by diffusion of chromium in ferrite. This conclusion was based on analysis of solution of Fick’s second law and Arrhenius plots constructed with DL-EPR data and microstructural observations. The calculus of the experimental energy of activation for precipitation produced a value of 255kJ/mol (energy of activation for chromium 7 diffusion in the ferrite reported by Arai, Takeda and Arata (1987) and Wolfe and Paxton (1964) is 219kJ/mol).

Pesquisas sobre a tenacidade à fratura dos aços ferríticos mostram uma grande dispersão dos resultados quando avaliados na região de transição dúctil-fragil. Esta dispersão é fortemente influenciada pela temperatura de ensaio, dimensões e geometria dos corpos-de-prova e também pelo nível de restrições plástica na ponta da trinca. Tais fatores dificultam a previsão, a partir de valores experimentais, de valores de tenacidade à fratura de aços ferríticos para aplicações em casos práticos. Uma forma de contornar essa dificuldade é através do uso das curvas de referencia, descritas no Código ASME. Estas curvas representam envoltórias inferiores de tenacidade à fratura obtida a partir de ensaios envolvendo diversos tipos de aços. Portanto os valores de tenacidade estabelecidos por essas curvas são, em geral, muito conservadores. Então foi proposta pela ASTM uma nova metodologia, chamada curva Mestra, que trata estatisticamente o comportamento à fratura dos aços ferríticos na região de transição e caracteriza um material em particular, através de um parâmetro denominado Temperatura de Referencia (T0). Nesta pesquisa, avaliou-se a influencia da sensibilidade dos parâmetros: Kmin, m e M envolvidos no procedimento do calculo de um parâmetro denominado temperatura de referencia. (T0). A metodologia da curva mestra foi aplicada através dos dados (experimentos) do euro-teste , para as temperaturas: -91 ºC, -60°C, -40°C e 20°C . Em análises de sensibilidade aos parâmetros com os seguintes valores kmin = 0, 10, 30; m= (3), (3,5), (4,5), (5,0) e M = 40, 50, 60. Os resultados apresentados são compatíveis comprovando a eficiência da metodologia para avaliação da tenacidade à fratura dos aços ferríticos na região de transição. Portanto, nestas condições, podemos afirmar que o conceito da curva mestra foi, realmente validado. / The caracterization of the fracture behavior in the ductile-to-brittle transition for ferritic steels is a hard task because fracture toughness is a strong function of temperature in the transition, with the toughness values increasing rapidly over a relatively narrow temperature baud/range and therefore cannot be easily used to evaluate integrity in structural components because of the uncertainty in how to handle these teste results. To overcome this problem in practice, the ASME code has provided reference curves that give estimates of toughness versus temperature. These curves represent lower envelopes to a large set of fracture toughness experimental data for several heats of steel . Therefore, the fracture toughness values obtained from these curves are in general too conservative. In the last decade, a new methodology, formalized in the ASTM standard method E1921-97, has revolutionized the approach used to caracterize transition fracture behavior and has given a rationale for treating the several factors that influence the scatter in the results. Statistical models are used to define a transition curve, called Master Curve, and the transition temperature of a given material is stated by a parameter called reference temperature (T0). In this research, it was evaluated the sensitivity influence of the parameter: Kmin, m and M, involved in the to measurement procedure. The master curve methodology was applied over the data (experiments) of EuroTest for the following temperatures: - 91°C, -60°C, -40°C and -20°C. A parameters sensitivity analysis was made with following values: Kmin=0, 10, 30; m=(3), (3,5), (4,5), (5,0) and M=40, 50, 60. The results are compatible, which confirm the efficiency of the methodology for evaluating the toughness to ferritic steel fracture in the transition region. Therefore, in these conditions, we can state the master curve concept has indeed been validated.

Les aciers inoxydables ferritiques stabilisés, aussi performants dans de nombreux domaines et moins chers que les aciers inoxydables austénitiques, souffrent cependant d’une formabilité inférieure (mise en forme + défaut de chiffonnage / roping). Il convient donc d’optimiser les microstructures et textures finales de ces produits, ce qui passe entre autres par une meilleure connaissance de l’évolution du matériau durant le laminage à chaud (LAC).Des essais de bipoinçonnement effectués sur une machine Gleeble®, simulant la compression plane à cœur du matériau durant le LAC, ont permis de simuler des schémas de laminage mono et multipasses. Les effets de la déformation, de la température, de la vitesse de déformation, de la taille de grains initiale et de la composition chimique sur les évolutions dynamiques (durant une passe de laminage) et post-dynamiques (durant un temps interpasse) ont été investigués.Une passe de LAC fragmente la microstructure en cristallites par recristallisation dynamique continue (RDC). Une partie de ces cristallites deviendront les germes de la recristallisation post-dynamique (RPD) au cours du temps interpasse. Celui-ci se caractérise par la simultanéité d’activation de nouveaux germes, de la croissance de grains recristallisés au sein de zones écrouies mais également au détriment d’autres grains recristallisés.Le couplage d’un modèle de RDC existant avec un modèle de RPD créé à partir des observations expérimentales, permet de simuler des schémas de LAC multipasses et de retranscrire les effets de la majorité des paramètres opératoires. / Stabilized ferritic stainless steels are as efficient as austenitic stainless steels in many areas and less expensive. However, they suffer from a lower formability (forming + roping defect). It is therefore necessary to optimize the final microstructures and textures of these products, which requires in particular a better understanding of the evolution of the material during hot rolling.Plane strain compression tests carried out on a Gleeble® machine, reproducing the deformation during hot rolling in the center of the material, permitted to perform single- and multi-pass rolling schedules. The effects of deformation, temperature, strain rate, initial grain size and chemical composition on dynamic (during a rolling pass) and post- dynamic (during an inter-pass time) evolutions were investigated.A hot rolling pass fragments the microstructure and creates crystallites by continuous dynamic recrystallization (CDRX). A part of these crystallites becomes nuclei for the post-dynamic recrystallization (PDRX) during inter-pass time. The latter is characterized by the simultaneous activation of new nuclei and growth of recrystallized grains, not only within strain-hardened zones but also at the expense of other grains already recrystallized.The coupling of an existing CDRX model with a PDRX model based on experimental results allows to simulate multi-pass hot rolling schedules and to reproduce the effects of most of the operating parameters.

AgÃncia Nacional do PetrÃleo / Os elevados teores de enxofre dos petrÃleos processados nas unidades de refino atacam o âcladâ de aÃo AISI 405 ou 410S, expondo o aÃo estrutural ao meio corrosivo. A recuperaÃÃo da regiÃo desgastada à feita pela aplicaÃÃo de um âliningâ de aÃo AISI 316L. Embora o aÃo AISI 316L garanta uma boa resistÃncia à corrosÃo naftÃnica, surgem trincas na zona afetada pelo calor da solda ( ZAC) apÃs um determinado perÃodo de operaÃÃo da unidade, associadas a problemas metalÃrgicos na ZAC e aos esforÃos de dilataÃÃo e contraÃÃo do conjnto âliningâ e parede da torre. Uma alternativa seria a aplicaÃÃo de um âliningâ de aÃo AISI 444 que tem resistÃncia à corrosÃo comparÃvel à do aÃo AISI 316L e coeficiente de expansÃo tÃrmica mais prÃximo do coeficiente do prÃprio material da torre. Contudo, ainda nÃo sÃo conhecidos os efeitos sobre o desempenho deste aÃo nas condiÃÃes de operaÃÃo da torre. Assim, neste trabalho estudou-se a viabilidade da aplicaÃÃo de um âliningâ de aÃo AISI 444 para a recuperaÃÃo da torre de destilaÃÃo em substituiÃÃo ao aÃo AISI 316L. Para tanto, foram avaliadas as condiÃÃes de fragilizaÃÃo do aÃo AISI 444 na temperatura mÃxima da torre ( em torno de 400ÂC) e na temperatura de 475ÂC, atravÃs da mediÃÃo da dureza Brinell e do ensaio de impacto Charpy-V. Corpos de prova de aÃo AISI 444 e AISI 316L soldados sobre chapas de aÃo ASTM A516 Gr60 foram submetidos a ciclos de Fadiga TÃrmica e, apÃs cada ciclo (20 ao todo), passaram por uma inspeÃÃo para verificar a existÃncia de trincas. Logo apÃs foi feita a caracterizaÃÃo microestrutural da ZAC. TambÃm foram retiradas amostras apÃs os ensaios de Fadiga TÃrmica para serem submetidas a tratamentos em petrÃleo na temperatura de 300 C. ApÃs o tratamento em petrÃleo, as amostras passaram por uma avaliaÃÃo no microscÃpio eletrÃnica de varredura. Foram medidas as massas dos corpos de prova antes e apÃs o tratamento em petrÃleo para determinar a perda de massa provocada pelo ambiente corrosivo. Os resultados indicam que a submissÃo do aÃo AISI 444 ao tratamento tÃrmico, nas temperaturas de 400 a 475ÂC, causa a fragilizaÃÃo do mesmo e um aumento da temperatura de transiÃÃo dÃctil frÃgil para valores acima de 30 C, mas abaixo de 60 C. Os aÃos AISI 316L e AISI 444 nÃo apresentam trincas apÃs os ensaios de Fadiga TÃrmica e nem apÃs o tratamento em petrÃleo. O uso do aÃo AISI 444 pode representar uma reduÃÃo nos custos nas paradas das torres de destilaÃÃo uma vez que este apresentou menores taxas de corrosÃo que o aÃo AISI 316L. / Os elevados teores de enxofre dos petrÃleos processados nas unidades de refino atacam o âcladâ de aÃo AISI 405 ou 410S, expondo o aÃo estrutural ao meio corrosivo. A recuperaÃÃo da regiÃo desgastada à feita pela aplicaÃÃo de um âliningâ de aÃo AISI 316L. Embora o aÃo AISI 316L garanta uma boa resistÃncia à corrosÃo naftÃnica, surgem trincas na zona afetada pelo calor da solda ( ZAC) apÃs um determinado perÃodo de operaÃÃo da unidade, associadas a problemas metalÃrgicos na ZAC e aos esforÃos de dilataÃÃo e contraÃÃo do conjnto âliningâ e parede da torre. Uma alternativa seria a aplicaÃÃo de um âliningâ de aÃo AISI 444 que tem resistÃncia à corrosÃo comparÃvel à do aÃo AISI 316L e coeficiente de expansÃo tÃrmica mais prÃximo do coeficiente do prÃprio material da torre. Contudo, ainda nÃo sÃo conhecidos os efeitos sobre o desempenho deste aÃo nas condiÃÃes de operaÃÃo da torre. Assim, neste trabalho estudou-se a viabilidade da aplicaÃÃo de um âliningâ de aÃo AISI 444 para a recuperaÃÃo da torre de destilaÃÃo em substituiÃÃo ao aÃo AISI 316L. Para tanto, foram avaliadas as condiÃÃes de fragilizaÃÃo do aÃo AISI 444 na temperatura mÃxima da torre ( em torno de 400ÂC) e na temperatura de 475ÂC, atravÃs da mediÃÃo da dureza Brinell e do ensaio de impacto Charpy-V. Corpos de prova de aÃo AISI 444 e AISI 316L soldados sobre chapas de aÃo ASTM A516 Gr60 foram submetidos a ciclos de Fadiga TÃrmica e, apÃs cada ciclo (20 ao todo), passaram por uma inspeÃÃo para verificar a existÃncia de trincas. Logo apÃs foi feita a caracterizaÃÃo microestrutural da ZAC. TambÃm foram retiradas amostras apÃs os ensaios de Fadiga TÃrmica para serem submetidas a tratamentos em petrÃleo na temperatura de 300 C. ApÃs o tratamento em petrÃleo, as amostras passaram por uma avaliaÃÃo no microscÃpio eletrÃnica de varredura. Foram medidas as massas dos corpos de prova antes e apÃs o tratamento em petrÃleo para determinar a perda de massa provocada pelo ambiente corrosivo. Os resultados indicam que a submissÃo do aÃo AISI 444 ao tratamento tÃrmico, nas temperaturas de 400 a 475ÂC, causa a fragilizaÃÃo do mesmo e um aumento da temperatura de transiÃÃo dÃctil frÃgil para valores acima de 30 C, mas abaixo de 60 C. Os aÃos AISI 316L e AISI 444 nÃo apresentam trincas apÃs os ensaios de Fadiga TÃrmica e nem apÃs o tratamento em petrÃleo. O uso do aÃo AISI 444 pode representar uma reduÃÃo nos custos nas paradas das torres de destilaÃÃo uma vez que este apresentou menores taxas de corrosÃo que o aÃo AISI 316L. / The high sulfur content of oil processed in the refining units attack the "clad" steel AISI 405 or 410S, exposing the structural steel to the corrosive medium. The recovery of the eroded region is made by applying a "lining" of AISI 316L steel. Although steel AISI 316L ensure good corrosion resistance naphthenic, cracks appear in the heat affected zone of the weld (HAZ) after a certain period of operation of the unit, metallurgical problems associated with the HAZ and the efforts of expansion and contraction of conjnto " lining "of the tower and wall. An alternative would be the application of a "lining" of AISI 444 steel having corrosion resistance comparable to the AISI 316L steel and the thermal expansion coefficient closer to the coefficient of the material itself of the tower. However, are not yet known effects on the performance of the steel in the conditions of operation of the tower. In this work we studied the feasibility of applying a "lining" steel AISI 444 for the recovery of the distillation tower to replace the steel AISI 316L. Thus, we evaluated the conditions of embrittlement of AISI 444 in the maximum temperature of the tower (about 400  C) and temperature of 475  C, by measuring the Brinell hardness and Charpy impact test-V. Specimens of AISI 444 and AISI 316L welded onto steel plates ASTM A516 Gr60 were subjected to thermal fatigue cycles and after each cycle (20 in all), passed an inspection to check for cracks. Soon after it was made microstructural characterization of ZAC. Also samples were taken after the thermal fatigue tests in order to undergo treatment in oil at a temperature of 300  C. After treatment in oil, the samples underwent an evaluation in the scanning electron microscope. Were measured masses of the samples before and after treatment in oil to determine the weight loss caused by the corrosive environment. The results indicate that the subjection of the AISI 444 steel to thermal treatment at temperatures 400-475  C, causes embrittlement of the same and increasing the temperature of transition ductile brittle to values ​​above 30  C but below 60  C. The AISI 316L and AISI 444 do not exhibit cracks after the tests and Thermal Fatigue or after treatment in oil. The use of steel AISI 444 may represent a cost savings in the charts of distillation towers since it showed the lowest corrosion rates than steel AISI 316L. / The high sulfur content of oil processed in the refining units attack the "clad" steel AISI 405 or 410S, exposing the structural steel to the corrosive medium. The recovery of the eroded region is made by applying a "lining" of AISI 316L steel. Although steel AISI 316L ensure good corrosion resistance naphthenic, cracks appear in the heat affected zone of the weld (HAZ) after a certain period of operation of the unit, metallurgical problems associated with the HAZ and the efforts of expansion and contraction of conjnto " lining "of the tower and wall. An alternative would be the application of a "lining" of AISI 444 steel having corrosion resistance comparable to the AISI 316L steel and the thermal expansion coefficient closer to the coefficient of the material itself of the tower. However, are not yet known effects on the performance of the steel in the conditions of operation of the tower. In this work we studied the feasibility of applying a "lining" steel AISI 444 for the recovery of the distillation tower to replace the steel AISI 316L. Thus, we evaluated the conditions of embrittlement of AISI 444 in the maximum temperature of the tower (about 400  C) and temperature of 475  C, by measuring the Brinell hardness and Charpy impact test-V. Specimens of AISI 444 and AISI 316L welded onto steel plates ASTM A516 Gr60 were subjected to thermal fatigue cycles and after each cycle (20 in all), passed an inspection to check for cracks. Soon after it was made microstructural characterization of ZAC. Also samples were taken after the thermal fatigue tests in order to undergo treatment in oil at a temperature of 300  C. After treatment in oil, the samples underwent an evaluation in the scanning electron microscope. Were measured masses of the samples before and after treatment in oil to determine the weight loss caused by the corrosive environment. The results indicate that the subjection of the AISI 444 steel to thermal treatment at temperatures 400-475  C, causes embrittlement of the same and increasing the temperature of transition ductile brittle to values ​​above 30  C but below 60  C. The AISI 316L and AISI 444 do not exhibit cracks after the tests and Thermal Fatigue or after treatment in oil. The use of steel AISI 444 may represent a cost savings in the charts of distillation towers since it showed the lowest corrosion rates than steel AISI 316L.

The need to develop light-weight and high strength materials for car frames which improve fuel efficiency and provide increased passenger safety during dynamic events such as automobile crashes has been the focus of the steel and automobile industries for the past 30 years. In recent years, the development of high strength steels such as multi-phase TRIP (Transformation-Induced Plasticity)-aided steels have shown great promise due to their excellent combination of high strength and ductility. The savings in automobile weight is provided by the inherent strength of TRIP steels which allows for the use of thinner sections. The TRIP effect is characterized by the phenomenon known as strain-induced martensitic transformation (SIMT) which enhances the work hardenability of such steels as the austenite phase transforms to the much harder martensite phase during plastic straining. This results in a resistance to local necking which subsequently enhances the strength, ductility, and formability of such steels. However, various factors exist which affect the mechanical behaviour of TRIP steels. This study will aim, through the use of finite element models, to investigate the role and influence of each of these factors on the TRIP effect in type 304 austenitic and multi-phase TRIP steels. These factors include the rate at which the martensitic transformation proceeds, the state of stress to which the material is subjected to, the interaction between the surrounding matrix and embedded retained austenite islands in multi-phase TRIP steels, and the volume fraction and morphology of the retained austenite islands. Investigation of these factors will provide further insight on each of their contributions to the TRIP effect in order to exploit the potential benefits offered by these steels.

Ferritic superalloys strengthened by coherent ordered NiAl B2-type precipitates are promising candidates for ultra-supercritical steam-turbine applications, due to their superior resistance to creep, coarsening, oxidation, and steam corrosion as compared to Cr ferritic steels at high temperatures. Combined computational and experimental tools have been employed to investigate the interrelationships among the composition, microstructure, and mechanical behavior, and provide insight into deformation micromechanisms at elevated temperatures. Self and impurity diffusivities in a body-centered-cubic (bcc) iron are calculated using first-principles methods. Calculated self and impurity diffusivities compare favorably with experimental measurements in both ferromagnetic and paramagnetic states of bcc Fe. The calculated impurity diffusivities of W and Mo are larger than the self diffusivity of Fe, mainly owing to the lower activation energies. The microstructural attributes of NiAl-type B2 precipitates are investigated in several designed ferritic superalloys. Ultra-small-angle X-ray scattering in conjunction with transmission electron microscopy is employed to quantify the average size, size distribution, inter-particle spacing, and volume fraction of the primary precipitates. It is observed that as the Al amount increases from 4 to 10 mass%, there is a decrease in the average inter-particle spacing and average particle diameter. An alloy with 6.5 weight percent Al exhibits the optimal creep resistance and an associated maximum Orowan stress at 973 K. The dislocations-particle interaction mode during the secondary creep regime is identified as a combination of Orowan looping and dislocation climb. In-situ neutron diffraction experiments during tensile and creep deformations reveal the intergranular and interphase load-sharing mechanisms during plastic deformation at elevated temperatures. The change of deformation mechanisms from dislocation slip below 773 K to power-law creep above 873 K is well captured by the evolution of the different lattice strains. High-temperature deformation above 873 K is possibly assisted by the relaxation processes, e.g., grain-boundary sliding and/or diffusional flow along grain boundaries and matrixparticle interfaces. The evolution of lattice strains during high-temperature deformation is further verified by crystal-plasticity finite-element simulations. The significant findings in the present work provide the crucial baseline information for further alloy optimization and improvement in high-temperature creep resistance of ferritic superalloys.

Compared to more common used austenitic stainless steels, ferritic stainless steels contain very low amounts of the expensive alloying element Ni. In addition, they have good corrosion properties, but are sometimes suffering from poor weldability and bad mechanical properties. This is mainly due to the presence of large grains after casting and large grain growth during heat treatment or welding. Processes for reducing the grain size (grain refining) of metal alloys are widely known and proven before to be suitable for many alloys. A successful grain refining process can increase the strength of an alloy without decreasing the ductility. This can be achieved by different methods, such as rolling or cooling. In this work, the focus has been on studying the aspect from a metallurgist point of view, to analyse the possibilities to create small particles in the liquid stage to enhance the solidification. The focus has been on oxide and nitride formation for nucleation of smaller grains during solidification. This study was made by forming particles, develop the analysis methods and thereafter to study the effect of particles on the structure of a ferritic stainless steel. The particles were formed by additions of Ti, Ce and Zr in to a liquid Fe-20mass% Cr alloy containing different amounts of oxygen and nitrogen. The electrolytic extraction technique was used to achieve a good understanding of the reaction processes and the particles size, number, composition and morphology. The grain sizes and the particles were then studied in as-cast samples as well as in specimens heat treated for 60 minutes at 1200, 1300 and 1400°C in a Confocal Scanning Laser Microscope (CSLM). Also, based on Scanning Electron Microscope (SEM) determinations and Thermo-Calc calculations, the precipitated particles were divided as primary and secondary particles. Thereafter, the grain refining potential was studied for each of these types. In this work, particles engineering by using small particles have been proven suitable for the Fe-20mass% Cr ferritic stainless steel alloys. Although the work has been based on small-scale samples and experiments, the results show good tendencies with respect to grain refining as well as a clear relationship between the particles in the steels and the microstructures. It was found that Ti-Ce additions in Fe-20mass% Cr alloys resulted in complex oxides including Ti, Ce and Cr. These oxides were observed to have high agglomeration tendencies and therefore to form larger particles or clusters. The grain refining potential on the solidification structure was insignificant, despite a relatively large amount of particles. However, Ti-Zr additions in Fe- 20mass% Cr alloys on the other hand resulted in primary precipitated particles such as ZrO2 and ZrO2+ZrN. Furthermore, ZrN nucleated ferrite during solidification, which lead to a clearly observed grain refining effect. This effect was also increased with an increased number of particles. The amount of particles (primary and secondary) was also found to increase with an increased amount of nitrogen. Secondary particles (mostly TiN) were precipitated near grain boundaries, which lead to a location based pinning effect of the grain growth during heat treatment at 1200 °C. This pinning effect was increased by an increased nitrogen content and thereby an increased number of particles. Finally, the pinning effect was clearly reduced during heat treatment at 1400 °C. / QC20100524

The ageing state of the world's nuclear power infrastructure, and the need to reduce humanity s dependency on fossil fuels, requires that this electrical energy generating capacity is replaced. Economic factors, and its physical and chemical properties, make high purity iron-chromium binary alloys a strong candidate for use in the construction of the pressure vessels of the next generation of nuclear reactors. This relatively inexpensive metal retains the oxidation resistance property of so-called stainless steel alloys, and has demonstrated dimensional stability and low degradation under harsh experimental environments of temperature and radiation. In this work, we consider radiation induced interstitial damage to the atomic lattices of iron-chromium binary alloys using the atomistic modelling methods, Molecular Dynamics and Adaptive Kinetic Monte Carlo, simulating collision cascade sequences, and the migration of defects in the aftermath. Variations in chromium content does not effect the initial damage production in terms of the number of Frenkel pairs produced, but iron and chromium atoms are not evenly distributed in defect atoms with respect to the bulk concentration. In simulations conducted at low temperature, chromium is under-represented, and at high temperature, a greater proportion of interstitial atoms are chromium than in the lattice overall. The latter phenomena is most strongly pronounced in systems of low bulk chromium content. During the simulation of post-cascade defect migration, interstitials atoms are observed to form temporary clusters and vacancies align along adjacent lattice sites, with the two types of defect also migrating to annihilate by recombination. Calculating the energy spectra of cascade events corresponding to an example experimental configuration using the SRIM package, we investigated the evolution of lattice systems in which a sequence of multiple cascade events occurred, both with and without a physically representative time gap between events. These simulations gave us the opportunity to observe the behaviour of cascades in the proximity of damage remaining from previous events, such as the promotion of defect clustering when this occurs.