Uma previsão razoável da durabilidade de estruturas ou equipamentos que operam em temperaturas elevadas e atmosferas agressivas requer um completo entendimento dos mecanismos de degradação dos materiais causados por cargas mecânicas e corrosão. O objetivo geral desse estudo é simular processos de corrosão em temperaturas elevadas em condições próximas àquelas encontradas na realidade. Isto requer um modelo termodinâmico para prever a estabilidade das fases e um modelamento matemático que descreva os processos cinéticos, por exemplo, difusão no estado sólido - difusão no interior do grão e ao longo dos contornos de grão. Um programa computacional foi desenvolvido para descrever a oxidação interna, nitretação e sulfetação de várias ligas comerciais. O subprograma termodinâmico ChemApp foi integrado em um modelo numérico que usa o método de diferenças finitas. O modelo desenvolvido simula processos de corrosão interna que são controlados por difusão no estado sólido e que envolvam precipitação de várias fases. Formação de zona de corrosão interna, incluindo corrosão intercristalina em aços contendo baixo teor de Cr, é também tratada pelo modelo computacional desenvolvido. Nesse artigo, são consideradas soluções diluídas e monofásicas.

A reasonable prediction of the service life of structures or equipment operating at high-temperatures in aggressive atmospheres requires a full understanding of the degradation mechanisms of the material due to mechanical loading and corrosion. The overall objective of this study is to simulate high-temperature corrosion processes under near-service conditions, which require both, a thermodynamic model to predict phase stabilities for given conditions and a mathematical description of the kinetic process, i.e., solid state diffusion. A computer program was developed in which the thermodynamic program library ChemApp is integrated into a numerical finite-difference diffusion calculation to treat internal oxidation, nitridation and sulfidization processes in various commercial alloys. The model is capable of simulating multi-phase internal corrosion processes controlled by solid-state diffusion into the bulk metal as well as intergranular corrosion occurring in low-alloy steels by fast inward oxygen transport along the grain boundaries of the substrate. In this article, dilute and monophase solutions are considered.

O objetivo deste artigo é introduzir uma ferramenta para simulação computacional, capaz de prever a vida útil de componentes que operam em condições corrosivas tais como oxidação, nitretação e carbonetação em temperaturas elevadas. Diferentes classes de materiais (aços ferríticos, aços austeníticos e ligas de níquel) foram expostas a diferentes atmosferas e temperaturas. O software desenvolvido para simulação de corrosão interna em temperaturas elevadas utiliza a técnica numérica de diferenças finitas para descrever a cinética de corrosão e o conceito de equilíbrio termodinâmico local para tratar a estabilidade das fases. Para isto, um link entre o ambiente MATLAB e a sub-rotina termoquímica ChemApp foi criado. Usando esta ferramenta, cinéticas de oxidação, nitretação e carbonetação foram calculadas levando em consideração a microestrutura das ligas, distinguindo precipitação no interior do grão e no contorno do grão. Foi observada uma excelente correlação entre os resultados experimentais e aqueles obtidos através de simulação computacional.

The aim of this paper is to introduce a computer simulation tool, which is designed for prediction of service-life of components operating under corrosive conditions such as carburization, oxidation and nitridation at high-temperature. Different classes of materials (low-Cr ferritic steels, austenitic steels and Ni-base superalloys) were exposed at temperatures between 550 ºC and 1000 ºC to different corrosive atmospheres (carburizing, oxidizing and nitriding). The tool for the prediction of internal/inwards corrosion processes at high-temperatures makes use of the numerical finite-difference technique to treat diffusional kinetics on the one hand and the concept of local equilibrium thermodynamics on the other hand. For this purpose, a link has been established between the numerical environment of MATLAB and the thermodynamic library ChemApp. Using this new tool, the kinetics of nitridation, oxidation and carburization processes were predicted numerically taking the material’s microstructure into consideration by distinguishing between precipitation along the grain boundaries and within the grain interior. Excellent agreement between experimental observations and simulation results revealed the high potential of the computer modeling for application to complex corrosion processes.

Metastable austenitic stainless steels are known to undergo a partial transformation of austenite to martensite as a consequence of plastic deformation. In the case of cyclic loading, a certain level of plastic strain must be exceeded, and phase formation takes place after an incubation period, during which the necessary amount of plastic deformation is accumulated. The susceptibility of the austenitic phase to deformation-induced martensite formation is strongly affected by the temperature of loading and the stability of austenite, which itself depends on the chemical composition. A key element in this regard is carbon which stabilizes the austenitic phase. It is shown in this study that the carbon concentration can be analysed systematically and reproducible by means of annealing treatments, if the parameters of these treatments are carefully defined on the basis of advanced theoretical thermodynamic and kinetic considerations. First results on the effect of carbon concentration and temperature of fatigue testing on the austenite/martensite transformation are presented, in order to illustrate the significance of these parameters on the martensite formation rate.

The global pressure for recycling and ecological energy production increases steadily in combination with the demand of cost-effective application of materials. However, some severe corrosion problems, associated with the high internal/intergranular corrosion rates in boiler components need to be avoid. Some commercial boiler materials contain a Cr content of 0.55 (wt. (%)) - 2.25 (wt. (%)). This Cr concentration in the alloys is not sufficient for the formation of a complete dense Cr2O3 scale. Hence, high oxidation kinetics may result. In this study, pure Fe and the steel 2.25Cr1Mo were oxidized in laboratory air at 550 °C using a thermobalance system. The surface as well as the cross section of oxidized specimens were analysed using scanning electron microscopy in order to quantify several factors (e.g. surface finishing, cold working and grain size) on the overall oxidation kinetics. For alloys with low Cr content, a decreasing in the grain size leads to an acceleration of the oxidation rate by facilitating the oxygen diffusion along alloy grain boundaries leading to an inward oxide layer formation. The study of effects of surface finish and cold working yielded results revealing that the oxidation process is complex and comparison of results from different laboratories is difficult and should be done.

Generally, oxide scales formed on high Cr steels are multi-layered and the kinetics are strongly influenced by the alloy grain boundaries. In the present study, the oxidation behaviour of an austenite steel TP347 with different grain sizes was studied to identify the role of grain-boundaries in the oxidation process. Heat treatment in an inert gas atmosphere at 1050 °C was applied to modify the grain size of the steel TP347. The mass gain during subsequent oxidation was measured using a microbalance with a resolution of 10-5 g. The scale morphology was examined using SEM in combination with energy-dispersive X-ray spectroscopy (EDS). Oxidation of TP347 with a grain size of 4 µm at 750 °C in air follows a parabolic rate law. For a larger grain size (65 µm), complex kinetics is observed with a fast initial oxidation followed by several different parabolic oxidation stages. SEM examinations indicated that the scale formed on specimens with smaller grain size was predominantly Cr2O3, with some FeCr2O4 at localized sites. For specimens with larger grain size the main oxide is iron oxide. It can be concluded that protective Cr2O3 formation is promoted by a high density of fast grain-boundary diffusion paths which is the case for fine-grained materials.