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Firstly, an existing thermodynamic model for the predicting of martensite start temperature of commercial steels has been improved to include more elements such as N, Si, V, Mo, Nb, W, Ti, Al, Cu, Co, B, P and S and their corresponding composition ranges for Martensitic transformation. The predicting ability of the existing model is improved considerably by critical assessment of different binary and ternary systems i.e. CALPHAD approach which is by wise selection of experimental data for optimization of the interaction parameters. Understanding the degree of variation in multi-component commercial alloys, various ternary systems such as Fe-Ni-X and Fe-Cr-X are optimized using both binary and ternary interaction parameters. The large variations between calculated and the experimental values are determined and reported for improvements in thermodynamics descriptions.Secondly, model for the prediction of Epsilon martensite start temperature of some commercial steels and shape memory alloys is newly introduced by optimizing Fe-Mn, Fe-Mn-Si and other Fe-Mn-X systems considering the commercial aspects in the recent development of light weight steels alloyed with Al and Si.Thirdly, the effect of prior Austenite grain size (pAGS) on martensite start temperature is introduced into the model in the form of non-chemical contribution which will greatly influence the Gibbs energy barrier for transformation. A serious attempt has been made to describe the dependency of transition between lenticular and thin-plate martensite morphologies on the refinement of prior Austenite grain size.Finally, the model is validated using a data-set of 1500 commercial and novel alloys. Including the newly modified thermodynamic descriptions for the Fe-based TCFE9 database by Thermo-Calc software AB, the model has the efficiency to predict the martensite start temperature of Multi-component alloys with an accuracy of (±) 35 K. The model predictability can be further improved by critical assessment of thermodynamic factors such as stacking faults and magnetism in Fe-Mn-Si-Ni-Cr systems.

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La mise au point de réacteurs nucléaires sous-critiques (Accelerator Driven System - ADS), intrinsèquement sûrs, pour incinérer les déchets nucléaires par transmutation d’actinides de durée de vie longue en radioéléments de plus courte durée de vie, réclament des sources intenses de neutrons. Ces sources sont produites par la technique de spallations « éjections », c’est-à-dire l’interaction d’un faisceau de protons de haute énergie et haute intensité avec une cible contenant des métaux lourds. Compte tenu de la puissance déposée par les protons dans la cible (de l'ordre de quelques MW) seuls des métaux sous forme liquide peuvent à la fois résister aux défauts induits et évacuer la chaleur. Dans ce contexte l'expérience MEGAPIE (MEGawatt PIlot Experiment) fonctionnant avec une fenêtre au niveau de la cible de spallation est pionnière et ouvre la voie vers des cibles de haute puissance. Pour la mise en œuvre de cette cible MEGAPIE, les choix de l’alliage de la cible de spallations, des matériaux de structures de la fenêtre et des parties chaudes sont portés respectivement sur l’eutectique plomb-bismuth, bon rendement neutronique, et l’acier T91 (1%Mo9%Cr en masse), bonne tenue à l’irradiation. Pour les parties froides l’acier 316L a été choisi. Toutefois, malgré sa bonne tenue à l’irradiation, le contact de ces deux alliages (eutectique plomb-bismuth et acier T91) présente quelques inconvénients qui nécessitent d’approfondir la connaissance de leurs propriétés physico-chimiques dans l’environnement MEGAPIE et motive cette présente étude. La contribution de ce travail au développement du réacteur de transmutation a consisté : - d’une part à l'élaboration de revêtements destinés à améliorer les performances de l'acier de structure T91 vis à vis de l'oxydation et de la fissuration par l'eutectique Pb-Bi liquide, - d'autre part à l'étude thermodynamique du système Pb-Bi-(Hg)-Fe-Cr-Al-O pour connaître l’ensemble des équilibres entre phases existant dans les conditions imposées par le fonctionnement du réacteur ADS. Le deuxième volet de ce travail trouve sa justification dans les résultats du premier qui ont mis en évidence le rôle primordial joué par les oxydes mixtes dans l'interaction corrosive entre l'acier et l'eutectique Pb-Bi faiblement oxygéné. / The development of sub-critical nuclear reactors (Accelerator Driven System - ADS), intrinsically safe to incinerate nuclear waste by transmutation of long-lived actinides to radionuclides with a shorter existence, requires intense sources of neutrons. These sources are produced by the "ejected" spallation technique, i.e. the interaction of a high energy, high intensity proton beam with a target containing heavy metals. Considering the power of the proton beam transferred to the target (of a few MW), only metals in the liquid form can be cooled in a closed cooling system and resist to nuclear reactor induced by the proton beam. In this context, the MEGAPIE project (MEGawatt PIlot Experiment), which works with a window at the spallation target, is pioneer and opens the way for high-power targets. The choice of the alloy for the MEGAPIE spallation target is a lead-bismuth eutectic, which is efficient for producing neutrons. For the window beam and hot parts, the best choice at present is the T91 steel (1%Mo9%Cr in mass), due to its good irradiation resistance. For cold parts, the 316L steel was chosen. However, the contact of the two alloys (eutectic lead-bismuth and T91 steel) presents some inconveniences that need to be investigated in relation to their physico-chemical properties in the MEGAPIE environment, which motivates this study. The contribution of this work to this subject consisted of : - In a part, the development of coatings designed to improve the chemical and mechanical performances of the T91 steel in contact of the lead-bismuth eutectic liquid alloy, - In another part, the investigation of the thermodynamic properties of the Pb-Bi-(Hg)-Fe-Cr-Al-O system for all phase equilibria within the conditions imposed by the operation of the ADS reactor. The second part of this work is justified by the results, which, for the first time, highlight the role played by the mixed oxide phases in the corrosive interaction between the T91 steel and Pb-Bi eutectic, in a poorly oxygenated environment.

O objetivo do presente projeto é a combinação de abordagens experimentais e teóricas para o desenvolvimento de bancos de dados termodinâmicos, visando o modelamento de aços e ligas de alto desempenho. Entre esses materiais estão as superligas fundidas por centrifugação para aplicações em fornos de reforma e pirólise, bem como aços-ferramenta reforçados por fases intermetálicas. Os métodos teóricos mencionados correspondem à combinação de cálculos de estrutura eletrônica e modelamento termodinâmico em temperaturas finitas, através do protocolo Calphad. Esta metodologia vem sendo aplicada com sucesso por vários grupos de pesquisa brasileiros e internacionais. Utilizando-nos de dados experimentais para o sistema Fe-Cr-Mo-C, obtidos recentemente em nosso laboratório, e cálculos de primeiros princípios para o sistema Ni-Nb-Si, aliados a outros resultados experimentais da literatura, aperfeiçoamos os bancos de dados termodinâmicos existentes para estes dois sistemas, minimizando as inconsistências quanto às evidências experimentais em relação aos campos de estabilidade e equilíbrio entre fases. No sistema Fe-Cr-Mo-C, utilizamo-nos de dados experimentais para uma reotimização da descrição termodinâmica. Adotamos novas descrições para os binários Cr-Fe, C-Cr e C-Fe, com novos modelos para as fases cementita no sistema C-Fe e sigma no sistema Cr-Fe. Com essas alterações, fomos levados a reavaliar todas as descrições dos ternários, reotimizando-os quando necessário (C-Cr-Fe) ou apenas revalidando os modelamentos pré-existentes (C-Cr-Mo). Por fim, reotimizamos o quaternário como um todo, chegando a resultados satisfatórios quando comparados a resultados experimentais. As propriedades termodinâmicas do sistema Nb-Ni-Si são pouquíssimo conhecidas. Por este motivo, não há dados suficientes na literatura para realizar um assessment completo deste sistema. Por isto, decidimos realizar cálculos de primeiros princípios de estrutura eletrônica, para a determinação de energias de formação dos compostos ternários presentes neste sistema. Os sistemas binários Nb-Ni, Nb-Si e Ni-Si, por outro lado, são bem conhecidos, cada um deles contando com diversas descrições termodinâmicas publicadas ao longo dos últimos anos. Por esta razão, adotamos as mais recentes descrições termodinâmicas dos binários como ponto de partida para o modelamento do sistema ternário. O resultado do modelamento, quando comparado aos poucos dados experimentais disponíveis, é bastante satisfatório. / The aim of this project is the combination of advanced experimental and theoretical approaches for the development of thermodynamic databases dedicated to modelling steels and high performance alloys. Examples of materials are centrifugally-cast superalloys designed for use in reforming and pyrolisis furnaces, as well as intermetallic-reinforced tool steels. The theoretical methods are the combination of electronic structure calculations and thermodynamic modeling at finite temperatures using the CALPHAD method. This methodology has been used by different scientific groups, both in Brazil and around the world. Using experimental data in the Fe-Cr-Mo-C sytem, recently determined in our laboratory, and first principles calculations in the Nb-Ni-Si system, together with other experimental results from the literature, we improved the existing thermodynamic databases for these two systems, minimizing discrepancies regarding the experimental evidence about phase stability fields and phase equilibria. In the Fe-Cr-Mo-C system, we employed experimental data for a reoptimization of the thermodynamic description. We adopted new descriptions for the binary Cr-Fe, C-Cr, and C-Fe systems, with new models for cementite in the C-Fe system, and sigma in the Cr-Fe system. Because of these alterations, a reevaluation of the ternary descriptions was necessary, reassessing them when required (C-Cr-Fe) or just revalidating existing models (C-Cr-Mo). After that, we re-optimized the quaternary system, arriving at satisfactory results, in comparison with experimental data. The thermodynamic properties of the Ni-Nb-Si system is almost completely unknown. For that reason, there are not enough data in the literature to perform a complete assessment of the system. With that in mind, we decided to perform first-principles electronic structure calculations, in order to determine the formation energies of the ternary compounds. The binary systems, on the other hand, are very well-known, each one of them with several published thermodynamic assessments during the last few years. For this reason, we adopted the most recent thermodynamic descriptions of the binaries as a starting point for the modelling of the ternary system. The result of the modelling is very satisfactory, in comparison with the few experimental information available.