O principal programa de pesquisa do Grupo de Diagrama de Fases e Termodinâmica Computacional do LOM/EEL-USP é o estudo de estabilidade de fases em ligas dos sistemas MR-Si-B (MR = Metal Refratário), os quais apresentam um interesse crescente na área de ligas com potencial para aplicações em altas temperaturas. Destes estudos, este Grupo está construindo uma base de informações termodinâmicas com a finalidade de extrapolá-las para sistemas de ordem superior. Diversos sistemas já foram ou estão sendo estudados. Dando continuidade a este programa, os objetivos principais deste trabalho são a avaliação experimental de pontos críticos do sistema Cr-Si-B na região rica em Cr e a modelagem termodinâmica completa do sistema. Foram utilizadas informações da projeção liquidus de Chad (2008) e realizadas medidas experimentais para a determinação das composições das fases em diversas relações de equilíbrio a 1200 ºC, ambas na região rica em Cr. As amostras foram produzidas por fusão em forno a arco, a partir de pedaços de Cr, Si e B de alta pureza; tratadas termicamente a 1200oC por 200 horas e caracterizadas via difração de raios X e MEV/Microssonda eletrônica. Nessa condição de preparação das amostras, não houve dificuldade em se alcançar o equilíbrio termodinâmico. De uma forma geral, as relações de fases a 1200oC de Chad (2008) são confirmadas no presente trabalho. Não foi verificada através de medida por análise térmica diferencial até a temperatura de 1550oC a transformação polimórfica ?Cr5Si3 _ ?Cr5Si3, que segundo Chang (1968) ocorre a 1505oC. Nenhuma modelagem termodinâmica para este sistema ternário é encontrada na literatura. Para a otimização do sistema ternário foram utilizados os coeficientes de Coughanowr, Ansara e Lukas (1998) para o binário Cr-Si; os coeficientes de Campbell e Kattner (2002) para o binário Cr-B e os coeficientes de Fries e Lukas (1998) para o binário Si-B. Foram usados dois modelos para as fases T1 e T2 para descrever suas solubilidades de B e Si, respectivamente. O modelo adotado para a fase ?Cr5Si3 (T1) foi o de solução com três sub-redes (Cr)4(Cr)1(Si,B)3 e o modelo adotado para a fase Cr5B3 (T2) foi o de solução com três sub-redes (Cr)5(B,Si)2(B)1. Estes dois modelos estão compatíveis com aqueles adotados para outros sistemas MR-Si e MR-Si-B. Para a fase CrSS (BCC_A2), o modelo escolhido para permitir a solubilidade de B e/ou Si foi o substitucional para o Si e o intersticial para o B, resultando em uma descrição com duas sub-redes (Cr,Si)1(B,Va)3. A adoção destes modelos compatíveis com otimizações já desenvolvidas e publicadas é importante para permitir o desenvolvimento de uma base de dados multicomponentes MRSi- B que possibilitará previsões confiáveis para as relações de fases em sistemas de ordem superior. A otimização atual reproduziu bem a seção isotérmica a 1200oC e a projeção liquidus do sistema Cr-Si-B na região rica em Cr. / Currently, the main research program of the Phase Diagram and Computational Thermodynamics Group of LOM/EEL-USP is the study of phase stability in MR-Si- B ternary systems (MR = Refractory Metal), which presents an increasing interest in the area of alloys with potential for applications at high temperatures. These research activities include the development of a thermodynamic database to evaluate systems of higher order. Several systems have already been studied. In a continuation of this program, the main objectives of this work are the experimental evaluation of the Cr-Si-B ternary system in the Cr-rich region and the thermodynamic modeling of the complete system. Experimental data from the liquidus projection of Chad (2008) were used and experimental measurements were performed to determine the compositions of various phases in equilibrium at 1200°C, both in the Cr-rich region. The samples were produced by arcmelting high-purity pieces of Cr, Si and B, followed by heat treatment at 1200oC for 200 hours. The samples were characterized by X-ray diffraction and SEM/WDS microanalysis. With this preparation procedure, no difficulty was found to bring the samples to the thermodynamic equilibrium condition. In general, the phase relations at 1200oC proposed by Chad (2008) were confirmed in this study. The polymorphic transformation ?Cr5Si3 _ ?Cr5Si3, which according to Chang (1968) occurs at 1505oC, has not been verified by differential thermal analysis experiments performed until 1550oC. No thermodynamic modeling for this ternary system was found in the literature. The binary coefficients of Coughanowr, Ansara and Lukas (1998) for the Cr-Si, Campbell and Kattner (2002) for the Cr-B and Fries and Lukas (1998) for the Si-B were used in the optimization of the ternary system. Two models for T1 and T2 phases were used to describe their B and Si solubilities, respectively. The model adopted for ?Cr5Si3 (T1) was the solution with three sublattices (Cr)4(Cr)1(Si,B)3 and for Cr5B3 (T2) was the solution with three sublattices (Cr)5(B,Si)2(B)1. These two models were consistent with those adopted in other RM-Si and RM-Si-B systems. For the phase CrSS, the substitutional and interstitial models were used to describe the solubility of Si and B in the BCC structure, respectively, resulting in a solution with two sublattices (Cr,Si)1(B,Va)3. These models are compatible with other previously published optimizations. This is important to enable the development of a multicomponent MR-Si-B database, which will enable reliable predictions for the phase relations in higher-order systems. The Cr-rich region of the isothermal section at 1200oC and of the liquidus projection are well reproduced by the coefficients of the present optimization.

Thesis advisor: Ethan F. Baxter / Samarium/Neodymium (Sm-Nd) garnet geochronology of eclogites from Syros, Greece provides constraints on timing of peak metamorphism while thermodynamic modeling of the same samples allows a comparison of pressure-temperature (P-T) paths. Sm-Nd geochronology of four eclogite samples give ages of 48.8 ± 3.2 Ma (high 147Sm/144Nd = 0.49, n = 6, MSWD = 0.67), 48.1 ± 2.3 Ma (high 147Sm/144Nd = 1.22, n = 4, MSWD = 2.4), 44.7 ± 1.0 Ma (high 147Sm/144Nd = 3.9, n = 6, MSWD = 1.4), and 43.6 ± 1.6 Ma (high 147Sm/144Nd = 1.39, n = 6,MSWD = 2). These garnet growth ages span several million years and are younger than the only other published garnet eclogite ages from the island which use Lutetium/ Hafnium (Lu-Hf) garnet geochronology to place peak metamorphism at ~52 Ma (Lagos et al, 2007). Another eclogite sample dated less precisely yielded an age of 57.7 ± 6.3 Ma (high 147Sm/144Nd = 0.40, n = 10, MSWD = 1.9), significantly older than the other garnets dated in this study. The garnet ages from eclogites presented here suggest that high pressure-low temperature metamorphism, and related garnet growth and dehydration, on Syros lasted ~9 myr, similar to what has been reported for nearby Sifnos Island (Dragovic et al., 2015). Thermodynamic modeling of three samples reveals similar prograde P-T paths despite differences in tectonic setting and chemistry between samples. Water loss from mineral breakdown during the span of subduction zone garnet growth varies between samples from 1.09 to 5.13 weight percent but is greatest for the most ultramafic sample due to chlorite stability permitting greater capacity for water to be carried to depth. P-T paths reach greater maximum pressures (up to 2.42 GPa) than what is reported for Sifnos island (Dragovic et al., 2015) and greater than most previously published pressure estimates for Syros (ie. Okrusch and Bröcker, 1990; Putlitz et al., 2005). / Thesis (MS) — Boston College, 2016. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Earth and Environmental Sciences.

The equilibrium diagrams are the starting point and the guideline to predict and control the microstructure that will form during processing materials. Despite experiments being necessary in binaries and ternaries systems, it is difficult to experimentally determine phase diagrams of higher orders systems over wide ranges of compositions and temperature. The CALPHAD (CALculation of PHAse Diagrams) method was developed in order to solve this problem. The essence is to optimize the parameters of thermodynamic models that describe the Gibbs free energies of each phase aiming to reproduce the experimental and estimated (abinitio) data. The compound energy formalism (CEF) is widely used in order to describe phases which present several sublattices. It allows the modeling of a large variety of phases and numerous methods have been developed to treat different situations. The activities in this work developed a new approach of the CEF (NACEF) based on a mathematic analysis of the parameters which leads to a new formulation of the Gibbs free energy function evolving new independent parameters in which new independent parameters are obtained to express the Gibbs free energy. This approach was used in this work to describe the intermetallic phases with two-sublattice in which the only defect type is anti-sites (A,B)a(A,B)b. The Al-Fe-Nb system was chosen due to its importance for the manufacturing process of several families of alloys currently used, e.g. steels, light alloys, and also for the development of new materials for high temperatures application. The binaries Al-Nb and Fe-Nb were reassessed and the Al-Fe-Nb system was assessed for the first time using literature information and new experimental data. / Os diagramas de equilíbrio são o ponto de partida e a diretriz para prever e controlar a microestrutura ao final do processamento de um material. Apesar de experimentos serem necessários em sistemas binários e ternários, é muito difícil determinar experimentalmente diagramas de fase de sistemas de ordens superiores numa vasta amplitude de composições e temperatura. A fim de solucionar este problema, o método CALPHAD (CALculation of PHAse Diagrams) foi desenvolvido. A essência consiste em aperfeiçoar os parâmetros de modelos termodinâmicos que descrevem as energias livres de Gibbs de cada fase de modo a reproduzir as informações experimentais ou estimadas (ab-initio). O compound energy formalism (CEF) é amplamente utilizado para descrever fases que apresentam várias sub-redes. Ele permite a modelagem de uma grande variedade de fases e vários métodos têm sido desenvolvidos para o tratamento de diferentes situações. As atividades deste trabalho ajudaram a desenvolver uma nova abordagem para o CEF (NACEF) com base em um estudo matemático dos seus parâmetros termodinâmicos que levou a uma nova formulação para função da energia livre de Gibbs envolvendo novos parâmetros independentes. Esta nova abordagem tem sido utilizado como parte do presente trabalho para modelar fases intermetálicas binárias constituídas de sub-redes cujo único defeito é do tipo anti-sítio (A,B)a(A,B)b. O sistema Al-Fe-Nb foi escolhido devido a sua importância para o processo de fabricação de diversas famílias de ligas usadas atualmente, e.g. aços, ligas leves e, além disto, é um sistema importante para o desenvolvimento de materiais para aplicações em altas temperaturas. Neste trabalho os binários Al-Nb e Fe-Nb foram reavaliados e o sistema Al-Fe-Nb foi modelado pela primeira vez utilizando as informações da literatura e novos dados experimentais.

Considerado a alternativa mais pesquisada para substituir o diesel, o biodiesel, oriundo da transesterificação, é cotado como a mais promissora opção de combustível obtido de fontes renováveis para o lugar dos ameaçados combustíveis de origem fóssil. A reação de transesterificação para produção do biodiesel pode ocorrer de forma catalítica, a mais utilizada atualmente, e não-catalítica, por meio de fluidos supercríticos. A grande diversidade de matérias-primas que pode ser usada na obtenção do biodiesel supercrítico é apenas um dos atrativos para sua produção, porém uma produção em larga escala esbarraria nos altos custos operacionais do processo. Devido ao potencial revelado nos processos supercríticos, o estudo do comportamento de fases dentro de um reator se mostra relevante ao domínio do processo, visto que pesquisas indicam que é possível balancear os custos de uma produção de biodiesel em condições supercríticas com os custos de uma produção de biodiesel com uso de catalisadores. Na termodinâmica, a modelagem é um método prático e rápido de se estimar o comportamento do equilíbrio líquido-vapor (ELV) do sistema e reduzir gastos com excessivos experimentos, através de um modelo termodinâmico apropriado. Para isso, os modelos testados foram obtidos pela equação de estado (EdE) de Peng-Robinson com as regras de misturas de van der Waals com um (vdW1) e dois (vdW2) parâmetros de interação binária em sistemas formados por componentes presentes na produção do biodiesel. Utilizando a abordagem phi-phi e o método de BOLHA P, sistemas binários em condições próximas ao ponto crítico e em condições supercríticas, encontrados na literatura, foram modelados. A modelagem termodinâmica foi realizada após a aplicação de um teste de consistência termodinâmica, uma vez que foram encontradas diferenças nas propriedades críticas de um mesmo composto em diferentes referências. A adequação dos modelos termodinâmicos variou de acordo com as condições do processo, o que fará necessária uma análise específica da situação de acordo com o caso em que estiver sendo empregada. Na simulação termodinâmica, as redes neurais artificiais foram utilizadas para o ajuste computacional dos dados experimentais, produzindo os melhores resultados com a introdução dos descritores moleculares, junto às variáveis independentes do processo (temperatura e composição na fase líquida), na primeira camada de neurônios nas diversas configurações analisadas dentre as arquiteturas utilizadas, demonstrando ser uma ferramenta interessante para o estudo do equilíbrio de fases. / Considered the most researched alternative to replace the diesel fuel, the biodiesel, from transesterification, is rated as the most promising fuel option from renewable sources for the place of threatened fossil fuels. The transesterification reaction for biodiesel production can occur catalytically, commonly used, and non-catalytic, through supercritical fluids. The diversity of raw materials that can be used to obtain supercritical biodiesel is only one of the attractions for its production, but a large-scale production would encounter obstacles in the high operating costs of the process. Due to the potential revealed in the supercritical processes, the study of phase behavior in a reactor is relevant for domaining the process, since researches indicates that it is possible to balance the costs of producing biodiesel in supercritical conditions with the costs of a production of biodiesel using catalysts. In thermodynamics, modeling is a quick and practical method of estimating the vapor-liquid equilibria (VLE) behavior of the system and reducing expenses with excessive experiments, using an appropriated thermodynamic model. For this, the models tested were obtained by the Peng-Robinson equation of state (EoS) with the mixture rules of van der Waals with one (vdW1) and two (vdW2) binary interaction parameters in systems formed by components present in the production of biodiesel. Using the phi-phi approach and the BOL P method, binary systems in conditions near to the critical point and under supercritical conditions, found in the literature, were modeled. The thermodynamic modeling was performed after the application of a thermodynamic consistency test, since differences were found in the critical properties of the same compound in different references. The suitability of the thermodynamic models varied according to the process conditions, which will require a specific analysis of the situation according to the case in which it is being used. In the thermodynamic simulation, the artificial neural networks were used for the computational adjustment of the experimental data, producing the best results when the molecular descriptors were used with the independent variables of the process (temperature and composition of the liquid phase) in the first layer of nodes in the different configurations analyzed among the architectures used, proving to be a tool of interest for the study of phase equilibria.

O principal programa de pesquisa do Grupo de Diagrama de Fases e Termodinâmica Computacional do LOM/EEL-USP é o estudo de estabilidade de fases em ligas dos sistemas MR-Si-B (MR = Metal Refratário), os quais apresentam um interesse crescente na área de ligas com potencial para aplicações em altas temperaturas. Destes estudos, este Grupo está construindo uma base de informações termodinâmicas com a finalidade de extrapolá-las para sistemas de ordem superior. Diversos sistemas já foram ou estão sendo estudados. Dando continuidade a este programa, os objetivos principais deste trabalho são a avaliação experimental de pontos críticos do sistema Cr-Si-B na região rica em Cr e a modelagem termodinâmica completa do sistema. Foram utilizadas informações da projeção liquidus de Chad (2008) e realizadas medidas experimentais para a determinação das composições das fases em diversas relações de equilíbrio a 1200 ºC, ambas na região rica em Cr. As amostras foram produzidas por fusão em forno a arco, a partir de pedaços de Cr, Si e B de alta pureza; tratadas termicamente a 1200oC por 200 horas e caracterizadas via difração de raios X e MEV/Microssonda eletrônica. Nessa condição de preparação das amostras, não houve dificuldade em se alcançar o equilíbrio termodinâmico. De uma forma geral, as relações de fases a 1200oC de Chad (2008) são confirmadas no presente trabalho. Não foi verificada através de medida por análise térmica diferencial até a temperatura de 1550oC a transformação polimórfica ?Cr5Si3 _ ?Cr5Si3, que segundo Chang (1968) ocorre a 1505oC. Nenhuma modelagem termodinâmica para este sistema ternário é encontrada na literatura. Para a otimização do sistema ternário foram utilizados os coeficientes de Coughanowr, Ansara e Lukas (1998) para o binário Cr-Si; os coeficientes de Campbell e Kattner (2002) para o binário Cr-B e os coeficientes de Fries e Lukas (1998) para o binário Si-B. Foram usados dois modelos para as fases T1 e T2 para descrever suas solubilidades de B e Si, respectivamente. O modelo adotado para a fase ?Cr5Si3 (T1) foi o de solução com três sub-redes (Cr)4(Cr)1(Si,B)3 e o modelo adotado para a fase Cr5B3 (T2) foi o de solução com três sub-redes (Cr)5(B,Si)2(B)1. Estes dois modelos estão compatíveis com aqueles adotados para outros sistemas MR-Si e MR-Si-B. Para a fase CrSS (BCC_A2), o modelo escolhido para permitir a solubilidade de B e/ou Si foi o substitucional para o Si e o intersticial para o B, resultando em uma descrição com duas sub-redes (Cr,Si)1(B,Va)3. A adoção destes modelos compatíveis com otimizações já desenvolvidas e publicadas é importante para permitir o desenvolvimento de uma base de dados multicomponentes MRSi- B que possibilitará previsões confiáveis para as relações de fases em sistemas de ordem superior. A otimização atual reproduziu bem a seção isotérmica a 1200oC e a projeção liquidus do sistema Cr-Si-B na região rica em Cr. / Currently, the main research program of the Phase Diagram and Computational Thermodynamics Group of LOM/EEL-USP is the study of phase stability in MR-Si- B ternary systems (MR = Refractory Metal), which presents an increasing interest in the area of alloys with potential for applications at high temperatures. These research activities include the development of a thermodynamic database to evaluate systems of higher order. Several systems have already been studied. In a continuation of this program, the main objectives of this work are the experimental evaluation of the Cr-Si-B ternary system in the Cr-rich region and the thermodynamic modeling of the complete system. Experimental data from the liquidus projection of Chad (2008) were used and experimental measurements were performed to determine the compositions of various phases in equilibrium at 1200°C, both in the Cr-rich region. The samples were produced by arcmelting high-purity pieces of Cr, Si and B, followed by heat treatment at 1200oC for 200 hours. The samples were characterized by X-ray diffraction and SEM/WDS microanalysis. With this preparation procedure, no difficulty was found to bring the samples to the thermodynamic equilibrium condition. In general, the phase relations at 1200oC proposed by Chad (2008) were confirmed in this study. The polymorphic transformation ?Cr5Si3 _ ?Cr5Si3, which according to Chang (1968) occurs at 1505oC, has not been verified by differential thermal analysis experiments performed until 1550oC. No thermodynamic modeling for this ternary system was found in the literature. The binary coefficients of Coughanowr, Ansara and Lukas (1998) for the Cr-Si, Campbell and Kattner (2002) for the Cr-B and Fries and Lukas (1998) for the Si-B were used in the optimization of the ternary system. Two models for T1 and T2 phases were used to describe their B and Si solubilities, respectively. The model adopted for ?Cr5Si3 (T1) was the solution with three sublattices (Cr)4(Cr)1(Si,B)3 and for Cr5B3 (T2) was the solution with three sublattices (Cr)5(B,Si)2(B)1. These two models were consistent with those adopted in other RM-Si and RM-Si-B systems. For the phase CrSS, the substitutional and interstitial models were used to describe the solubility of Si and B in the BCC structure, respectively, resulting in a solution with two sublattices (Cr,Si)1(B,Va)3. These models are compatible with other previously published optimizations. This is important to enable the development of a multicomponent MR-Si-B database, which will enable reliable predictions for the phase relations in higher-order systems. The Cr-rich region of the isothermal section at 1200oC and of the liquidus projection are well reproduced by the coefficients of the present optimization.

Considerado a alternativa mais pesquisada para substituir o diesel, o biodiesel, oriundo da transesterificação, é cotado como a mais promissora opção de combustível obtido de fontes renováveis para o lugar dos ameaçados combustíveis de origem fóssil. A reação de transesterificação para produção do biodiesel pode ocorrer de forma catalítica, a mais utilizada atualmente, e não-catalítica, por meio de fluidos supercríticos. A grande diversidade de matérias-primas que pode ser usada na obtenção do biodiesel supercrítico é apenas um dos atrativos para sua produção, porém uma produção em larga escala esbarraria nos altos custos operacionais do processo. Devido ao potencial revelado nos processos supercríticos, o estudo do comportamento de fases dentro de um reator se mostra relevante ao domínio do processo, visto que pesquisas indicam que é possível balancear os custos de uma produção de biodiesel em condições supercríticas com os custos de uma produção de biodiesel com uso de catalisadores. Na termodinâmica, a modelagem é um método prático e rápido de se estimar o comportamento do equilíbrio líquido-vapor (ELV) do sistema e reduzir gastos com excessivos experimentos, através de um modelo termodinâmico apropriado. Para isso, os modelos testados foram obtidos pela equação de estado (EdE) de Peng-Robinson com as regras de misturas de van der Waals com um (vdW1) e dois (vdW2) parâmetros de interação binária em sistemas formados por componentes presentes na produção do biodiesel. Utilizando a abordagem phi-phi e o método de BOLHA P, sistemas binários em condições próximas ao ponto crítico e em condições supercríticas, encontrados na literatura, foram modelados. A modelagem termodinâmica foi realizada após a aplicação de um teste de consistência termodinâmica, uma vez que foram encontradas diferenças nas propriedades críticas de um mesmo composto em diferentes referências. A adequação dos modelos termodinâmicos variou de acordo com as condições do processo, o que fará necessária uma análise específica da situação de acordo com o caso em que estiver sendo empregada. Na simulação termodinâmica, as redes neurais artificiais foram utilizadas para o ajuste computacional dos dados experimentais, produzindo os melhores resultados com a introdução dos descritores moleculares, junto às variáveis independentes do processo (temperatura e composição na fase líquida), na primeira camada de neurônios nas diversas configurações analisadas dentre as arquiteturas utilizadas, demonstrando ser uma ferramenta interessante para o estudo do equilíbrio de fases. / Considered the most researched alternative to replace the diesel fuel, the biodiesel, from transesterification, is rated as the most promising fuel option from renewable sources for the place of threatened fossil fuels. The transesterification reaction for biodiesel production can occur catalytically, commonly used, and non-catalytic, through supercritical fluids. The diversity of raw materials that can be used to obtain supercritical biodiesel is only one of the attractions for its production, but a large-scale production would encounter obstacles in the high operating costs of the process. Due to the potential revealed in the supercritical processes, the study of phase behavior in a reactor is relevant for domaining the process, since researches indicates that it is possible to balance the costs of producing biodiesel in supercritical conditions with the costs of a production of biodiesel using catalysts. In thermodynamics, modeling is a quick and practical method of estimating the vapor-liquid equilibria (VLE) behavior of the system and reducing expenses with excessive experiments, using an appropriated thermodynamic model. For this, the models tested were obtained by the Peng-Robinson equation of state (EoS) with the mixture rules of van der Waals with one (vdW1) and two (vdW2) binary interaction parameters in systems formed by components present in the production of biodiesel. Using the phi-phi approach and the BOL P method, binary systems in conditions near to the critical point and under supercritical conditions, found in the literature, were modeled. The thermodynamic modeling was performed after the application of a thermodynamic consistency test, since differences were found in the critical properties of the same compound in different references. The suitability of the thermodynamic models varied according to the process conditions, which will require a specific analysis of the situation according to the case in which it is being used. In the thermodynamic simulation, the artificial neural networks were used for the computational adjustment of the experimental data, producing the best results when the molecular descriptors were used with the independent variables of the process (temperature and composition of the liquid phase) in the first layer of nodes in the different configurations analyzed among the architectures used, proving to be a tool of interest for the study of phase equilibria.

With the increased interest in bainitic steels, fundamental understanding of the bainite transformationis of major importance. Unfortunately, the research on bainite has been hampered by an oldcontroversy on its formation mechanism. Over the years two quite different theories have developedclaiming to describe the bainite transformation i.e. the diffusionless and the diffusion controlledtheory. In this thesis, attention is directed towards fundamental understanding of the bainitetransformation and both experimental and theoretical approaches are used in order to reveal its truenatureIn the first part of this thesis the symmetry in the Fe-C phase diagram is studied. It is based on ametallographic mapping of microstructures using light optical microscopy and scanning electronmicroscopy in a high carbon steel. The mapping revealed symmetries both with respect to temperatureand carbon content and an acicular eutectoid with cementite as the leading phase was found andidentified as inverse bainite. By accepting that all the eutectoid microstructures forms by diffusion ofcarbon, one may explain the existence of symmetries in the Fe-C phase diagram. Additional supportof its existence is obtained from an observation of symmetries in an alloyed steel. From the performedwork it was concluded that the existence of symmetries among the eutectoid microstructures fromaustenite supports the idea that bainite forms by a diffusion controlled transformation.In the second part the growth of bainite is considered. An experimental study using laser scanningconfocal microscopy was performed and growth rates of the transformation products from austenite ina high carbon, high chromium steel was analysed. The growth rate measurements reveals the kineticrelation between Widmanstätten cementite and the acicular eutectoid previously identified as inversebainite which confirms its existence and the conclusions drawn in the first part. In addition, in-situobservations of bainite formation below Ms provide additional support for the diffusion controlledtheory for bainite formation.The final part of the work is a study of the critical conditions for the formation of acicular ferrite.Based on experimental information found in the literature a thermodynamic analysis is performed inview of the two theories. The results demonstrate that the governing process for Fe-C alloys cannot bediffusionless but both kinds of processes can formally be used for predicting Bs temperatures for Fe-Calloys. / <p>QC 20130503</p>

The Mo-Ni-Re system is one of the important subsystems of the Ni based superalloys engineered for use in high temperature applications. Considering the contradictions among previously reported information, the present study was devoted to the complete experimental determination of the phase equilibria in the Mo-Ni-Re system, structural characterization of its intermetallic phases and thermodynamic modeling of the system with the help of the CALPHAD method. The experimental investigation of phase equilibria was carried out with the help of equilibrated alloys and phase diagrams of the Ni-Re and Mo-Ni-Re system (at 1200°C and 1600°C) were proposed. In comparison with previous investigations, the Ni-Re phase diagram determined during the present study showed significant difference in terms of homogeneity domains, freezing ranges and peritectic reaction temperature. The 1200°C isothermal section of the Mo-Ni-Re system proposed during the present study showed large extension of the Mo-Re σ phase and Mo-Ni δ phase in the ternary region. In addition, presence of two previously unknown ternary phases was also observed. The isothermal section of the Mo-Ni-Re system at 1600°C also showed large extension of σ phase in the ternary region whereas extension of the Mo-Re χ phase in both isothermal sections was restricted to narrow composition range. The presence of the ternary phases observed in the 1200°C isothermal was not evidenced in 1600°C isothermal section. On the other hand, partial investigations of phase boundaries in the Mo-Ni and Mo-Re binary systems and determination of liquidus projection of the Mo-Ni-Re system was also carried out. The liquidus projection of the Mo-Ni-Re system proposed during present study also showed largely extended primary crystallization fields of the Mo-Re σ phase and Re solid solution in the ternary region. Since isothermal sections of the Mo-Ni-Re system showed largely extended homogeneity domain of σ, structural characterization of the Mo-Ni-Re σ with particular emphasis on determination of site occupancy trends as a function of composition was carried out by combined Rietveld refinement of the X-ray and neutron diffraction data. The experimental results gathered during the present study along with the information available in the literature were used as input for thermodynamic modeling of the Mo-Ni-Re system. The thermodynamic description of the Mo-Re system was taken from literature whereas thermodynamic modeling of the Mo-Ni, Ni-Re and Mo-Ni-Re system was carried out during the present study with the help of the CALHAD method.Keywords: Mo-Ni; Mo-Re; Ni-Re; Mo-Ni-Re; phase diagram; isothermal section; structural characterization; thermodynamic modeling; CALPHAD method

In their attempts to understand the unwritten past of human technology and progression, archaeologists have borrowed aspects of the natural sciences to answer big questions. In one such pursuit, fundamental aspects of the sciences have been employed towards the chemical compositional analysis of copper-based artifacts, often to simply classify which is bronze, brass, or pure copper, and to explain why they are significant in limited space and time. This thesis takes the variety of identified metal types and compositions from these analyses and builds the beginnings of an ambitious thermodynamic model based on the accepted premise of consistent and widespread recycling of ancient metals over time. Following the laws of thermodynamics, in systems at equilibrium, the model predicts the outcome of metal losses over the course of ancient pyrometallurgical processes from molten systems through both volatilization and oxidation using rigorous and established mathematics and theory. Elemental loss likelihoods are modeled for all binary copper-based metals, using activity coefficients, and ternary copper and zinc-based systems, with the excess Gibbs free energy, respectively. The calculations are performed using custom-written software designed to account for hundreds of thousands of compositional permutations after the method described by Redlich and Kister (1948). The results of these calculations are given as activity (binary) and isoactivity (ternary) contour lines. Quantified tables for the oxidation and volatilization of elements from a copper melt at 1200 ºC and 1 atm are also given as rough indicators of element loss in ancient pyrometallurgical systems. A proof of concept of the models viability is also provided for binary Cu-M and ternary Cu-M-Zn (M = Ag, As, Au, Bi, Co, Fe, Ni, Pb, Sb, Sn, Zn), Cu-Sn-Pb, and Cu-Sb-As systems from the Late Bronze Age to post-medieval periods in Britain, which is based on several substantial artifact chemical datasets. For each ternary system, the interaction parameters used for higher-order calculations from the fitted behavior of each contributing binary systems are provided. Comparison of the calculated models to available experimental system assessments, and to published archaeological chemical datasets, show that in both respects the proposed modeling of ancient copper-based metal losses works. And given the near ubiquity of ancient metal use around the world, the consistency in metal production and recycling technology, and the chemical analyses available, this preliminary model can be applied virtually anywhere the technology for smelting and recycling existed. In addition to loss modeling, this thesis has the additional offshoots of predicting ancient furnace conditions based on the calculated behavior of interacting metals, and of the controlling thermodynamic factors in the ancient calamine process.

Le massif de l'Agly a subit un métamorphisme hercynien haute température – basse pression dont le gradient apparent est comparable à celui des zones volcaniques actuelles (120°C.km-1). Ce gradient anormal a donné lieu à plusieurs hypothèses (i) des déformations structurales (amincissement crustal, délamination), (ii) un apport thermique (activité magmatique).Les affleurements du massif de l'Agly permettent l'observation d'une succession sans hiatus apparent des faciès métamorphiques de schistes verts à granulites. Le socle est constitué de gneiss précambriens et d'orthogneiss cambriens. En discordance sur le socle repose une couverture de sédiments paléozoïques. De nombreux granitoïdes tardi-carbonifère se sont mis en place à dans le massif.Nous avons actualisé les données thermobarométrique selon deux approches (la modélisation thermodynamique NKFMASHTL et des calibrations thermobarométrique). Les résultats barométriques indiquent une pression maximale de 4,5 ± 0,5 kbar pour les terrains les plus profonds et un hiatus de l’ordre de 1,5 kbar entre socle et couverture. Le pic du métamorphisme est suivi par des réactions correspondant à une décompression.Une modélisation thermique de la conduction de sills nous a permis de tester l'effet de différents paramètres : conductivité, capacité calorifique ; géotherme initial ; épaisseur de la croûte ; réactions métamorphiques ; fréquence, géométrie, température et profondeur d'injection des sills. Un amincissement crustal ou un apport de chaleur mantellique purement conductif ne sont pas suffisant, sans la mise en place de sills à une profondeur équivalente à celle du haut du socle, pour expliquer les observations. / The Agly massif undergone a high temperature - low pressure metamorphism which shows an apparent thermal gradient comparable to that of present-day volcanic zones (120°C.km-1). Such abnormal thermal gradients have given way to various hypotheses, including structural deformations (crustal thinning, delamination), or heat input due to a magmatic activity.The outcrops through the Agly massif allow the study of an apparently hiatus-free succession of metamorphic facies ranging from greenschists to granulites. The massif is composed of a basement of precambrian gneisses and cambrian orthogneisses. The basement is unconformably overlain by a paleozoïc sedimentary cover. The late-Carboniferous granitoïds, associated to mafic intrusions, are observed at all levels.We have used thermodynamic modelling and thermobarometric calibrations to revisited the thermobarometric data for both cover and basement rocks. Both methods provide consistent barometric results, 4,5 ± 0,5 kbar for the deepest parts of the massif and a hiatus in the range of 1,5 kbar between the basement and the cover. Post-peak reactions correspond to a decompression. A conductive thermal modelling of sills injection allow us to test the influence of various parameters on the heat flow through the crust modeled : thermal conductivity and heat capacity ; initial geotherm ; crust thickness ; metamorphic reactions ; timing, geometry, temperature and depth of sill injection. Crustal delamination, thinning or magma emplacement in the lower crust cannot reproduce the observed HT-LP metamorphic conditions, unless associated with magma injection at the depth corresponding to the one of the top of the Agly basement.