Orientador: Prof. Dr. Sydney Ferreira Santos / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2015. / Combustiveis nucleares baseados em materiais compositos obtidos pela dispersao de ligas de uranio em matrizes metalicas sao alternativas interessantes para o avanco da tecnologia de geracao nucleoeletrica. Ligas de U-Mo tem grande potencial para serem utilizadas como elemento combustivel nos combustiveis tipo placa e as ligas de zirconio, como o zircaloy-4, como material de matriz e revestimento. A fase ¿Á do uranio e isotropica e garante estabilidade mecanica e termica ao uranio em diferentes condicoes de operacao, mas essa fase apenas e estavel em altas temperaturas. A adicao de molibdenio tem se mostrado eficiente na estabilizacao dessa fase em baixa temperatura e o zircaloy-4 possui caracteristicas interessantes para a industria nuclear, tais como alto ponto de fusao, alta condutividade termica e baixa secao de choque de absorcao de neutrons. No presente trabalho, foram estudadas rotas para a obtencao de pos de Zircaloy-4, sendo esta uma etapa muito importante para a fabricacao de compositos de combustivel nuclear tipo placa. Estudou-se tambem sintese de ligas de U-Mo, com estruturas ¿Á por rotas de fusao, sendo investigadas as composicoes U-7%Mo, U-8,5%Mo e U-10%Mo. Essas ligas foram fundidas em um forno a arco e de inducao e tratadas termicamente para a estabilizacao da fase ¿Á. Os resultados obtidos mostraram que independente do processo de fusao e da composicao das ligas, e necessario um tratamento termico para a dissolucao das dendritas e homogeneizacao das ligas. O tratamento termico seguido de tempera se mostrou eficiente para a estabilizacao completa da fase ¿Á para as ligas com adicao de apenas 7% em peso de molibdenio. Por outro lado, o tratamento termico seguido de resfriamento lento conseguiu estabilizar a fase ¿Á apenas nas ligas com 10% em peso de molibdenio. As ligas com 7% e 8,5% de Mo que sofreram um resfriamento lento apresentavam uma fracao de fase ¿¿. Quanto a obtencao de pos de zircaloy, esta pode ser realizada atraves da tecnica de hidretacao, cominuicao e desidretacao. A cinetica de absorcao e desorcao de hidrogenio apresentou melhores resultados nas amostras laminadas a frio antes do processo de hidretacao. O tempo de absorcao de hidrogenio das amostras como recebida (770 segundos) e apos (18 segundos) diminuiu 96,75% quando hidretadas a 450 ¿C e 1000kP de H2. A temperatura de desorcao do hidrogenio das amostras hidretadas passou de 1000 ¿C para as amostras como recebida para 850 ¿C para as amostras apos 25 passes. Alem disso, o processo de moagem de alta energia tambem se mostrou eficaz para a producao de pos de hidreto. Os resultados e discussoes contidos nesta tese sao importantes para demonstrar a viabilidade de diversas rotas de obtencao de materiais metalicos utilizados na producao de combustiveis nucleares tipo placa. / Nuclear fuels based on composite materials obtained by dispersion of uranium alloys in metal matrices are interesting alternatives to the improvement of the nuclear energy generation technology. U-Mo alloys have great potential to be used as fuel element in dispersion fuels and zirconium alloys, such as zircaloy-4, as coating and matrix material. The ã-U phase is isotropic and provides mechanical and thermal stability to the uranium in different operating conditions, but it is only stable at high temperatures. The addition of molybdenum has been considered effective for the stabilization of this phase at low temperatures while the zircaloy-4 has interesting features for the nuclear industry, such as high melting point, high thermal conductivity and low neutron absorption cross section. In this present work several routes for obtaining zircaloy-4 powder were investigated, which is a very important step for the production of plate type nuclear fuels. It was also studied the synthesis of U-Mo alloys by melting techniques. The investigated alloys have the following compositions: U-7% Mo, U-8,5% Mo and U-10% Mo. These alloys were prepared by arc and induction melting followed by heat treatments aiming to stabilize the ã phase. The results showed that regardless the melting process and alloy composition, annealing at high temperature is required for the dissolution of dendrites and homogenization of the alloy. The complete stabilization of the ã phase was achieved to the alloy with 7% Mo heat treated by annealing and quenching. The alloys with 7% and 8,5% Mo subject to slow cooling after the annealing showed of the presence of á phase into their microstructures. On the obtaining of zircaloy powder, it could be accomplished by hydriding, comminution and dehydriding techniques. Hydriding kinetics of zircaloy was faster for cold rolled samples. Cold rolling was also effective for reducing the temperature of hydride decomposition. Moreover, the high-energy ball milling process also proved effectiveness for the production of powder hydride. The results and discussions of this thesis are important to shed some light on the feasibility of the investigated processing routes for producing the metallic materials necessary to the fabrication of plate type nuclear fuels.

L'objectif de cette thèse est de développer un matériau cimentaire monolithe ayant une forte teneur en ettringite, capable de stocker et de déstocker de la chaleur, respectivement, par déshydratation endothermique et réhydratation exothermique. Une étude numérique et expérimentale du stockage de chaleur dans un réacteur thermochimique (prototype) contenant le matériau développé est aussi réalisée dans le cadre de cette étude. Pour atteindre ces objectifs, l'hydratation de différents liants ettringitiques a été suivie par DRX, ATG et MEB. Une simulation thermodynamique de l'hydratation a aussi été effectuée au moyen du logiciel GEMS (Gibbs Energy Minimization Sofware) afin d'optimiser la formulation du matériau. Le réseau poreux du matériau résultant a ensuite été amélioré par moussage chimique. Nous avons aussi étudié la durabilité et la stabilité du matériau ettringitique synthétisé (carbonatation, stabilité à la température, réversibilité du processus de stockage/déstockage sur plusieurs cycles). Pour prédire le comportement du système de stockage, un modèle bidimensionnel, prenant en compte les spécificités du matériau cimentaire, a été utilisé. Le bilan énergétique et massique dans le matériau poreux génère un système d'équations différentielles non-linéaires et couplées. La résolution numérique du système, effectuée en utilisant MatLab (r), est effectuée par discrétisation spatiale en utilisant la méthode des différences finies, et par intégration temporelle des variables d'état (température et pression de vapeur d'eau). La simulation du modèle, basée sur les propriétés mesurées du matériau en laboratoire, est ensuite utilisée comme outil de conception pour réaliser un premier prototype de réacteur thermochimique au laboratoire. Suite à ces essais, un prototype amélioré est ensuite élaboré et testé. Le résultat des essais de stockage et de déstockage de chaleur avec ces deux prototypes ont servi de validation du modèle numérique d'une part, et de preuve de concept du principe de stockage d'autre part. / The objective of this study is to develop an ettringite-based material with high energy storage density in low temperature conditions, allowing to charge and discharge heat by endothermic dehydration and exothermic rehydration, respectively; then to perform the numerical and experimental study of heat storage in a thermochemical reactor containing the produced material (prototype). To achieve these goals, the hydration of ettringite binders was followed by XRD, TGA and SEM. The thermodynamic simulation of the hydration was also performed using GEMS (Gibbs Energy Minimization Sofware). The porous network of the resulting material was improved by chemical foaming. Furthermore, the carbonation, thermal stability and reversibility tests were performed on the produced material. Physicochemical stability of the material over time was followed by XRD, TGA, SEM and IR. To predict the behavior of the storage system, a bidimensional model, taking account the specificities of the cementitious material, was developed. The heat and mass balance in the thermochemical reactor generates a system of non-linear and coupled differential equations. The numerical resolution was first made by spatial discretization using the finite difference method, then by temporal integration of variables (temperature and water vapor pressure) on MatLab (r). The model simulation, with material properties, was used as concept design to build the thermochemical reactor prototype in the laboratory (cylindrical adsorber). The result of heat storage tests with the prototype was used as proof of concept of the principle on the one hand, and a way to validate the numerical model.