Programa Internacional de Becas da FundaÃÃo Ford / O processamento de materiais cerÃmicos, que envolve a queima de tijolos e demais produtos das indÃstrias cerÃmicas vermelhas, està associado à liberaÃÃo de componentes gasosos e material particulado que em fortes concentraÃÃes podem prejudicar o meio-ambiente e principalmente a saÃde humana, uma vez que os gases emitidos por estas indÃstrias, na maioria das vezes, nÃo sÃo tratados antes de serem lanÃados à atmosfera. O escopo desta pesquisa foi desenvolver um suporte cerÃmico visando, principalmente, à remoÃÃo de material particulado da indÃstria cerÃmica vermelha. Para sua obtenÃÃo foi usado resÃduo de terra diatomÃcea, ignimbrita (Sillar), e como aglomerante a bentonita, as quais possuem aproximadamente 70% a 80% de sÃlica. A sÃlica apresentando-se sob duas formas cristalinas: quartzo e cristobalita. O resÃduo, terra diatomÃcea, coletado em uma indÃstria cervejeira, foi submetido a um tratamento tÃrmico para a eliminaÃÃo da matÃria orgÃnica absorvida durante a etapa de filtraÃÃo. As matÃrias-primas foram submetidas a uma anÃlise quÃmica e mineralÃgica mediante FluorescÃncia de raios X e DifraÃÃo de raios X. Para a fabricaÃÃo do suporte cerÃmico foram preparadas espumas cerÃmicas pelo mÃtodo da replica. As espumas polimÃricas foram imersas na suspensÃo (diatomita, ignimbrita, bentonita e Ãgua), secas e tratadas termicamente. A eliminaÃÃo da espuma cerÃmica polimÃrica ocorreu a 400ÂC e, em seguida, o corpo cerÃmico foi sinterizado a 1100ÂC, em um intervalo de tempo compreendido de 45 e 60 min. Foram testadas quatro formulaÃÃes com duas variÃveis: tamanho de grÃo e composiÃÃo. A formulaÃÃo quatro (10% de diatomita e 16% de ignimbrita), foi a mais Ãtima, com uma resistÃncia mecÃnica à compresao de 0,8 MPa e uma porosidade de 81%. A reduÃÃo de material particulado, apÃs o uso do suporte cerÃmico, foi de aproximadamente 84% e de 72% de monÃxido de carbono, estando dentro dos padrÃes estabelecido pela ResoluÃÃo nÂ382/2006 do CONAMA. / The processing of ceramic materials which involves burning of the bricks and other ceramic product red ceramic industries is associated with the release of gaseous components and particulate material in high concentrations that affect the environment and human health, considering that the gases emitted by these industries are not mostly treated before being released to the atmosphere. The purpose of this research was to develop a ceramic support with the main objective of the removal of particulate matter. Was used diatomaceous earth residue, ignimbrita (Sillar) and the bentonite as a binder, which possess a high amount of silica. The silica exists in two crystalline forms: quartz, cristobalite. The residue, diatomaceous earth, collected in a beer industry, was submitted to a thermal treatment for the elimination organic matter absorbed during filtration. The raw materials were subjected to chemical and mineralogical analysis by XRF and XRD. Were processed by the replication method. The Polymeric foams were immersed in the ceramic suspension (diatomite, ignimbrita, bentonite and water), and then dried and heat-treated for consolidation. The polymer foam was burned out at 400 ÂC and sintering was carried out at 1100 ÂC for 45 - 60 min. We‟re working four formulations with two variables, grain size and composition. The four formulations (10% diatomite and 16% ignimbrita) was more excellent, mechanical strength compresao of 0,8MPa and porosity of 81%. The reduction of particulate matter after using the ceramic support was approximately 84% and carbon monoxide was 72% is within the standards established by the Resolution nÂ382/2006 do CONAMA.

Le projet Européen UNIfHY a vu le jour dans une optique de production d’hydrogène à partir de biomasse pour le remplacement des énergies fossiles. La purification des gaz produits par la gazéification de la biomasse permet l’obtention d’hydrogène pur pour une utilisation dans les piles à combustible. Cette thèse s’inscrit dans ce projet avec pour but le développement de catalyseurs Fe/CeO2 et Cu/CeO2 déposés sur des supports de mousse céramique pour la réaction de conversion du gaz à l’eau à haute et basse températures, de manière à augmenter la production d’hydrogène et diminuer la perte de charge dans le système. Les principaux objectifs de la thèse sont la synthèse et les caractérisations des catalyseurs à base de fer et de cuivre, l’optimisation des conditions réactionnelles dans la limite du cadre fixé par le projet, la modélisation cinétique en présence des catalyseurs Fe/CeO2 et Cu/CeO2 et la transposition à grande échelle des catalyseurs pour une utilisation en réacteur pilote. / The UNIfHY European project was launched in an optic of producing hydrogen from biomass to replace fossil fuels. Purification of gases produced by biomass gasification allows obtaining pure hydrogen which can be used in fuel cells. This thesis takes part in this project with the development of Fe/CeO2 and Cu/CeO2 catalysts deposited on ceramic foam supports for high temperature and low temperature water gas shift reaction to increase the production of hydrogen and decrease the pressure drop in the system. The main objectives of this thesis are the synthesis and characterizations of iron and copper based catalysts, the optimization of reaction conditions within the limits of the framework set by the project, the kinetic modeling of the reaction in the presence of Fe/CeO2 and Cu/CeO2 catalysts and the scale-up of catalysts to use them in a pilot reactor.

Les matériaux cellulaires sont des échantillons à très forte porosité qui peuvent être décrits à deux échelles : la mésostructure et la microstructure. Le lien entre l'architecture des matériaux et les propriétés mécaniques a été largement étudié dans la littérature. Les caractéristiques microstructurales peuvent avoir une influence importante sur les propriétés macroscopiques. Le but de ce travail est de relier les caractéristiques architecturales et microstructurales des matériaux cellulaires à leurs propriétés mécaniques grâce notamment à la tomographie aux rayons X. Une nouvelle approche combinant l'imagerie 3D à plusieurs résolutions, le traitement d'images et la modélisation éléments finis a permis de prendre en compte la microstructure de la phase solide. Quatre matériaux cellulaires modèles ont ainsi été étudiés : des mousses d'aluminium, des structures cellulaires périodiques en alliage de cobalt-chrome, des échantillons de β-TCP et des composites hydroxyapatite/β-TCP. Les matériaux métalliques ont été fournis par des collègues d'autres laboratoires, tandis que les matériaux céramiques ont été fabriqués dans le cadre de cette étude. Pour chaque type de matériaux (métaux et céramiques), une structure régulière et une stochastique ont été comparées. Pour utiliser la méthode multi-échelle développée dans ce travail, les échantillons ont d'abord été scannés grâce à la tomographie locale dans laquelle l'échantillon est placé près de la source de rayons X. La tomographie locale permet de scanner la petite partie irradiée de l'échantillon et d'obtenir une image agrandie par rapport aux images à plus basse résolution. Ces images permettent d'observer certains détails de la phase solide non visibles à plus basse résolution. Différentes étapes de traitement d'images ont ensuite été mises en œuvre pour obtenir une image à basse résolution incluant les informations provenant des images à haute résolution. Ceci a été réalisé grâce à une série d'opération de seuillage et sous-résolution des images à haute résolution. Le résultat de ces différentes étapes de traitement d'images donne une image de l'échantillon initial à basse résolution mais qui inclut l'information supplémentaire décelée à haute résolution. Ensuite, des essais mécaniques in situ ont été réalisés dans le tomographe pour suivre à basse résolution l'évolution des échantillons pendant la déformation. Les images initiales citées plus haut ont été utilisées pour produire des maillages éléments finis. Des programmes Java ont été adaptés pour créer des fichiers d'entrée pour les modèles éléments finis à partir des images initiales et des maillages. Les images initiales contenant les informations à propos de la phase solide, les images des essais mécaniques et les modèles éléments finis ont permis d'expliquer le comportement mécanique des échantillons en reliant les sites d'endommagement expérimentaux et les lieux de concentrations de contraintes calculés. / Cellular materials are highly porous systems for which two scales are mainly important: the mesostructure and the microstructure. The mesostructure corresponds to the architecture of the materials: distribution of solid phase “walls” and macroporosity and can be characterized by X-ray tomographic low resolution images. The link between the architecture of the materials and the mechanical properties has been frequently studied. The microstructure refers to the characteristics of the solid phase. Its microstructural features (presence of a secondary phase or of defects due to the sintering) can have a strong influence on the macroscopic properties. The aim of this work is to link the morphological and microstructural features of metallic and ceramic based cellular materials and their mechanical properties thanks to X-ray tomography and finite element modelling. A new method combining X-ray tomography at different resolutions, image processing and creation of finite element modelling enabled to take into account some microstuctural features of the cellular samples. Four different cellular materials were studied as model materials: aluminium foam fabricated by a liquid state process, cobalt periodic structures made by additive manufacturing, β-TCP porous samples fabricated by conventional sacrificial template processing route and hydroxyapatite/β-TCP composites made by additive manufacturing (robocasting). The metal based materials were provided by colleagues while the ceramic based porous materials were fabricated in the frame of the current study. For each type (metals or ceramics), a stochastic and a regular structure have been compared. For implementing the multiscale method developed in this work, the samples were firstly scanned in a so called “local” tomography mode, in which the specimen is placed close to the X-ray source. This allowed to reconstruct only the small irradiated part of the sample and to obtain a magnified image of a subregion. These images enable to observe some details which are not visible in lower resolution. Different image processing steps were performed to generate low resolution images including microstructural features imaged at high resolution. This was done by a series of thresholding and scaling of the high resolution images. The result of these processing steps was an image of the initial sample. Then, in situ mechanical tests were performed in the tomograph to follow the deformation of the sample at low resolution. The above mentioned initial images were used to produce finite element meshes. Special Java programs were adapted to create finite element input files from initial images and meshes. The initial images containing information about the solid phase, the images from the mechanical tests and the finite element models were combined to explain the mechanical behaviour of the sample by linking the experimental damage locations in the sample and the simulated stress concentration sites.