This thesis deals with the problem of no-cement corundum refractory castables. In the theoretical part, it focuses on NCC refractory and its use, production technology and input raw materials. The second part of the theoretical work deals with MgAl2O4 spinel. The practical part of the thesis then continues in the topic and focuses on cement-free refractory concrete and the influence of MgO content on their properties.

Doctoral thesis is focused on the study, research and development of heat insulating moulded refractory materials. The replacement of shaped instead of unshaped refractories is recently and strongly industrially demanded and belongs to ongoing research topics. With the increasing demand of energy savings, the excellent insulation properties are essential. The insulating properties of castables are the result of targeted porosity formation. The porosity is coming from the controlled air intrusion into material resulted to foamed structure. The foaming process was achieved by mixing of separately prepared aqueous foam into raw castable slurry or by in situ foaming of intensively mixed castable slurry with the surfactant additive. Nevertheless, the study of foam behaviour and the influence of additives on binder hydration and setting processes (i.e. calciumaluminate cement) was substantial for successful preparation of the experimental samples. The two types of the experimental samples were prepared. The first one was based on mixing of kaolin slurry with pre-prepared aqueous foam, whereas the de-aglomeration ability of kaolin specie was utilized to water-particle film formation. In situ foaming of multicomponent system is the second one. The both processes brought some negative attributes, so the optimal properties of prepared castables were achieved by their combination.

O amortecimento, fenômeno pelo qual energia mecânica em um sistema dinâmico é dissipada, é uma das propriedades mais sensíveis dos materiais quanto a presença de trincas e microtrincas. O estudo do amortecimento já é bem estabelecido em áreas como engenharia civil, em que é de importância na resistência mecânica de um sistema sujeito a abalos sísmicos e vibrações, porém vem sendo cada vez mais estudado na indústria de materiais para analisar e quantificar o dano em concretos refratários que sofrem ciclos de choque térmico. Este trabalho apresenta uma metodologia e algoritmo para a determinação do amortecimento das ressonâncias de um material, para avaliação de danos em concretos refratários, através da análise espectral de tempo-frequência. São também apresentados os resultados obtidos para um sinal simulado, uma barra de alumina densa e um par de barras de concreto refratário comercial de alta alumina, sendo uma com e outra sem dano por choque térmico. Com o uso do método foi possível recuperar o valor do amortecimento e a frequência usada para gerar o sinal simulado. O resultado apresentado para a alumina é compatível com o valor encontrado em literatura e, com o resultado obtido para os concretos refratários, foi possível mostrar o potencial de aplicação do método para caracterização de dano, sendo significativa a diferença do amortecimento do concreto com dano para o concreto sem dano. / Damping, phenomenon by which mechanical energy is reduced in dynamic systems, is one of the most sensible properties of materials in relation to the presence of cracks and micro-cracks. The study of the damping is well stablished in areas such as civil engineering, where it has fundamental importance in the mechanical resistance of a system exposed to seismic waves or vibration, although it is beginning to be used more often in the material industry to analyze and quantify the damage in castables that suffered thermal-shock cycles. This work presents a methodology and an algorithm to determine the resonances damping factors of a material, to evaluate the damage caused by thermal shock in castables, through the use of time-frequency spectral analysis. Results are presented for a simulated signal, an alumina beam, a pair of commercial high alumina with low-aggregate content castable, a pair of high alumina with high-aggregate content castable and a pair of silico-aluminous castable impregnated with coke. Each pair contains one sample with damage through thermal-shock cycle(s) and the other without. By using this method it was possible to retrieve the damping value and frequency used to generate the simulated signal. The result for the alumina beam was in accordance to the literature values and, with the results achieved for the castables, it was possible to expose the potential application of the method to characterize damage: there were a considerable difference between the damping value of the castables with and without damages.

O amortecimento, fenômeno pelo qual energia mecânica em um sistema dinâmico é dissipada, é uma das propriedades mais sensíveis dos materiais quanto a presença de trincas e microtrincas. O estudo do amortecimento já é bem estabelecido em áreas como engenharia civil, em que é de importância na resistência mecânica de um sistema sujeito a abalos sísmicos e vibrações, porém vem sendo cada vez mais estudado na indústria de materiais para analisar e quantificar o dano em concretos refratários que sofrem ciclos de choque térmico. Este trabalho apresenta uma metodologia e algoritmo para a determinação do amortecimento das ressonâncias de um material, para avaliação de danos em concretos refratários, através da análise espectral de tempo-frequência. São também apresentados os resultados obtidos para um sinal simulado, uma barra de alumina densa e um par de barras de concreto refratário comercial de alta alumina, sendo uma com e outra sem dano por choque térmico. Com o uso do método foi possível recuperar o valor do amortecimento e a frequência usada para gerar o sinal simulado. O resultado apresentado para a alumina é compatível com o valor encontrado em literatura e, com o resultado obtido para os concretos refratários, foi possível mostrar o potencial de aplicação do método para caracterização de dano, sendo significativa a diferença do amortecimento do concreto com dano para o concreto sem dano. / Damping, phenomenon by which mechanical energy is reduced in dynamic systems, is one of the most sensible properties of materials in relation to the presence of cracks and micro-cracks. The study of the damping is well stablished in areas such as civil engineering, where it has fundamental importance in the mechanical resistance of a system exposed to seismic waves or vibration, although it is beginning to be used more often in the material industry to analyze and quantify the damage in castables that suffered thermal-shock cycles. This work presents a methodology and an algorithm to determine the resonances damping factors of a material, to evaluate the damage caused by thermal shock in castables, through the use of time-frequency spectral analysis. Results are presented for a simulated signal, an alumina beam, a pair of commercial high alumina with low-aggregate content castable, a pair of high alumina with high-aggregate content castable and a pair of silico-aluminous castable impregnated with coke. Each pair contains one sample with damage through thermal-shock cycle(s) and the other without. By using this method it was possible to retrieve the damping value and frequency used to generate the simulated signal. The result for the alumina beam was in accordance to the literature values and, with the results achieved for the castables, it was possible to expose the potential application of the method to characterize damage: there were a considerable difference between the damping value of the castables with and without damages.

Refractory materials are irreplaceable in all industrial fields where it is necessary to use high temperatures. This paper deals with the use of metakaolin in refractory materials that allows the operation of such facilities. In recent decades has the development made significant progress in quality parametres, which extended life period of refractory materials in their use and significantly decreased the specific consumption of refractory materials in various technologies. This phenomenon is also called "harakiri effect". At the same time a constant pressure to the lowest prices of products is on the refractory market. Metakaolin seems to be appropriate raw material, which may help to achieve interesting qualitative effects. It may affect many properties of the influence on the behavior of materials during processing, through physico-mechanical parameters and dipping to the economic efficiency of production.

Ces travaux de thèse visent à trouver des solutions pour minimiser autant que possible la présence de microporosités dans les alliages aéronautiques conventionnels et nouveaux. Ces microporosités résultent notamment de la réaction de l’aluminium liquide, durant la phase de coulée, avec l’hydrogène apportée par la vapeur d’eau contenue dans les réfractaires. La plupart de ces produits sont des bétons hydrauliques à matrice cimentaire alumineuse. Dans une première étape, l’identification physico-chimique et minéralogique des matériaux et des produits élaborés a été réalisée. Le comportement thermo-hydrique de différentes de bétons et de pâtes cimentaires durcies a ensuite été étudié par des essais de reprise d'humidité réalisés dans diverses conditions hygrothermiques, y compris à températures élevées (300°C). On montre ainsi que les variations hydriques dépendent fortement de la nature du liant, en particulier de sa teneur en alumine. Les phénomènes de physisorption et chimisorption sont mobilisés. Parallèlement, le comportement thermique d'une goulotte réfractaire a été modélisé, première étape pour quantifier les transferts de vapeur d’eau au sein des matériaux. Des mesures continues de température et de pression ont été obtenues sur des éprouvettes de pâtes et de bétons diversement conditionnées, placées au contact d’une frette métallique maintenue à 700°C. D’autres mesures ont été faites. Elles ont consisté à immerger des échantillons (pâtes et bétons), préalablement conservés dans différentes conditions hygrothermiques, dans l’aluminium liquide, afin de comparer leur réactivité en termes de relargage d’hydrogène, d’oxygène et de vapeur d’eau / This thesis aims to find solutions to minimize as much as possible the presence of micro-porosities in conventional and new aerospace alloys. These micro-porosities resulting especially from the reaction of the molten aluminum, during the casting phase, with the hydrogen provided by the steam contained in the refractory castables. Most of these castables are composites obtained with hydraulic binders based on aluminous cements. Firstly, a physico-chemical and mineralogical characterization of the basic materials and processed products was performed. Then, the thermo-hydric behavior of different castables and hardened cement pastes (principal source of the physical water and the chemical water) was then studied by moisture pick up tests made in various hygrothermal conditions, including at high temperatures (300 °C). It was shown that the hydric variations amplitudes strongly depend on the binder’s nature, in particular on its alumina content. The phenomena of physisorption and chemisorption are mobilized. Meanwhile, the transient thermal behavior in the time through the thickness of a refractory launder was modeled as a first step to quantify the water vapor transfer in the materials. Continuous measurements of temperature and pressure were obtained on pastes and concretes samples variously packged, placed in contact with a heated metal band maintained at 700 °C. Other measurements were made. They consisted into immersing samples (cement pastes and castables), previously stored in different hygrothermal conditions in liquid aluminum, in order to compare their reactivity in terms of release of hydrogen, oxygen and water vapor