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Le secteur aéronautique connaît un important essor depuis les années 1960, avec pour conséquence l’augmentation majeure des températures de fonctionnement des turbines. L’utilisation de capteurs, au plus proche de la chambre de combustion, est nécessaire pour maîtriser les performances des turboréacteurs. Cela justifie le besoin industriel de développer des assemblages céramique-métal résistants à un environnement sévère (>1100°C sous air, vibrations, etc.)L’alumine est sélectionnée en raison de son caractère isolant à haute température. La principale difficulté réside dans le choix du substrat métallique, qui doit être à la fois : réfractaire, résistant à l’oxydation, pour un coût abordable. Le potentiel d’un carbure ternaire (de type phase MAX) est évalué en tant que substrat métallique. La composition des brasures est ajustée pour chaque système afin de garantir : une tenue en température, une excellente ductilité et une compatibilité métallurgique vis-à-vis du substrat métallique.Des brasures ternaires Au-Pd-Pt sont formulées et élaborées. Les contours de solidus et de liquidus de ce ternaire sont déterminés expérimentalement. Les mécanismes de diffusion, de dissolution ou encore de pénétration inter-granulaire, à l’interface métal/brasure, sont décrits afin d’apporter des améliorations aux systèmes développés. Au cours du brasage, la diffusion de l’aluminium des substrats alumino-formeurs vers la brasure est prédominante, malgré la mise en place d’une barrière de diffusion. Le recours à des substrats métalliques nobles s’avère incontournable.Les paramètres géométriques et chimiques de l’assemblage sont établis pour chaque nouveau système étudié sur la base des processus physico-chimiques survenant au cours du brasage et du vieillissement sous air. Les meilleurs assemblages développés présentent une excellente herméticité après brasage. Les essais de vieillissement en cyclage thermique, dans des conditions sévères, sollicitent fortement la liaison céramique-brasure jusqu’à la rupture interfaciale. Deux voies d’améliorations sont proposées pour assurer la durabilité de la liaison céramique-brasure au cours du cyclage thermique. / Aerospace technology developments are blooming. Since the 1960’s the Turbine Entry Temperature for aero-engines gas turbines keeps rising to improve their efficiency. Sensors working close to the combustion chamber are required in order to master the turbine performances. This results in an industrial urge to develop ceramic-to-metal assemblies able to endure severe engine environment (>1100°C under air, vibrations, etc.)The choice of an alumina as the ceramic part ensures a good insulation at high temperature. The main issue remains the metallic material which must be refractory, resistant to oxidation and affordable. The application of a ternary carbide (phase MAX) is tested. The braze alloy composition is adjusted to each system so as to provide a good ductility, thermal stability and a metallurgical matching as regards dissolution and brittle compounds formation.Braze alloys based on the Au-Pd-Pt system are investigated. The aforesaid liquidus and solidus surfaces are defined from experimental measures. Diffusion, dissolution and inter-granular penetration at the metal/braze alloy interface are described to suggest improvements. Aluminum diffusion from alumina-forming materials towards the braze alloy is the dominant phenomenon during brazing, despite the use of a diffusion barrier. The use of noble materials for the metallic substrate is mandatory.Geometrical and chemical assembly parameters are defined for selected brazed system based on the physicochemical interactions occurring during brazing and aging under air. The best brazed assemblies present an excellent hermeticity after brazing. Thermal cycling aging in severe conditions is detrimental to ceramic-braze alloy bonding, leading to interfacial cracks. Two promising strategies are suggested to ensure a reliable ceramic-to-braze alloy bonding during thermal cycling.

Les bétons légers, formés des fibres de bois et d’une pâte de ciment Portland, constituent une nouvelle alternative à explorer pour réduire l’impact environnemental des bâtiments. Ils sont utilisés dans la construction durable, comme des éléments secondaires, pour leurs performances thermiques, hydriques et mécaniques. Cependant, la généralisation de leur utilisation dans le bâtiment ne sera rendue possible sans résoudre certains verrous scientifiques liés à leur caractérisation et à leur formulation. Le présent travail s’inscrit dans cet objectif. Il s’agit de contribuer à la caractérisation de ces bétons légers à base des fibres de bois à travers l’expérience et la modélisation. Le module d’Young et la résistance à la rupture ont été mesurés par des tests de flexion et de compression. Un modèle numérique a été également développé pour prédire le comportement des éprouvettes en flexion et la réponse structurale des systèmes de coffrage permanent. La méthodologie numérique permet ainsi d’aider dans le choix des paramètres optimums pour une meilleure conception des panneaux de coffrage destinés à la construction. L’étude du comportement hygrothermique du matériau de construction bois-ciment a été abordée en s’appuyant sur l’expérience et la simulation. Les équations des transferts couplés de chaleur et d’humidité d’un milieu poreux ont été implémentées dans le logiciel Comsol Multiphysics®. En dernier, le modèle développé a été appliqué et validé sur plusieurs réponses dynamiques issues des tests hygrothermiques réalisés en interne. Les mesures des propriétés physico-thermique du matériau composite bois-ciment ont été ensuite intégrées dans le code Abaqus via une routine utilisateur Umatht dans l’objectif de simuler le comportement thermique à hautes températures des panneaux composites bois-ciment. Les profils des températures sont évalués et comparés à ceux des tests de carbonisation réalisés, à l’aide d’un panneau rayonnant, sur des échantillons exposés à un flux de chaleur uniforme de 6kW/m2. Les simulations montrent que le modèle développé est capable de prédire les profils de températures, la zone et la profondeur de la couche du charbon durant l’exposition au feu / Lightweight concretes made from wood fibres and Portland cement paste are a new alternative for the reduction of the environmental impact of buildings. They are used in sustainable constructions as secondary elements for their thermal, hydric and mechanical performance. However, the generalisation of their use is not possible without resolving certain scientific obstacles related to their characterisation. Hence the aim of the present work, which is to contribute towards their characterisation through experimentation and numerical simulation. The Young's modulus and tensile strength were measured through flexural and compression tests. A numerical model has also been developed to predict the behaviour of specimens under bending test as well as their structural response when used as permanent formwork. In particular, the model helps to choose the optimum parameters for a better design of the formwork system. The study of the hygrothermal behaviour of the wood-cement material was carried out using both experimental work and simulation. The equations of coupled heat and moisture transfers for a porous medium have been implemented in the Comsol Multiphysics® software. The developed model has been applied and validated on several dynamic responses resulting from hygro-thermal tests carried out in the laboratory. The obtained physico-thermal properties of the wood-cement composite material were then incorporated into the Abaqus code via a Umatht user subroutine to simulate its high temperature behavior. The temperature profiles are evaluated and compared with the charring tests performed using a radiant panel on samples exposed to a uniform heat flux of 6kW/m². The simulations show that the developed model is able to predict the temperature profiles, the area and the depth of the charred layer during fire exposure

Les transferts thermiques par rayonnement dans des mousses sont modélisés à partir de la morphologie du matériau et des propriétés de sa phase solide. Dans ce travail de thèse, une attention particulière est portée sur les modèles radiatifs de Monte Carlo. Les différentes approches d’homogénéisation telles que « Homogeneous Phase » (HPA) and « Multi Phase » (MPA) sont discutées et comparées. Des développements novateurs sont proposés pour améliorer la précision des résultats. Nos avancées permettent de générer numériquement trois types de mousses périodiques couvrant un large domaine de matériaux cellulaires: mousse à pores fermés à haute porosité, mousse à cellules ouvertes à basse et haute porosité. Pour ces dernières, des comparaisons morphologiques avec des données expérimentales tomographiques, montrent des résultats satisfaisants et tendent à valider nos modèles de génération. Des mousses dont la phase solide est opaque ont tout d’abord été étudiées. Nos simulations ont permis de trouver de nouvelles lois analytiques précises permettant d’estimer les propriétés radiatives de ces matériaux à partir de données morphologiques. Ensuite, nous avons considéré des mousses, dont la phase solide est semi transparente. La modélisation du transfert radiatif au sein de ces milieux cellulaires est plus complexe. Les méthodes de modélisation des propriétés radiatives de la littérature, HPA et MPA, sont testées. Des simulations de Monte carlo directes dans les matériaux ont permis de mettre en exergue les limites de ces modèles. Des modèles novateurs ont été proposés afin d’ améliorer la précision des simulations. Ils sont basés sur une méthode hybride directe-inverse et une modification de l’équation de transfert radiatif classique. Ces nouveaux modèles (HPA+ et MPA+) ont été testés sur un ensemble varié de morphologies générées numériquement. Les modèles améliorés sont systématiquement plus précis que les modèles existants / Cellular media such as plastic, ceramic and metal foams present specific characteristics that make them interesting for a number of applications related to thermal engineering. Their ability to minimize natural convection makes them ideal candidates for insulation applications, while the high specific surface and permeability to fluid of open cell foams makes them interesting heat transfer enhancers. In addition, their permeability to light makes them an ideal candidate for thermal radiation based applications, such as porous burners or solar energy collectors. In many of these application, thermal radiation heat transfer can have a significant influence on the heat transfer process. Both accurate radiation models and accurate morphological models of the structure of the foam are required. This work provides an original contribution on both these accounts. A discussion of the literature on numerical methods for radiation heat transfer in cellular media is presented, with focus on Monte Carlo methods. Homogeneous Phase (HPA) and Multi Phase (MPA) methods are discussed. Further efforts are required to accurately model and digitally replicate of foam morphologies. Our goal is to digitally generate three commonly occurring types of foam structures, covering a large range of real materials: high-porosity open cell foams, high-porosity closed cell foams, low-porosity open-cell structures. For high-porosity open cell foams, the automated parametric digital generation technique was validated against a dataset consisting of raw morphological data obtained by tomographic analysis. The generation capabilities were then applied to parametrically investigate the influence of morphological parameters on the radiative properties (namely, the extinction coefficient) of an opaque open-cell foam. Highly accurate analytical relationships were subsequently deduced and validated by comparison with results obtained from tomography samples. Modeling radiation in foams with a semi-transparent solid phase is substantially more complex. A Direct Monte-Carlo Homogenization reference technique is proposed, that allows to simulate radiation within arbitrary cavities and calculate macroscopic radiative quantities based on a Representative Elementary Volume (REV) of cellular material. The technique is validated against full scale Monte Carlo simulations. Improvements of the existing Homogeneous Phase and Multi Phase approach are proposed, through extensive use of inverse methods and the addition of one equation to take into account specific phenomena taking place in the semi-transparent solid phase. The resulting Improved Homogenized Approaches are extensively tested by comparing them with Direct Monte Carlo Homogenization simulations and existing homogenized models, on a varied set of morphologies making full use of the previously developed digital generation techniques. The improved models consistently outperform existing homogenized models.

O composto SbxCoSb3-x foi produzido em altas pressões e altas temperaturas em uma reação de auto-inserção a partir da escuterudita binária CoSb3. A reação de auto-inserção é caracterizada pelo colapso de átomos de Sb para o sítio 2a, no interior das cavidades formadas pelos átomos de Co e Sb na estrutura da escuterudita. A reação inversa, de desinserção de Sb, ocorre quando o composto SbxCoSb3-x é aquecido à pressão ambiente. O acompanhamento desta reação de desinserção por meio de medidas de calorimetria exploratória diferencial (DSC), difração de raios X (DRX) e de resistividade elétrica constitui o objetivo principal deste trabalho. A amostra de CoSb3 foi sintetizada conforme rota proposta pela literatura. A síntese foi confirmada por meio de DRX, e não foi observada a presença de fases contaminantes. Amostras cilíndricas da fase SbxCoSb3-x foram obtidas submetendo CoSb3 a pressões de 7,7 GPa e temperaturas de até 550ºC, com o auxílio de prensas hidráulicas e câmaras toroidais disponíveis no Laboratório de Altas Pressões e Materiais Avançados LAPMA no Instituto de Física da Universidade Federal do Rio Grande do Sul IF/UFRGS. A presença da fase SbxCoSb3-x foi comprovada por meio de análises de DRX. Para determinação da resistividade elétrica de amostras ricas de fase SbxCoSb3-x foi desenvolvido um sistema DC, aplicável a amostras cilíndricas de pequeno volume tal como as obtidas em altas pressões e altas temperaturas. A aferição do sistema foi feita através de medidas de resistividade elétrica de materiais de referência (NIST-SRM 1461 e NIST-SRM 8426). As medidas de DSC revelaram a presença de dois eventos térmicos. Um pico endotérmico foi observado em 118ºC e não está associado a alterações estruturais e nem a variações significativas na resistividade elétrica. O evento exotérmico, que inicia em 180ºC, constitui a assinatura da desinserção dos átomos de Sb do interior da escuterudita, como verificado por análises de DRX e medidas elétricas. Após aquecimento até 350ºC, a amostra rica na fase SbxCoSb3-x retorna à fase estável, CoSb3. A reação de desinserção obedece a uma cinética de primeira ordem, cuja entalpia de transição é de aproximadamente 50 J /g e uma energia de ativação de 83 kJ/mol. A resistividade elétrica à temperatura ambiente de amostras ricas em SbxCoSb3-x é cerca de dez vezes inferior à do CoSb3. Este resultado, aliado possivelmente a uma baixa condutividade térmica, sugere que a fase de auto-inserção SbxCoSb3-x pode constituir um material termoelétrico de alto desempenho. / Submitted by Marcelo Teixeira (mvteixeira@ucs.br) on 2014-06-03T19:52:12Z No. of bitstreams: 1 Dissertacao Fernanda Miotto.pdf: 1202367 bytes, checksum: b66708b3e1d417eab6ba5104702a3458 (MD5) / Made available in DSpace on 2014-06-03T19:52:12Z (GMT). No. of bitstreams: 1 Dissertacao Fernanda Miotto.pdf: 1202367 bytes, checksum: b66708b3e1d417eab6ba5104702a3458 (MD5) / The compound SbxCoSb3-x was produced at high pressures and high temperatures in a self-insertion reaction from the binary skutterudite CoSb3. The self-insertion reaction is characterized by the collapse of Sb atoms to the 2a site, into the cage formed by the Co and Sb atoms in the skutterudite structure. The opposite reaction, i.e., Sb desinsertion, occurs when the SbxCoSb3-x compound is heated at room pressure. This desinsertion reaction was followed by means of differential scanning calorimetry (DSC), X-ray diffraction (XRD) and electrical resistivity measurements, and its study constitutes the main objective of this work. The CoSb3 sample was synthesized as described in the literature. The synthesis was confirmed by XRD, and the presence of contaminant phases was not observed. Cylindrical samples of the SbxCoSb3-x phase were obtained by submitting CoSb3 at pressures of 7.7 GPa and temperatures up to 550ºC, with the aid of a toroidal high pressure cell available at the Laboratório de Altas Pressões e Materiais Avançados - LAPMA in the Instituto de Física of the Universidade Federal do Rio Grande do Sul - IF/UFRGS. The presence of the SbxCoSb3-x phase was confirmed by XRD analysis. In order to determine the electrical resistivity of samples rich in SbxCoSb3-x phase, a DC system was developed which is applicable to small volume cylindrical samples such as those obtained at high pressures and high temperatures. The calibration of the DC system was made by measurements of the electrical resistivity of reference materials (NIST-SRM 1461 and NIST-SRM 8426). The DSC measurements revealed the presence of two thermal events. An endothermic peak was observed at 118ºC which is not associated to structural changes neither significant variation in the electrical resistivity. The exothermic event that starts at 180ºC is the signature of the desinsertion of Sb atoms from the skutterudite cage, as verified by XRD analysis and electrical measurements. After heating to 350°C, the sample rich in the SbxCoSb3-x phase converts back to the stable phase, CoSb3. The desinsertion reaction follows a first-order kinetics, with a transition enthalpy of approximately 50 J/g and an activation energy of 83 kJ/mol. The electrical resistivity at room temperature of samples rich in SbxCoSb3-x is about ten times smaller than that of CoSb3. This result, along with a possible low thermal conductivity, suggests that SbxCoSb3-x may constitute a high performance thermoelectric material.

O composto SbxCoSb3-x foi produzido em altas pressões e altas temperaturas em uma reação de auto-inserção a partir da escuterudita binária CoSb3. A reação de auto-inserção é caracterizada pelo colapso de átomos de Sb para o sítio 2a, no interior das cavidades formadas pelos átomos de Co e Sb na estrutura da escuterudita. A reação inversa, de desinserção de Sb, ocorre quando o composto SbxCoSb3-x é aquecido à pressão ambiente. O acompanhamento desta reação de desinserção por meio de medidas de calorimetria exploratória diferencial (DSC), difração de raios X (DRX) e de resistividade elétrica constitui o objetivo principal deste trabalho. A amostra de CoSb3 foi sintetizada conforme rota proposta pela literatura. A síntese foi confirmada por meio de DRX, e não foi observada a presença de fases contaminantes. Amostras cilíndricas da fase SbxCoSb3-x foram obtidas submetendo CoSb3 a pressões de 7,7 GPa e temperaturas de até 550ºC, com o auxílio de prensas hidráulicas e câmaras toroidais disponíveis no Laboratório de Altas Pressões e Materiais Avançados LAPMA no Instituto de Física da Universidade Federal do Rio Grande do Sul IF/UFRGS. A presença da fase SbxCoSb3-x foi comprovada por meio de análises de DRX. Para determinação da resistividade elétrica de amostras ricas de fase SbxCoSb3-x foi desenvolvido um sistema DC, aplicável a amostras cilíndricas de pequeno volume tal como as obtidas em altas pressões e altas temperaturas. A aferição do sistema foi feita através de medidas de resistividade elétrica de materiais de referência (NIST-SRM 1461 e NIST-SRM 8426). As medidas de DSC revelaram a presença de dois eventos térmicos. Um pico endotérmico foi observado em 118ºC e não está associado a alterações estruturais e nem a variações significativas na resistividade elétrica. O evento exotérmico, que inicia em 180ºC, constitui a assinatura da desinserção dos átomos de Sb do interior da escuterudita, como verificado por análises de DRX e medidas elétricas. Após aquecimento até 350ºC, a amostra rica na fase SbxCoSb3-x retorna à fase estável, CoSb3. A reação de desinserção obedece a uma cinética de primeira ordem, cuja entalpia de transição é de aproximadamente 50 J /g e uma energia de ativação de 83 kJ/mol. A resistividade elétrica à temperatura ambiente de amostras ricas em SbxCoSb3-x é cerca de dez vezes inferior à do CoSb3. Este resultado, aliado possivelmente a uma baixa condutividade térmica, sugere que a fase de auto-inserção SbxCoSb3-x pode constituir um material termoelétrico de alto desempenho. / The compound SbxCoSb3-x was produced at high pressures and high temperatures in a self-insertion reaction from the binary skutterudite CoSb3. The self-insertion reaction is characterized by the collapse of Sb atoms to the 2a site, into the cage formed by the Co and Sb atoms in the skutterudite structure. The opposite reaction, i.e., Sb desinsertion, occurs when the SbxCoSb3-x compound is heated at room pressure. This desinsertion reaction was followed by means of differential scanning calorimetry (DSC), X-ray diffraction (XRD) and electrical resistivity measurements, and its study constitutes the main objective of this work. The CoSb3 sample was synthesized as described in the literature. The synthesis was confirmed by XRD, and the presence of contaminant phases was not observed. Cylindrical samples of the SbxCoSb3-x phase were obtained by submitting CoSb3 at pressures of 7.7 GPa and temperatures up to 550ºC, with the aid of a toroidal high pressure cell available at the Laboratório de Altas Pressões e Materiais Avançados - LAPMA in the Instituto de Física of the Universidade Federal do Rio Grande do Sul - IF/UFRGS. The presence of the SbxCoSb3-x phase was confirmed by XRD analysis. In order to determine the electrical resistivity of samples rich in SbxCoSb3-x phase, a DC system was developed which is applicable to small volume cylindrical samples such as those obtained at high pressures and high temperatures. The calibration of the DC system was made by measurements of the electrical resistivity of reference materials (NIST-SRM 1461 and NIST-SRM 8426). The DSC measurements revealed the presence of two thermal events. An endothermic peak was observed at 118ºC which is not associated to structural changes neither significant variation in the electrical resistivity. The exothermic event that starts at 180ºC is the signature of the desinsertion of Sb atoms from the skutterudite cage, as verified by XRD analysis and electrical measurements. After heating to 350°C, the sample rich in the SbxCoSb3-x phase converts back to the stable phase, CoSb3. The desinsertion reaction follows a first-order kinetics, with a transition enthalpy of approximately 50 J/g and an activation energy of 83 kJ/mol. The electrical resistivity at room temperature of samples rich in SbxCoSb3-x is about ten times smaller than that of CoSb3. This result, along with a possible low thermal conductivity, suggests that SbxCoSb3-x may constitute a high performance thermoelectric material.

Ce mémoire est constitué de deux parties relativement indépendantes, dont la première partie porte sur les méthodes de mesure de température par méthodes Multi-Spectrales (pyrométrie optique passive), et la seconde sur la Caractérisation Thermique à haute température par transformations intégrales de matériaux orthotropes. Dans chacune de ces deux parties, les méthodes/modèles développés ont été traités du point de vue théorique, numérique, et expérimental. Dans la partie multi-spectrale, une méthode de mesure de température permettant de prendre en compte les variations spectrales de la chaine de mesure globale (incluant l’émissivité) a été présentée. De plus, une méthode de détermination des longueurs d’ondes optimales au sens de la minimisation de l’écart-type sur la température, a été développée. Enfin, il a également été montré que les longueurs d’ondes optimales pour les mesures mono-spectrales et bi-spectrales pouvaient être déterminées à l’aide de lois analogues à la loi de déplacement de Wien. Dans la partie Caractérisation Thermique, différentes méthodes et modèles ont été développés. Les méthodes proposées effectuent l’estimation des diffusivités longitudinales et transversales sur l’ensemble des harmoniques simultanément. De plus, ces méthodes permettent de s’affranchir du couplage thermique dû à la présence d’un porte-échantillon, et/ou d’effectuer des mesures de diffusivités pseudo-locales, en injectant comme conditions aux limites les informations expérimentales obtenues par caméra infrarouge. Enfin, les notions de corrélation entre les paramètres et de durée d’exploitabilité des harmoniques ont également été abordées / This thesis consists of two relatively independent parts, the first part focuses on methods of temperature measurement using Multi-Spectral (passive optical pyrometry) methods, and the second on the Thermal Characterization by integral transforms at high temperature of orthotropic materials. In each of these two parts, methods / models developed were treated from a theoretical point of view, numerical and experimental. In the multi-spectral part, a method of temperature measurement to take into account a spectral variation of the overall measurement chain (including the emissivity) was introduced. Moreover, a method of determining the optimal wavelengths in the sense of minimizing the standard deviation of temperature, has been developed. Finally, it has also been shown that the optimal wavelengths for mono-spectral and bi-spectral measurements could be determined with similar laws to Wien's displacement law. In the Thermal Characterization part, different methods and models have been developed. The proposed methods perform the estimation of longitudinal and transverse diffusivities on all harmonics simultaneously. Furthermore, they allow overcoming the thermal coupling due to the presence of a sample holder, and / or making pseudo-local measurements of diffusivities. Finally, the concepts of correlation between parameters and duration of harmonics exploitability were also discussed.This thesis consists of two relatively independent parts, the first part focuses on methods of temperature measurement using Multi-Spectral (passive optical pyrometry) methods, and the second on the Thermal Characterization by integral transforms at high temperature of orthotropic materials. In each of these two parts, methods / models developed were treated from a theoretical point of view, numerical and experimental. In the multi-spectral part, a method of temperature measurement to take into account a spectral variation of the overall measurement chain (including the emissivity) was introduced. Moreover, a method of determining the optimal wavelengths in the sense of minimizing the standard deviation of temperature, has been developed. Finally, it has also been shown that the optimal wavelengths for mono-spectral and bi-spectral measurements could be determined with similar laws to Wien's displacement law. In the Thermal Characterization part, different methods and models have been developed. The proposed methods perform the estimation of longitudinal and transverse diffusivities on all harmonics simultaneously. Furthermore, they allow overcoming the thermal coupling due to the presence of a sample holder, and / or making pseudo-local measurements of diffusivities. Finally, the concepts of correlation between parameters and duration of harmonics exploitability were also discussed

This study shows how the composition of gases released from a single magmatic source may be modified during their ascending path. The main processes that influence the composition of the gases in these high temperature fumarolic environments, are: 1) interactions with wallrocks during gas ascent, which change the fugacities of the metal volatile species and affect the equilibrium between major species (fH2S/fSO2; fH2/fH2O); 2) mixing with meteoric water with consequent Cl adsorption, which may account for the Cl depletion of the gases; 3) remobilisation of previously formed sublimates and/or incrustation deposits. Comparison between the thermochemical models and the mineralogical composition of the silica tubes at Kudryavy and Satsuma-Iwojima volcanoes suggests that high fO2 due to the mixing of the gases with air during their injection into the atmosphere significantly reduces the volatility of several trace elements (As, Sb, Sn, Na, K, Tl, Te, Se and Cd). Comparisons between the enriched metals in aerosols and in the gases suggest that Mo, Pb, Bi, Na, K, Cu, Zn or Fe, which are enriched in the gases, are preferentially deposited in the gas conduits and vents whereas the highly volatile metals (Te, Tl, Sb, As and Se) and Cd condense in the plume.<p>This study determines the reactions that may occur during the alteration of rocks in high temperature fumarolic environments. Three different processes of alteration prevail: <p>(1) Acidic alteration which is characterized by the complete absence of clays, because the constant supply of gases to these systems allows for the pH values of the acidic fluids to be maintained low enough to prevent the precipitation of clay minerals. Complete leaching of all cations, except Si, from the primary silicates leads to important "silicification" of the wall rock. The primary mineral cations are leached in the following order: K, Na > Ca > Fe, Mg > Al > Si, Ti. The fluids enriched in these cations circulate in microcracks at different temperatures and different redox conditions and lead to the precipitation of secondary incrustations. At Kudryavy the incrustations are mainly sulfates. At Usu the lower sulfur/fluoride ratio of the gases allows the occurrence of aluminum fluoride incrustations. The order of primary minerals dissolution (olivine > plagioclase > pyroxene > matrix glass > Fe-Ti oxides) is established for both sites studied. <p>(2) Alteration by an oxidized volcanic gas, resulting from mixing with the atmosphere (500 to 300°C). At Kudryavy, thermochemical modeling suggests that anhydrite and anhydrous sulfates, which occur at intermediate temperatures, are formed by interactions of the rock with oxidized gas. <p>(3) The most important outcome of this work is the identification of the features of alteration by the volcanic gas that directly reacts with the rock at high temperatures (T > 500°C). The Kudryavy rocks show evidences for mineral transformations, which occur in the presence of the volcanic gas phase. Volcanic gas directly reacts with rocks at high temperatures (T > 500°C). The gas destabilizes the primary minerals, remobilizes the rock-bearing cations, and leads to the formation of second mineral assemblages. These transformations occur in situ, without significant mobility (gain or loss) of the cations. The high temperature secondary associations are characterized by the presence of andradite, hedenbergite, hercynite, tridymite/cristobalite. Anhydrite and anhydrous Al sulfate may occur within these mineral assemblages if the gas is oxidized.<p> / Doctorat en sciences, Spécialisation géologie / info:eu-repo/semantics/nonPublished

Master`s thesis is divided in to two parts, practical and theoretical. In theoretical part are listed basic information’s about light weight concrete, special emphasis are given to characteristic and practical application of compact light weight concrete with Liapor aggregates. In this study is described influence of high temperature on concrete structure and chemical, mechanical and physical changes, which take place during exposal to high temperatures. Further is evaluated surface permeability of concrete and addition of polypropylene fibres to concretes resistive to high temperatures. The practical part deals with design, production and testing of cement based concrete with use of different aggregates (light weight aggregates Liapor, basalt). The properties and use for applications in high temperatures is also mentioned. The influence of high temperature on strength, absorption, thermal conductivity, changes of surface permeability and degradation of testing specimens due to heat loads according to normative heat curve (ISO 834). For better transparency are experimental tests divided in to five phases and the measured values are evaluated on the end of each phase. In conclusion are resumed all knowledge’s obtained by testing and evaluated the most suitable formulation. The approach for further research is also mentioned.