L’objectif de cette thèse est de développer des outils et des procédures pour l’approche par lamicro-cinétique expérimentale, de la réaction CO/O2 appliquée aux catalyseurs à base d’iridium et departicules bimétalliques Pt-Pd supportées sur alumine. La caractérisation de la première étape cléd’adsorption du réactif CO sur différents métaux (type d’adsorption, chaleurs d’adsorption de chaqueespèce) a nécessité le développement d’une méthode initialement adaptée à l’analyse IR en modetransmission dite méthode AEIR (Adsorption Equilibrium InfraRed spectroscopy). Les conditionsexpérimentales permettant une exploitation quantitative des spectres IR en mode réflexion diffuse ontété déterminées pour l’utilisation de la méthode AEIR. Cette méthode a ensuite été développée enétendant son domaine d’application à des catalyseurs reconnus comme dissociant fortement le COd’une part en mode réflexion diffuse pour des catalyseurs ne pouvant être étudiés en modetransmission (Fe/Al2O3) et d’autre part en mode transmission (Co/Al2O3). L’impact des paramètres liésà la préparation du catalyseur (nature du support, dispersion de la phase métallique et formation departicules bimétalliques) sur les chaleurs d’adsorption a ensuite été évalué sur des catalyseurs à based’iridium et des catalyseurs tels que Pt-Pd, Pt-Cu respectivement. Enfin l’approche micro-cinétique dela réaction CO/O2 appliquée aux catalyseurs à base d’iridium et de particules bimétalliques Pt-Pd, viaune étude par oxydation isotherme des espèces CO adsorbées à basses températures, a montré que lesétapes superficielles impliquées étaient similaires à celles sur platine et palladium. Les impacts dedivers paramètres expérimentaux sur l’oxydation des espèces CO adsorbées caractérisée par unepériode d’induction sont qualitativement identiques, seuls les paramètres cinétiques tels que l’énergied’activation apparente de la réaction sont modifiés. / The aim of this thesis is to develop tools and procedures to study by the experimentalmicrokinetic approach, in particular for the CO/O2 reaction applied to metal supported catalystcontaining iridium particles and bimetallic Pt-Pd particles. The characterization of the first elementarystep of CO adsorption on different metals (nature of adsorption, heat of adsorption of each species) hasrequired the development of a method initially adapted for the IR analysis in transmission mode:AEIR method (Adsorption Equilibrium InfraRed spectroscopy). The experimental conditions allowinga quantitative exploitation of IR spectra in diffuse reflectance mode has been established allowing theuse of the AEIR method. This method has been developed extending the range of application oncatalysts that dissociate strongly CO firstly using diffuse reflectance mode for catalyst which can notbe study in transmission mode (Fe/Al2O3) and then in transmission mode (Co/Al2O3). The impact ofparameters linked to the preparation of catalyst (nature of the support, dispersion of metallic phase,and formation of bimetallic particles) on the heat of adsorption has been evaluated on Ir catalysts andbimetallic particles like Pt-Pd, Pt-Cu respectively. Then, the microkinetic approach of the CO/O2reaction dedicated to Ir and Pt-Pd catalysts, considering the isothermal oxidation of CO adsorbedspecies at low temperature, has shown that the superficial steps involved were similar to those for Ptand Pd catalysts. The impacts of several experimental parameters on the oxidation of CO adsorbedspecies characterized by an induction period are qualitatively identical, only the kinetic parameterslike the apparent activation energy are modified.

Le matériau étudié est un alliage Al A356, utilisés pour produire des têtes de cylindres pour l'industrie automobile par fonderie. Le matériau présente une microstructure dendritique assez grossière dans une matrice eutectique, avec une taille moyenne de grains de 25 microns, des précipités intermetalliques et des porosités. Les propriétés de traction sont fortement affectées par la température d'essai, avec une baisse assez sensible du module de Young, de la limite d'élasticité lorsque la température augmente. La durée de vie de fatigue isotherme chute de façon marquée (approximativement d'un facteur 10) lorsque la température d'essai est portée de 120 à 280 °C, en déformation imposée. Du essais thermomecaniques cycliques en phase, avec une température variant de 120 à 280 °C, on montré que la durée de vie en anisotherme est assez similaire à celle obtenue en conditions isothermes à 280 oC. Dans ce cas, les dommages causés par le chargement thermomécanique cyclique se produisent à la température la plus élevée du cycle. Les essais de relaxation ont montré l'existence de deux comportements distincts. À basse température, le matériau présente de l'écrouissage cyclique tandis qu'il s'adoucit cycliquement à des températures plus élevées. A partir des résultats de croissance des fissures de fatigue, on a observé que la température et la forme du cycle de fatigue a une forte influence sur la vitesse de fissuration par fatigue ainsi que sur le facteur d'intensité des contraintes seuil. Une loi de comportement élastique visco-plastique non-isotherme a été identifiée pour le matériau. Les paramètres de comportement mécanique sont statistiquement distribués du fait de la fabrication du matériau par fonderie. Toutefois, il a été démontré que le modèle était capable de se reproduire, avec une approximation raisonnable, les essais contrainte-déformation à des températures différentes, pour le cas isotherme et anisotherme. / The studied material is an A356 Al alloy, used to produce engine cylinder heads for the automotive industry by die casting process. The material displays a quite coarse dendritic microstructure in a eutectic matrix, with a mean grains size of 25 microns, intemetallic precipitates and porosities. The tensile properties are strongly affected by testing temperature, with a quite sensitive drop of the Young's modulus, the Yield stress as the temperature was raised. The isothermal fatigue life dropped of markedly (approximately 10 times) when the testing temperature is raised from 120 to 280 °C, under strain control. From the themomechanical in-phase cyclic tests, with temperature varying from (120 to 280 oC), it was possible to observe that life is quite similar to the isothermal fatigue test at 280 oC. In this case, the more sensitive damage caused the in-phase mechanical and thermal cycle take place at the highest temperature. Relaxation tests indicated two distinct behaviors, with the temperature of 240°C being a threshold. At lower temperatures, the material hardens cyclically whereas it softens cyclically at higher temperatures. From the fatigue crack growth results, it was observed that temperature and wave shape has a strong influence on the crack growth rate as well as on the stress intensity threshold. Considering sinusoidal wave shape (10 Hz), as the temperature increased the DKth decreased and the crack propagation rate increased. However, the rate as da/dN change with temperature is quite similar, as an indicative that the micromechanism of crack growth has not changed due to the high frequency used, and it was due only to loss of mechanical strength. An elastic-visco-plastic non-isothermal constitutive law was identified for the material. For the cast material studied in this work, the mechanical behavior parameters are statistically distributed. However, it was shown that the model was able to reproduce, with a reasonable approximation, the stress – strain relationship at different temperatures, for the isothermal and anisothermal cases. / Para caracterizar componentes usados em aplicações de alta responsabilidade não basta apenas conhecer a composição química e os resultados de ensaios de tração, impacto e dureza, pois estes podem não fornecer os subsídios necessários que permitam prever, de maneira confiável, o comportamento dos componentes nas condições reais de trabalho. Exemplo disto são os cabeçotes de motor automotivos, submetidos a tensões térmicas e mecânicasrelativamente altas durante seu uso normal e altíssimo em condições extremas. Durante longos tempos de funcionamento e eventuais falhas na refrigeração e ou lubrificação a temperatura pode chegar a valores próximos de 300ºC. Esta variação de temperaturas provoca choques térmicos que podem gerar trincas e/ou uma grande quantidade de deformação plástica em regiões próximas aos pistões. Desconsiderando a presença de choques térmicos provocadospor falhas, ainda assim, uma pequena quantidade de ciclos de acionamento e parada do motor, é considerada como os principais causadores de pequenas trincas. Isso indica que o surgimento de trincas em cabeçotes de motor deve ser considerado um problema de fadiga termomecânica de baixo ciclo. Outro problema é a heterogeneidade microestrutural no componente devido ao processo de fundição, levando a propriedades mecânicas e físicas diferentes em uma mesma peça. Além da presença de porosidade gerada por bolhas de gás e vazios de solidificação, que podem adquirir tamanho tal que se aproximem de pequenas trincas, diminuindo a vida para a nucleação e assim mudando o foco do problema para o de propagação de trinca por fadiga. A proposta deste trabalho foi a de determinar as propriedades de fadiga isotérmica e termomecânica através de ensaios de fadiga de baixo ciclo, bem como as propriedades de propagação de trinca por fadiga, relaxação, caracterização microestrutural e modelagem do comportamento mecânico por elementos finitos para a liga de alumínio utilizada na fabricação de cabeçotes de motores automotivos pela indústria nacional. Todos os ensaios e análises computacionais foram realizados nos laboratórios da Universidade de São Paulo (EESC-USP) e da École Normale Supérieure de Cachan (ENS-LMT). Os ensaios de fadiga isotérmica foram realizados nas temperaturas de 120ºC e 280ºC e os ensaios termomecânicos foram realizados em fase entre as temperaturas de 120ºC e 280ºC. Os ensaios de relaxação foram realizados em várias temperaturas com carregamento de onda trapezoidal, enquanto que os ensaios de propagação de trinca por fadiga foram realizados nas temperaturas de 120ºC, 200ºC e 280ºC para arregamentos de onda senoidal e trapezoidal em controle de carga e de deslocamento. Foi feita também análise microestrutural nos corpos de prova, após os ensaios de fadiga, por microscopia óptica e por microscopia eletrônica de varredura MEV.Os resultados destes ensaios mostraram que os defeitos de fundição e a falta de homogeneidade no material, aliados a longos tempos de exposição a carregamentos e em altas temperaturas, constituem um fator crítico no desempenho do componente. Estes resultados ajudarão a estabelecer modelos precisos de previsão de vida para os cabeçotes de motor.

The study of protein and surfactant interactions is of great significance in a number of applications, such as the cosmetic, food or pharmaceutical industries and many others. However, they require further study due to their compositional complexity and the limitations of current analytical approaches. In this thesis, the cationic surfactant septonex in combination with two differently charged proteins lysozyme and bovine serum albumin under different physiological conditions (temperature, surfactant concentration, environment and others) was selected to study the interactions. Characterization of protein-surfactant interactions is a very important but challenging task, therefore it is essential to use appropriate approaches to explore the nature of these interactions. In order to unify the information to provide rational models, calorimetric methods (DSC, ITC) and dynamic light scattering were used. Isothermal titration calorimetry monitors the evidence for the formation of the system of the mentioned substances and information on aggregation behavior, differential scanning calorimetry characterizes the thermal stability of proteins and dynamic light scattering made it possible to monitor changes in particle size. Both proteins have been proven to interact with positive septonex, even if the lysozyme molecule is also positively charged. However, significant differences were found between the two proteins. From the obtained results it is evident that the identical charge of the protein with the surfactant has an effect on the intensity of the measurement, although all measured interactions showed an endothermic character.

Biopolymer surfactant systems have been studied by using different physico chemical methods. As the biopolymer, it was chosen high (1400–1600 kDa), medium (250–450 kDa) and low (8–15 kDa) molecular weight sodium hyaluronate. Two cationic surfactants – cetyltrimethylammonium bromide (CTAB) and carbethopendecinium bromide (Septonex) were selected to provide polyelectrolyte complexes with oppositely charged hyaluronan. The critical aggregation concentration of the surfactant in the system was monitored by dynamic light scattering (Zetasizer Nano ZS). SEC-MALS method was used for the description of the conformation of sodium hyaluronate of different molecular weights and polyelectrolytes complexes hyaluronan surfactant after reaching the aggregation point. Isothermal titration calorimetry (ITC) was used to determine the critical aggregation concentration of the surfactant by monitoring the thermal changes accompanying the aggregation of the system. It was found out that the increasing molecular weight of hyaluronan in these systems decreases the critical aggregation concentrations and conversely.

With the growing trend of construction, the demand for building materials is growing steadily. Porous concrete is widely used in the building industry, that makes efforts to discount production and simultaneously save the environment. The aim of this thesis is to develop high-quality porous concrete by using alternative raw materials as a substitute for silicate sand. As a possible substitute were chosen: Silica masonry, foundry sand and fireclay boulders. The influence of two key parameters - the specific surface (130, 240 and 350 m2·kg-1) and the amount of silica sand substitution (10, 30 and 50 %) were monitored. Two autoclaving modes (7 and 12 hours of isothermal durations at 190 ° C) were tested. Based on the physico-mechanical and mineralogical characteristics of the porous concrete composites was chosen the ideal surface area of 240 m2·kg-1 and time of isothermal endurance was determined at 7 hours (temperature 190 ° C, pressure 1,4 MPa). From the optimal intentions were created samples with a macroporous structure, using an aluminum powder. Physical-mechanical properties and microstructural analysis (XRD, SEM) were subsequently determined on the samples. Ideal recipes were proposed with 50% sand substitution of fireclay boulders and 10% substitution of foundry sand. This was due to a 10% higher compressive strenght and an increase of the coefficient of constructiveness, compared to the reference sample.

This diploma thesis is aimed to the corona-like discharge in solutions of alcohols, specifically in ethanol, methanol, glycerol, butanol and isopropyl alcohol. The electric discharge was diagnosed by two methods. The first method was the measuring of electrical characteristics. Current-voltage characteristics were constructed from the measured average values of voltage and current. The breakdown voltages were determined from the current-voltage characteristics. The breakdown voltages of the individual alcohol solutions were dependent on the alcohol concentration, polarity of the electrodes in the reactor and solution conductivity. The breakdown voltage was determined for solutions of butanol, glycerol and isopropyl alcohol with a concentration of 20 vol. % and conductivity of 200 µS. The highest value of the breakdown voltage was determined for solution of glycerol at 580 V. The lowest voltage at which the discharge was observed was estimated for butanol (320 V), but due to the limited miscibility with water this value is inaccurate, and therefore in the second part of experiment butanol was not used. Alcohol series was supplemented with methanol. The second diagnostic method was the proton ionization mass spectrometry with the time of flight analyzer. The products formed in the reactor due to the plasma discharge were identified from the mass spectrum. Mostly, aliphatic hydrocarbons and their radicals were detected. The amount of products was observed in the dependence on the changing experimental conditions: alcohol concentration in the solution, the polarity of the electrodes in the reactor and the duration of the discharge. Only a small amount of compounds were detected in methanol. However, more molecules were formed with the increasing carbon chain in the alcohol molecule. More compounds were also detected with the increasing alcohol concentration and in case of the negative polarity of the main electrode. The formation of acetaldehyde as a typical discharge product was studied in details. Its production in time was observed and the reaction pathways of its formation in the ethanol solution were suggested.

The master thesis analyses electrical conductivity of lead-free solder joints. The test method design for monitoring the electrical conductivity of the soldered joint is described in the practical part. Simulated BGA package with four pin (BGA4) is used for experiments. Tested PCBs are subjected to isothermal aging and current load. During isothermal aging is measured electrical conductivity and optical microscope is used for intermetallic layer (IMC) growth observation. Two types of surface finish (OSP and ENIG) are used for tests and three diameters of solder terminal balls (solder alloy SAC405). The influence of the ratio area connection / solder volume (ratio S / V) on lead-free solder joints conductivity was evaluated.

This master thesis deals with the study of thermodynamic and structural aspects of the interactions of humic acids with organic ions. Methylene blue (dye) was used as a model organic ion. The interactions were studied by isothermal titration calorimetry, dissolution calorimetry and by diffusion in diffusion cells.

Ce travail de thèse a été consacré au développement de nouvelles méthodologies de caractérisation des affinités intermoléculaires par le biais de la calorimétrie de titration isotherme (ITC), après validation de systèmes modèles par l'intermédiaire des spectroscopies UV-visible, RMN et de l'électrophorèse capillaire. Nous avons en particulier montré que la mise en place et le couplage d'expériences non conventionnelles avec les protocoles classiques permettait d'améliorer la caractérisation calorimétrique, avec notamment une diminution parfois spectaculaire des incertitudes liées aux paramètres thermodynamiques. Ce potentiel de l'analyse globale d'expériences différenciées a été évalué sur un plan théorique, permettant ainsi la définition et l'optimisation des expériences à mettre en oeuvre en fonction du type de complexe étudié. L'exploitation expérimentale de ces stratégies a également permis l'étude de complexations problématiques sur le plan analytique, dans le cadre de complexes impliquant des molécules telles que les cyclodextrines ou l'albumine, et s'inscrivant dans des applications liés aux domaines de l'environnement et de la santé. Ainsi, nos stratégies ont levé les difficultés liées aux complexes athermiques, aux complexes de faibles affinités, aux équilibres multiples et aux faibles solubilités de l'un ou l'autre des partenaires de la complexation. Enfin, l'évaluation d'un nouveau modèle de traitement thermo-cinétique du thermogramme ITC a été réalisée, accroissant encore le potentiel de cette technique vis-à-vis de la caractérisation des interactions moléculaires. / This work was dedicated to the development of new isothermal titration calorimetry (ITC) methodologies for the characterization of intramolecula affinities, after validation of model system via capillary electrophoresis, UV-visible and NMR spectroscopy. We have demonstrated that the coupling of unconventional experiments with the conventional protocols generally improves the calorimetric characterization, with a dramatic decrease of the uncertainties on thermodynamic parameters. The potential of global analysis applied to differentiated experiments was evaluated on a theoretical level, allowing the definition of optimal experiments, depending on the type of studied complex. These strategies also enabled, on a experimental point of view, the study of complexations which cannot be analyzed by conventional approaches, in the case of complexes involving cyclodextrins or albumin. Indeed, our strategies overcomes the difficulties associated with athermic complexes, with complexes of low affinity, with multiple equilibria and with the low solubility of interacting partners. Finally, the evaluation of a new thermo-kinetic treatment of ITC thermograms has been achieved, further increasing the potential of this technique in the characterization of molecular interactions.

La compréhension des écoulements souterrains est importante pour de nombreuses applications comme l’énergie ou le stockage des déchets nucléaires. Cette thèse, effectuée en collaboration avec le Bureau de Recherches Géologiques et Minières (BRGM), est dédiée à la simulation des écoulements diphasiques compositionnels thermiques en milieux poreux et ses applications à la géothermie haute énergie et plus particulièrement au champ géothermique de Bouillante (Guadeloupe). Tout d’abord, deux formulations à variables persistantes sont comparées en termes d’implémentation et de convergence numérique. Dans ces deux formulations, les fractions molaires d’une phase absente sont étendues par celles à l’équilibre thermodynamique avec la phase présente. Il en résulte que l’ensemble des variables principales et des équations ne dépend pas de l’ensemble de phases présentes. De plus, l’équilibre thermodynamique est exprimé par une contrainte de complémentarité pour chacune des phases, ce qui permet l’utilisation de méthodes de type semi-smooth Newton pour résoudre les systèmes non-linéaires. D’autre part, cette thèse présente une nouvelle méthodologie combinant des discrétisations centrées aux noeuds (le schéma Vertex Approximate Gradient - VAG) et aux faces (le schéma Hybrid Finite Volume - HFV) sur une partition arbitraire des ensembles de mailles ou de faces, dans le but d’adapter le choix du schéma aux différentes parties du maillage. En effet, les maillages hybrides composés de différents types de mailles sont plus adaptés à la discrétisation de la géologie et de la géométrie des différents domaines d’un système géothermique. Ainsi le schéma peut être choisi localement en fonction de la géométrie de la maille et des propriétés pétrophysiques. L’analyse de convergence est effectuée dans le cadre des discrétisations Gradient pour des problèmes de diffusion du second ordre et la convergence est confirmée numériquement sur différents types de maillages hybrides 3D. Ensuite la discrétisation VAG-HFV est étendue au cas des écoulements de Darcy diphasiques non-isothermes compositionnels et est appliquée au cas test 2D représentant le plan de faille vertical du réservoir géothermique de Bouillante. Un autre aspect important de la modélisation des flux géothermiques consiste à prendre en compte les interactions entre le flux dans le milieu poreux et l’atmosphère. Puisque le couplage entre le modèle poreux et un modèle 2D surfacique ou 3D atmosphérique n’est pas réaliste en terme de coût de calcul aux échelles spatiale et temporelle géologiques, l’interaction sol-atmosphère est modélisée grâce à une condition limite prenant en compte l’équilibre de matière et d’énergie à l’interface. Ce modèle considère une couche limite atmosphérique avec transfert convectif molaire et thermique (en supposant l’évaporation de la phase liquide), une condition de débordement liquide aux surfaces d’infiltration, ainsi que le rayonnement thermique et la recharge en eau douce due aux précipitations. Cette condition limite est évaluée à l’aide d’une solution de référence couplant les écoulements non-isothermes liquide-gaz en milieu poreux et le gaz dans le milieu libre. Elle est ensuite étudiée numériquement en terme de convergence et de solution sur des cas tests géothermiques, dont le plan de faille vertical du réservoir géothermique de Bouillante. En complément est présenté le travail issu d’une collaboration lors de l’école d’été du CEMRACS 2016. Le projet consistait à ajouter un modèle de puits multi-branche thermique au code ComPASS, un nouveau simulateur géothermique parallèle basé sur des maillages non-structurés avec la possibilité de représenter des fractures. / The study of the subsurface flows is important for various applications such as energy or nuclear waste storage. This thesis, performed in collaboration with the French Geological Survey (BRGM), is dedicated to the simulation of non-isothermal compositional two-phase flows in porous media and its applications to high-energy geothermal fields and more precisely to the Bouillante field (Guadeloupe, French West Indies). First of all, two persistent variable formulations are compared in terms of implementation and numerical convergence. In these two formulations, the choice of the principal variables is based on with the extension of the phase molar fractions by the one at thermodynamic equilibrium with the present phase. It results that the set of principal variables and equations does not depend on the set of present phases. It also has the advantage to express the thermodynamic equilibrium as complementarity constraints, which allows the use of semi-smooth Newton methods to solve the non-linear systems. Moreover, this thesis presents a new methodology to combine a node-centered discretization (the Vertex Approximate Gradient scheme - VAG) and a face-centered discretization (the Hybrid Finite Volume scheme - HFV) on arbitrary subsets of cells or faces in order to choose the best-suited scheme in different parts of the mesh. Indeed, hybrid meshes composed of different types of cells are best suited to discretize the geology and geometry of the different parts of the geothermal system. Then, the scheme is adapted locally to the type of mesh/ cells and to petrophysical properties. The convergence analysis is performed in the gradient discretization framework over second order diffusion problems and the convergence is checked numerically on various types of hybrid three-dimensional meshes. Then, the VAG-HFV discretization is extended to non-isothermal compositional liquid-gas Darcy flows and is applied on the two dimensional cross-section of the Bouillante high temperature geothermal reservoir. Another important aspect of the geothermal flows modelling consists in considering the interactions between the porous medium and the atmosphere. Since the coupling between the porous medium and the 2D surface of 3D atmospheric flows is not computationally realistic at the space and time scales of a geothermal flow, the soil-atmosphere interaction is modelled using an advanced boundary condition accounting for the matter (mole) and energy balance at the interface. The model considers an atmospheric boundary layer with convective molar and energy transfers (assuming the vaporization of the liquid phase in the atmosphere), a liquid outflow condition at seepage surfaces, as well as the heat radiation and the precipitation influx. This boundary condition is assessed using a reference solution coupling the Darcy flow to a full-dimensional gas free flow. Then, it is studied numerically in terms of solution and convergence of the Newton-min non-linear solvers on several geothermal test cases including two-dimensional simulations of the Bouillante geothermal field. In addition is presented the collaborative project which took place during the CEMRACS summer school 2016. The project consisted in adding a multibranch thermal well model into the ComPASS code, a new geothermal simulator based on unstructured meshes and adapted to parallel distributed architectures with the ability to represent fractures.