L’utilisation des métaux nobles en catalyse hétérogène est limitée par la rareté de ces métaux, leur coût et les difficultés d’approvisionnement, le marché mondial étant régi par deux producteurs. Le but de ce travail a consisté à étudier l’association du platine et du cobalt afin de substituer en partie Pt par Co tout en préservant les propriétés catalytiques du métal noble en hydrogénation. Différentes synthèses de catalyseurs bimétalliques 1%Pt-5%Co supportés (coimprégnation, voie redox et voie colloïdale) ont été réalisées et les performances de ces catalyseurs comparées à celles des catalyseurs monométalliques et des mélanges mécaniques (Pt + Co) pour deux réactions d’hydrogénation d’intérêt industriel : l’hydrogénation de l’acétonitrile et celle du furfural. Les caractérisations par des techniques physicochimiques (MET, XPS, …) ou par réactions modèles (déshydrogénation du cyclohexane, hydrogénolyse du méthylcyclopentane) ont permis d’obtenir les résultats suivants : - la présence de Pt augmente la réductibilité du Co pour les catalyseurs coimprégnés ou pour les mélanges mécaniques, ce qui permet d’améliorer les performances catalytiques en hydrogénation du furfural ou de l’acétonitrile ;- la préparation par voie colloïdale oriente vers la formation de particules PtCo de type alliage de composition homogène, peu actives pour les réactions étudiées ;- la synthèse par voie redox permet de déposer précisément le platine au contact du cobalt créant un effet synergétique bénéfique. Il est ainsi possible d’obtenir la même activité que le platine seul en hydrogénation de l’acétonitrile mais avec un catalyseur PtCo présentant une quantité de Pt cinq fois moins importante. / The use of noble metals in heterogeneous catalysis is limited by the scarcity of these metals, their cost and the supply difficulties due to the monopole of only two countries on the world market. The aim of this work consisted to study the association of platinum and cobalt in order to substitute partly Pt with Co while preserving the catalytic performances of the noble metal in hydrogenation. Various syntheses of 1%Pt- 5%Co supported bimetallic catalysts have been achieved and their performances have been compared with those of monometallic catalysts as well as (Pt + Co) mechanical mixtures for two hydrogenation’s reactions of industrial interest: the hydrogenation of acetonitrile and that of furfural. The physicochemical characterizations carried out (TEM, XPS …) and the model reactions (dehydrogenation of cyclohexane, hydrogenolysis of methylcyclopentane) studied have pointed out several results: - the presence of Pt increases the reducibility of Co for co-impregnated catalysts and mechanical mixtures leading to an enhancement of the catalytic performances in hydrogenation of acetonitrile or furfural; - the colloidal preparation favors the formation of PtCo alloy particles with a homogeneous composition, which are not very active for the reactions studied; - the redox route synthesis can accurately deposit Pt in contact with Co creating an improvement of the catalytic performances by a synergistic effect. Thus, in the hydrogenation of acetonitrile, the same activity was obtained by using a Pt-Co catalyst containing five times less noble metal’s content than the 1% Pt catalysts.

Dans le cadre du développement des technologies Na-ion, le composé NaFePO4, équivalent chimiquedu matériau très attractif LiFePO4, représente une alternative intéressante aux problèmes deressourcement du lithium. Toutefois, les composés LiFePO4 et NaFePO4 de structure olivineprésentent des divergences de comportement structural et électrochimique lors de l'insertioncationique. Ce travail présente une analyse des mécanismes de (dés)insertion des ions Li+ et Na+ ausein de la phase FePO4 par voie chimique et électrochimique. Les échantillons de LiFePO4 ont étésynthétisés par deux méthodes différentes (hydrothermale et précipitation), puis délithiéschimiquement via différents procédés. Dans un premier temps, les analyses structurales (DRX)associées aux analyses nucléaires ont permis d'effectuer un suivi de la cinétique de réaction. Nousavons montré que la présence de joints de grains, issus du traitement thermique effectué, limitefortement la vitesse de délithiation. L'analyse de l’évolution des domaines de cohérences a permis deproposer un mécanisme de délithiation original de type "Coeur-Coquille" avec un coeur de LiFePO4,confirmé par HRTEM et STEM-EELS. Dans un deuxième temps, afin de comparer les mécanismes dedélithiation chimique et électrochimique, l’insertion et la cyclabilité des ions Li+ et Na+ ont étécaractérisées en demi-cellules lithium et sodium. Bien que la signature électrochimique des matériauxLiFePO4 et NaFePO4 soit différente, les performances en termes de capacité restituée ou de tenue enpuissance s'avèrent similaires. Enfin, l'insertion électrochimique des ions Li+ et Na+ au sein d'unepoudre comportant des défauts structuraux a été caractérisée par DRX Operando durant un cycle decharge / décharge effectué à régime lent. Ces analyses ont révélées que la co-insertion cationiques'effectue via une solution solide de type LixNayFePO4 (0<x+y<1). / As part of the development of Na-ion technology, NaFePO4 compound, chemical equivalent of theattractive LiFePO4 material, would be a promising option facing possible lithium shortage. However,olivine-type LiFePO4 and NaFePO4 display different structural and electrochemical behaviors duringcationic insertion. This thesis presents an analysis of the (de)insertion mechanisms of Li+ and Na+ ionswithin olivine-type FePO4 by chemical and electrochemical means. Samples of LiFePO4 weresynthesized by two different methods (hydrothermal and precipitation), then chemically delithiated bydifferent processes. In a first step, structural analysis (XRD) associated with nuclear analyses enabledfollowing the reaction kinetics. We have pointed out that the presence of grain boundaries, resultingfrom the heat treatment, strongly limits the delithiation kinetics. The analysis of the evolution of thecoherency domains enabled us to propose an original "Shrinking Core" type delithiation mechanismwith a core of LiFePO4, observed by HRTEM and STEM-EELS. In a second step, in order to comparechemical and electrochemical mechanisms, insertion and cyclability of Li+ and Na+ were characterizedin lithium and sodium half-cells. Although the electrochemical signature of LiFePO4 and NaFePO4materials is different, the performances in terms of restored capacity or power capability are similar.Finally, electrochemical insertion of Li+ and Na+ in a powder comprising structural defects wascharacterized by operando XRD, during a charge / discharge cycle performed at low rate. Theseanalyses revealed that the cationic co-insertion takes place via a solid solution LixNayFePO4(0<x+y<1).

O Brasil é produtor de argilas e conta com grandes reservas deste recurso natural. Porém, grande parte da sua produção é comercializada seca e moída. O desenvolvimento de argilas para seu uso como reforço em nanocompósitos poliméricos constitui uma opção para os produtores desta matéria prima que teriam assim um produto com maior valor agregado. Este trabalho visa avaliar o potencial uso como nanocarga de duas argilas nacionais provenientes da Bacia de Taubaté, São Paulo, denominadas ALIGRA e SANTA FÉ. As frações de tamanho de partícula médio menor de 0,02 mm, obtidas por peneiramento á úmido da argila homogeneizada e seca, foram utilizadas no desenvolvimento do trabalho experimental. Os estudos de caracterização, envolvendo análise granulométrica, química, mineralógica, morfológica, térmica e textural, revelaram características muito semelhantes em ambas às argilas. Fração argila, maior de 70% em massa. Composição química conforme a definição química de uma argila e os teores de seus componentes mostram valores intermédios entre as apresentadas pelas bentonitas e argila caulinítica usadas com fins de comparação. Ressaltamse boas propriedades adsorventes. Área superficial específica BET ao redor de 120 m2/g, valor maior do que o apresentado por muitas bentonitas naturais (74,5 m2/g). Predominantemente mesoporosas, com poros, maiormente em forma de fenda, característicos da estrutura em camadas das argilas. Baixa capacidade de troca catiônica, 12 meq/100g. Difratogramas de raios-X revelaram a predominância do estratificado ilita/esmectita, caulinita e quartzo na argila ALIGRA, e de ilita, caulinita e quartzo na argila SANTA FÉ. Prosseguiu-se com a argila ALIGRA a preparação da argila organofílica. A argila organofílica foi obtida por troca catiônica com o sal quaternário de amônio: cloro cetril trimetil amônio, depois de homogeneizada em sódio com cloreto de sódio. Análises FTIR e TGA indicaram que houve inserção dos cátions orgânicos. Testes preliminares foram feitas, preparando misturas das argilas com matriz de polipropileno e usando como agente compatibilizante polipropileno enxertado com anidrido maleico. Resultados de ensaios de tração reportam algumas melhoras nas propriedades testadas com as composições preparadas com as argilas purificadas. Com as composições com argilas organofílicas somente foi melhorado o alongamento na rotura. Estudos ais aprofundados são recomendados. / Brazil is a producer of clay and has large reserves of this natural resource. However, most of its production is sold dried and milled." The development of clays for use as reinforcement in polymer nanocomposites is an option for these raw material producers, who would thus have a product with higher added value. This study aims to evaluate the potential use as nanofiller of two national clays from Taubaté basin, São Paulo, called ALIGRA and SANTA FE. In this experiment, the fractions of particles with average size of less than 0.02 obtained through wet sieving were used. The characterization studies involving granulometric, chemical, mineralogical, morphological, thermal and textural analysis, revealed very similar characteristics in both the clays. Clay fraction (< 2&#956;m) is higher 70%. Chemical composition as the definition of clay and its components show intermediate values between those present by bentonite and kaolinitic clays used here for purposes of comparison. It should be underlined good adsorptive properties. Specific surface area BET (aBET) around of 120 m2/g, this value is higher than showed by many bentonites (74.5 m2/g). They are predominantly mesoporous, the pores predominantly in slit-shape in accordance to the characteristic layered structure of the clays. Low cationic exchange capacities (CEC), 12 meq/100 g. XRD results for samples saturated with ethylene glycol and heated revealed the predominance of illite/smectite, kaolinite and quartz in ALIGRA clay, and illite, kaolinite and quartz in the clay SANTA FE. Work continued with the clay ALIGRA the preparation of organoclay. The organoclay was obtained by ion exchange with the quaternary ammonium salt: cetril trimethyl ammonium chloride, after homogenized in sodium with sodium chloride. FTIR and TGA analyzes indicated that there was integration of organic cations Preliminary tests were performed by preparing mixtures of clays with a polypropylene matrix, and using polypropylene grafted with maleic anhydride as a compatibilizer. Results of tensile tests made in the polypropilene- purified clay compositions have reported some improvements in some tested properties. With polipropilene-organofilized compositions only improved elongation on break. More detailed studies are which would be required.

O Brasil é produtor de argilas e conta com grandes reservas deste recurso natural. Porém, grande parte da sua produção é comercializada seca e moída. O desenvolvimento de argilas para seu uso como reforço em nanocompósitos poliméricos constitui uma opção para os produtores desta matéria prima que teriam assim um produto com maior valor agregado. Este trabalho visa avaliar o potencial uso como nanocarga de duas argilas nacionais provenientes da Bacia de Taubaté, São Paulo, denominadas ALIGRA e SANTA FÉ. As frações de tamanho de partícula médio menor de 0,02 mm, obtidas por peneiramento á úmido da argila homogeneizada e seca, foram utilizadas no desenvolvimento do trabalho experimental. Os estudos de caracterização, envolvendo análise granulométrica, química, mineralógica, morfológica, térmica e textural, revelaram características muito semelhantes em ambas às argilas. Fração argila, maior de 70% em massa. Composição química conforme a definição química de uma argila e os teores de seus componentes mostram valores intermédios entre as apresentadas pelas bentonitas e argila caulinítica usadas com fins de comparação. Ressaltamse boas propriedades adsorventes. Área superficial específica BET ao redor de 120 m2/g, valor maior do que o apresentado por muitas bentonitas naturais (74,5 m2/g). Predominantemente mesoporosas, com poros, maiormente em forma de fenda, característicos da estrutura em camadas das argilas. Baixa capacidade de troca catiônica, 12 meq/100g. Difratogramas de raios-X revelaram a predominância do estratificado ilita/esmectita, caulinita e quartzo na argila ALIGRA, e de ilita, caulinita e quartzo na argila SANTA FÉ. Prosseguiu-se com a argila ALIGRA a preparação da argila organofílica. A argila organofílica foi obtida por troca catiônica com o sal quaternário de amônio: cloro cetril trimetil amônio, depois de homogeneizada em sódio com cloreto de sódio. Análises FTIR e TGA indicaram que houve inserção dos cátions orgânicos. Testes preliminares foram feitas, preparando misturas das argilas com matriz de polipropileno e usando como agente compatibilizante polipropileno enxertado com anidrido maleico. Resultados de ensaios de tração reportam algumas melhoras nas propriedades testadas com as composições preparadas com as argilas purificadas. Com as composições com argilas organofílicas somente foi melhorado o alongamento na rotura. Estudos ais aprofundados são recomendados. / Brazil is a producer of clay and has large reserves of this natural resource. However, most of its production is sold dried and milled." The development of clays for use as reinforcement in polymer nanocomposites is an option for these raw material producers, who would thus have a product with higher added value. This study aims to evaluate the potential use as nanofiller of two national clays from Taubaté basin, São Paulo, called ALIGRA and SANTA FE. In this experiment, the fractions of particles with average size of less than 0.02 obtained through wet sieving were used. The characterization studies involving granulometric, chemical, mineralogical, morphological, thermal and textural analysis, revealed very similar characteristics in both the clays. Clay fraction (< 2&#956;m) is higher 70%. Chemical composition as the definition of clay and its components show intermediate values between those present by bentonite and kaolinitic clays used here for purposes of comparison. It should be underlined good adsorptive properties. Specific surface area BET (aBET) around of 120 m2/g, this value is higher than showed by many bentonites (74.5 m2/g). They are predominantly mesoporous, the pores predominantly in slit-shape in accordance to the characteristic layered structure of the clays. Low cationic exchange capacities (CEC), 12 meq/100 g. XRD results for samples saturated with ethylene glycol and heated revealed the predominance of illite/smectite, kaolinite and quartz in ALIGRA clay, and illite, kaolinite and quartz in the clay SANTA FE. Work continued with the clay ALIGRA the preparation of organoclay. The organoclay was obtained by ion exchange with the quaternary ammonium salt: cetril trimethyl ammonium chloride, after homogenized in sodium with sodium chloride. FTIR and TGA analyzes indicated that there was integration of organic cations Preliminary tests were performed by preparing mixtures of clays with a polypropylene matrix, and using polypropylene grafted with maleic anhydride as a compatibilizer. Results of tensile tests made in the polypropilene- purified clay compositions have reported some improvements in some tested properties. With polipropilene-organofilized compositions only improved elongation on break. More detailed studies are which would be required.

Les travaux présentés s'intéressent à la réalisation de piles SOFC de 3éme génération. La problématique essentielle de cette configuration concerne le processus de mise en forme de la cellule devant permettre l'obtention d'un électrolyte dense (haute température) associé à un métal poreux (basse température). Afin de répondre à cette problématique, nous proposons une approche innovante consistant à élaborer et mettre en forme, à haute température, un empilement de précurseurs oxydes réduits dans une deuxième étape à température modérée pour générer les parties métalliques. La voie sol-gel dérivée du procédé Pechini réputée pour permettre l'obtention à moindre coût d'échantillons homogènes de composition complexe et à microstructure contrôlée a permis d'obtenir les précurseurs oxydes des constituants de la cellule. Leur mise en forme a été réalisée par frittage flash, technique sélectionnée pour la rapidité de traitement permettant de contrôler la densification, préserver la microstructure et limiter les réactions interfaciales lors de l'assemblage de matériaux différents. Les paramètres de densification puis les conditions de réduction ont été optimisés pour chaque précurseur avant d'être transférés pour la réalisation d'une demi-cellule. Le départ de l'oxygène se traduit par une augmentation de la porosité sans coalescence des parties métallique ni décollement au niveau des interfaces entre constituants. Ainsi, les résultats présentés valident l'approche proposée montrant le bénéfice attendu de l'utilisation de précurseurs oxydes permettant la dissociation de l'étape mise en forme et densification de l'électrolyte de celle de l'obtention du métal poreux. Après réalisation des tests électrochimiques sur la demi-cellule, la réalisation d'une cellule complète pourra être proposée avant d'envisager un transfert d'échelle, rendu possible par l'utilisation de procédés facilement industrialisables. / The works presented concern in the realization of a third generation of SOFC cell. The main problem is the shaping process of the cell which must allows obtaining a dense (high temperature) electrolyte associated with a porous metal (low temperature). In order to solve this issue, we propose an innovative approach consisting in developing and shaping, at high temperature, a stack of oxide precursors which will be reduced in a second step at moderate temperature to generate the metal parts. The sol-gel route derived from the Pechini process, known to allow obtaining at low cost homogeneous samples of complex composition and controlled microstructure, was used to obtain the oxide precursors of the constituents of the cell. Their shaping was carried out by flash sintering, a technique selected for the speed of treatment allowing to control the densification, to preserve the microstructure and to limit the interfacial reactions during the assembly of different materials. The densification parameters and then the reduction conditions were optimized for each precursor before being transferred for the production of a half-cell. The departure of the oxygen results in an increase in the porosity without coalescence of the metal parts or detachment at the interfaces between constituents. Thus, the results presented validate the proposed approach showing the expected benefit of the use of oxide precursors allowing the dissociation of the shaping and densification step of the electrolyte from that of the obtaining of the porous metal. After carrying out the electrochemical tests on the half-cell, the full cell will be produced the upscaling, facilitated by the use of adequate chemical processes will be considered.

Les environnements ont tendance à être plus sévères (plus chauds et quelquefois plus froids). À ce titre, l’électronique de puissance haute température est un enjeu majeur pour le futur. Concernant les technologies d’assemblage à haute température, les brasures haute température comme l'alliage 88Au/12Ge, 97Au/3Si et 5Sn/95Pb pourraient supporter ces niveaux de contraintes thermiques, qui sont actuellement développées pour répondre à ces exigences. Nous avons effectué les caractérisations électriques, mécaniques et thermomécaniques des matériaux d’assemblage. Une étude thermique a réalisée par des méthodes expérimentales et des simulations numériques, l’étude numérique est réalisée sous ANSYS dans le but d’estimer les influences des différents paramètres sur la performance thermique de l’assemblage. En plus, les cyclages thermiques passif de grande amplitude sont effectués pour analyser la fiabilité des modules de puissance dans ces conditions d’utilisation. / The environments tend to be more severe (hotter and sometimes colder). As such, the high temperature power electronics is a major challenge for the future. Concerning the technologies for high temperature assembly, high temperature brazing alloy as 88Au / 12Ge, 97Au / 3Si and 5Sn / 95Pb could support these levels of thermal stresses, which are being developed to answer these requirements. We performed the electric, mechanical and thermomechanical characterizations for the materials of assembly. A thermal study was realized by experimental methods and numerical simulations, the numerical study is carried out in ANSYS in order to estimate the influences of the various parameters on the thermal performance of the assembly. In addition, the passive thermal cycles of large amplitude are conducted to analyze the reliability of the power modules in these conditions.

La thèse s'inscrit dans le cadre du projet GENOME « Gestion Optimisée de l'Energie » dont l'enjeu majeur est la conception d'un avion plus électrique. L'augmentation de l'efficacité énergétique et de la compacité des systèmes électriques de ces avions entraîne de fortes sollicitations en température. Ces sollicitations sont liées à la compacité des systèmes (réduction de masse et de volume) ainsi qu'à leur localisation par rapport aux sources chaudes (réacteur d'avion par exemple). De ce fait, les matériaux magnétiques des nouveaux convertisseurs électriques doivent pouvoir fonctionner sous des conditions de hautes températures, supérieures à 200°C. Il s'agit du polycristallin FeCoV dédié à la fabrication des tôles du stator et du rotor des génératrices rapides (situées à proximité des réacteurs) et le nanocristallin FeCuNuSiB dédié à la conception des inductances et transformateurs des convertisseurs statiques. Ce manuscrit s'intéresse à l'étude du vieillissement thermique de ces deux familles de matériaux magnétiques. Ces matériaux, fournis par la société APERAM, se déclinent sous plusieurs nuances et finitions. L'étude du vieillissement consiste en l'application de plusieurs essais de vieillissement continus sous différentes températures (jusqu'à 300 °C pour les FeCoV et 240 °C pour les nanocristallins). Plusieurs grandeurs macroscopiques magnétiques, électriques et mécaniques (pour les FeCoV) sont mesurées à chaque intervalle de vieillissement. Grâce à ces mesures macroscopiques et à des mesures complémentaires effectuées à l'échelle microscopique, des analyses sont faites et des hypothèses sont proposées afin d'expliquer les mécanismes de vieillissement de ces deux familles de matériaux et dans le but de proposer des modèles phénoménologiques fiables / The thesis takes part of the project GENOME “Gestion Optimisée de l’Energie” whose major issue is the design of the more electrical aircraft. The increase in the energy efficiency and the compactness of the electrical systems of these aircrafts lead to high temperature stresses. These thermal stresses are related to the compactness of the systems (reduction of mass and volume) as well as their location with respect to the hot sources (aircraft engine for example). Thus, the magnetic materials of the new electrical converters must be able to operate under conditions of high temperatures, above 200 °C. Typically, the FeCoV polycrystalline materials are dedicated to the fabrication of the stator and rotor sheets of the fast generators (located near the aircraft engine) and the FeCuNbSiB nanocrystalline materials are dedicated to the design of inductors and transformers of the static converters.This manuscript concerns the thermal ageing study of these two magnetic material families. These materials, supplied by the company APERAM, are available in several shades. The ageing study consists on applying several continuous ageing treatments at different temperatures (up to 300 °C for FeCoV and 240 °C for FeCuNbSiB). At each ageing step, several macroscopic properties namely: magnetic, electrical and mechanical (for the FeCoV materials) properties are measured. Using these macroscopic properties and complementary measurements carried out on a microscopic scale, analyses are made and hypotheses are proposed in order to explain the ageing mechanisms of these magnetic material families. The understanding of the magnetic ageing mechanisms is necessary towards establishing of phenomenological ageing models

Ce travail de thèse porte sur la valorisation de granulats recyclés dans la fabrication de nouveaux liants hydrauliques. Il s’inscrit dans une problématique actuelle de gestion des déchets du BTP, de sauvegarde des ressources naturelles et de réduction des gaz à effets de serre liés à la production de matériaux cimentaires. En quelques chiffres, sur les 260 millions de tonnes de déchets inertes produits annuellement par le secteur du BTP en France, 90 millions sont encore déposés en installations de stockage. C’est ce gisement qu’il convient de réduire pour accentuer la fabrication de granulats recyclés estimée aujourd’hui à 15 millions de tonnes/an. Dans cette perspective, ce travail de recherche a pour double objectif de valoriser des granulats recyclés sous forme de fines (Dmax < 80 µm) comme addition minérale en substitution du ciment pour les mortiers et bétons ou bien comme constituant principal de Liants Hydrauliques Routiers (LHR) pour le traitement des sols en place. Deux matériaux source sont utilisés, à savoir : un béton aux propriétés connues et maitrisées et un granulat issu d’une plateforme de recyclage représentatif d’une filière de production. De ces deux matériaux, des fines sont fabriquées par un protocole couplé de concassage et criblage avec ou sans traitement thermique à haute température puis caractérisées (caractérisation physico-chimique, minéralogique et réactivité hydraulique résiduelle) en vue d’établir une cartographie complète de leur potentiel de valorisation en fonction de leur origine. Le premier objectif intitulé « fabrication d’une addition minérale à base de fines » traite de l’effet de cette addition sur le comportement rhéologique, mécanique et sur les propriétés de durabilité de mortiers. Malgré un verrou normatif lié à l’utilisation de matières non référencées dans les normes des matériaux cimentaires, les résultats de ce travail démontrent la faisabilité d’introduire des fines en substitut d’additions classiques tel que le filler calcaire dans des proportions largement supérieures à celles imposées. Le second objectif intitulé « fabrication de liants hydrauliques routiers à base de fines » traite de la conception de LHR à base de fines pour le traitement des sols en place. C’est à partir d’un sol témoin reconstitué en laboratoire que deux familles de LHR à base de fines traitées et non traitées sont conçues, testées et comparées à des liants hydrauliques routiers commercialisés et enfin optimisées. / This thesis work focuses on the valorization of recycled aggregates as main component for hydraulic binders. This is included in a current issue of waste management, protection of natural resources and environment, reduction of greenhouse gases emissions in cement production. In France, on 260 millions tons of inert wastes produced per year, 90 millions tons are still stored in non-hazardous landfill. This waste deposit has to be reduced to increase the production of recycled aggregates currently estimated at 15 million tons per year. In view of this, this research is aimed to enhance the valorization of recycled aggregates into powder form (Dmax < 80 microns) as a mineral addition in substitution of cement for mortar and concrete or as main constituent of Hydraulic Road Binders (HRB). Two sources of materials are used : a five years old concrete and a recycled aggregates come from a recycling plant. Powders are prepared by crushing and sieving with or without high-temperature heat treatment and characterized (physical, chemical and mineralogical characterizations : residual hydraulic reactivity) to evaluate their potential valorization based on their origin.The first objective, entitled “Conception of mineral addition using powder of recycled aggregates”, deals with of the influence of this new materials on rheological, mechanical and durability properties of mortars. The results of this study allow us to evaluate the benefits of incorporating powder obtained by crushing/sieving of recycled aggregates as cement or limestone substitute used in the composition of a mortar. The second objective, entitled "conception of the Hydraulic Road Binders using powders of recycled aggregates", deals with the design of HRB by a comparative approach with HRB manufactured. The characteristics of binders are tested on mortars and on samples of treated soil and the results show that it's possible to produce an HRB rich in powders of recycled aggregates with or without cement which can efficiently stabilize clayey soils.

Les HEMT AlGaN/GaN sont en passe de devenir incontournables dans le monde de l'amplification de puissance radiofréquence, grâce à leurs performances exceptionnelles. Cependant,en raison de la relative jeunesse de cette technologie, des études de fiabilité dans plusieurs modes de fonctionnement sont toujours nécessaires pour comprendre les mécanismes de défaillance propres à ces composants et responsables de leur vieillissement. Cette étude porte sur l'analyse des défaillances dans les transistors HEMT AlGaN/GaN de puissance,en régime de fonctionnement de type RADAR (pulsé et saturé). Elle s'appuie sur la conception d'amplificateurs de test, leur caractérisation et leur épreuve sur bancs de vieillissement. La mise en place d'une méthodologie visant à discriminer les mécanismes de dégradation prépondérants, conjointement à une analyse micro-structurale des composants vieillis, permet d'établir le lien entre l'évolution des performances électriques et l'origine physique de ces défauts. / AlGaN/GaN HEMTs are on the way to lead the radiofrequency power amplificationfield according to their outstanding performances. However, due to the relative youth of this technology, reliability studies in several types of operating conditions are still necessaryto understand failure mechanisms peculiar to these devices and responsible for their wearingout. This study deals with the failure analysis of power AlGaN/GaN HEMTs in RADARoperating mode (pulsed and saturated). This is based on the design of test amplifiers, theircharacterization and their stress on ageing benches. The setting up of a methodology aimingat discriminating predominant degradation modes, jointly with a micro-structural analysisof aged devices, permits to link the evolution of electrical performances with the physicalroots of these defects.

<div>Power semiconductor devices play an important role in many areas, including household</div><div>appliances, electric vehicles, high speed trains, electric power stations, and renewable energy</div><div>conversion. In the modern era, silicon based devices have dominated the semiconductor</div><div>market, including power electronics, because of their low cost and high performance. The</div><div>applications of devices rated 600 V - 6.5 kV are still dominated by silicon devices, but they</div><div>are nearly reaching fundamental material limits. New wide band gap materials such as silicon</div><div>carbide (SiC) offer significant performance improvements due to superior material properties</div><div>for such applications in and beyond this voltage range. 4H-SiC is a strong candidate</div><div>among other wide band gap materials because of its high critical electric field, high thermal</div><div>conductivity, compatibility with silicon processing techniques, and the availability of high</div><div>quality conductive substrates.</div><div>Vertical DMOSFETs and insulated gate bipolar transistors (IGBT) are key devices for</div><div>high voltage applications. High blocking voltages require thick drift regions with very light</div><div>doping, leading to specific on-resistance (R_ON,SP ) that increases with the square of blocking</div><div>voltage (V_BR). In theory, superjunction drift regions could provide a solution because of a</div><div>linear dependence of R_ON,SP on V_BR when charge balance between the pillars is achieved</div><div>through extremely tight process control. In this thesis, we have concluded that superjunction</div><div>devices inevitably have at least some level of charge imbalance which leads to a quadratic</div><div>relationship between V_BR and R_ON,SP . We then proposed an optimization methodology to</div><div>achieve improved performance in the presence of this inevitable imbalance.</div><div>On the other hand, an IGBT combines the benefits of a conductivity modulated drift</div><div>region for significantly reduced specific on-resistance with the voltage controlled input of a</div><div>MOSFET. Silicon carbide n-channel IGBTs would have lower conduction losses than equivalent</div><div>DMOSFETs beyond 6.5 kV, but traditionally have not been feasible below 15 kV. This</div><div>is due to the fact that the n+ substrate must be removed to access the p+ collector of the</div><div>IGBT, and devices below 15 kV have drift layers too thin to be mechanically self-supporting.</div><div>In this thesis, we have demonstrated the world’s first functional 10 kV class n-IGBT with</div><div>a waffle substrate through simulation, process development, fabrication and characterization.</div><div><div>The waffle substrate would provide the required mechanical support for this class of devices.</div><div>The fabricated IGBT has exhibited a differential R_ON,SP of 160 mohm</div><div>.cm², less than half of</div><div>what would be expected without conductivity modulation. An extensive fabrication process</div><div>development for integrating a waffle substrate into an active IGBT structure is described</div><div>in this thesis. This process enables an entirely new class of moderate voltage SiC IGBTs,</div><div>opening up new applications for SiC power devices.</div></div>