E système Mo-Ni-Re est un sous-système majeur des superalliages à base de Ni conçus pour une utilisation dans les applications à haute température. Compte tenu des contradictions entre les informations publiées antérieurement, cette étude a été consacrée à la détermination expérimentale complète des équilibres entre phases dans le système Mo-Ni-Re, à la caractérisation structurale des phases intermétalliques et à la modélisation thermodynamique du système à l'aide de la méthode CALPHAD. L'étude expérimentale des équilibres entre phases a été effectuée en utilisant des alliages à l'équilibre, et les diagrammes de phases du système Ni-Re et Mo-Ni-Re (à 1200°C et à 1600°C) ont été proposées. En comparaison avec les études précédentes, le diagramme de phases Ni-Re déterminé au cours de ce travail a montré des différences significatives en termes de domaines d'homogénéité, des domaines de cristallisation et de température de réaction péritectique. La coupe isotherme à 1200°C du système Mo-Ni-Re proposée lors de cette étude a montré l'extension importante de la phase σ du système binaire Mo-Re et de la phase δ du système Mo-Ni dans le diagramme ternaire. En outre, la présence de deux phases ternaires jusque-là inconnues a également été observée. La coupe isotherme du système Mo-Ni-Re à 1600°C a également montré une grande extension de la phase σ dans le diagramme ternaire tandis que l'extension de la phase χ du système Mo-Re dans les deux coupes isothermes est limitée à un étroit domaine de composition. Les phases ternaires observées dans la coupe isotherme à 1200°C ne sont pas présentes dans la coupe isotherme à 1600°C. D'autre part, les études partielles des domaines de composition des phases dans les systèmes binaires Mo-Ni et Mo-Re ainsi que la détermination de la projection du liquidus du système Mo-Ni-Re ont également été effectuées. La projection du liquidus du système Mo-Ni-Re proposée lors de la présente étude a également montré des champs de cristallisation primaire de la phase σ de système Mo-Re et la solution solide de Re dans la région ternaire qui sont largement étendus. Puisque la coupe isotherme du système Mo-Ni-Re a montré un domaine d'homogénéité de la phase σ très étendu, la caractérisation structurale de la phase σ du système ternaire Mo-Ni-Re a été effectuée en mettant l'accent sur la détermination de l'occupation des sites en fonction de la composition par affinement de Rietveld combiné des données de diffraction des rayons X et des neutrons. Les résultats expérimentaux recueillis au cours de cette étude ainsi que les informations disponibles dans la littérature ont été utilisés comme données d'entrée pour la modélisation thermodynamique du système Mo-Ni-Re. La description thermodynamique du système Mo-Re a été prise de la littérature tandis que les optimisations thermodynamiques des systèmes Mo-Ni, Ni-Re et Mo-Ni-Re ont été effectuées au cours de ce travail avec la méthode CALHAD.Mots-clés: Mo-Ni, Mo-Re, Ni-Re, Mo-Ni-Re; diagramme de phases; coupe isotherme; caractérisation structurale; modélisation thermodynamique; méthode CALPHAD / The Mo-Ni-Re system is one of the important subsystems of the Ni based superalloys engineered for use in high temperature applications. Considering the contradictions among previously reported information, the present study was devoted to the complete experimental determination of the phase equilibria in the Mo-Ni-Re system, structural characterization of its intermetallic phases and thermodynamic modeling of the system with the help of the CALPHAD method. The experimental investigation of phase equilibria was carried out with the help of equilibrated alloys and phase diagrams of the Ni-Re and Mo-Ni-Re system (at 1200°C and 1600°C) were proposed. In comparison with previous investigations, the Ni-Re phase diagram determined during the present study showed significant difference in terms of homogeneity domains, freezing ranges and peritectic reaction temperature. The 1200°C isothermal section of the Mo-Ni-Re system proposed during the present study showed large extension of the Mo-Re σ phase and Mo-Ni δ phase in the ternary region. In addition, presence of two previously unknown ternary phases was also observed. The isothermal section of the Mo-Ni-Re system at 1600°C also showed large extension of σ phase in the ternary region whereas extension of the Mo-Re χ phase in both isothermal sections was restricted to narrow composition range. The presence of the ternary phases observed in the 1200°C isothermal was not evidenced in 1600°C isothermal section. On the other hand, partial investigations of phase boundaries in the Mo-Ni and Mo-Re binary systems and determination of liquidus projection of the Mo-Ni-Re system was also carried out. The liquidus projection of the Mo-Ni-Re system proposed during present study also showed largely extended primary crystallization fields of the Mo-Re σ phase and Re solid solution in the ternary region. Since isothermal sections of the Mo-Ni-Re system showed largely extended homogeneity domain of σ, structural characterization of the Mo-Ni-Re σ with particular emphasis on determination of site occupancy trends as a function of composition was carried out by combined Rietveld refinement of the X-ray and neutron diffraction data. The experimental results gathered during the present study along with the information available in the literature were used as input for thermodynamic modeling of the Mo-Ni-Re system. The thermodynamic description of the Mo-Re system was taken from literature whereas thermodynamic modeling of the Mo-Ni, Ni-Re and Mo-Ni-Re system was carried out during the present study with the help of the CALHAD method.Keywords: Mo-Ni; Mo-Re; Ni-Re; Mo-Ni-Re; phase diagram; isothermal section; structural characterization; thermodynamic modeling; CALPHAD method

Les sources d'approvisionnement en énergie proviennent essentiellement des matières fossiles, qui se raréfient et dont la combustion relargue dans l'atmosphère des polluants et gaz à effet de serre.Un vecteur d'énergie apparaît comme l'avenir pour subvenir aux besoins énergétiques de la planète : l'hydrogène ; cependant, son coût de production reste très élevé.Dans la nature, des enzymes, les hydrogénases, sont capables de produire et d'oxyder l'hydrogène de manière très efficace. Les scientifiques se sont alors inspirés de ces enzymes afin de concevoir des complexes qui seraient des catalyseurs bien plus robustes pour produire de l'hydrogène.Au cours de cette thèse, nous avons pris comme source d'inspiration les hydrogénases [NiFe], dont le site actif est composé d'un coeur bimétallique Ni-Fe coordiné par quatres ligands thiolates.Nous avons synthétisé divers ligands en vue d'obtenir des complexes polymétalliques de Ni, Fe ou Ru, rassemblant ce qui semble être quelques unes des propriétés clés de l'activité des hydrogénases [NiFe] : ligands thiolate sur le nickel, dont deux pontants avec le second métal, géométrie tétraédrique du nickel. Pour cela, de nouvelles familles de ligands polythiolates ont été conçues et préparées.Les complexes ainsi préparés ont été caractérisés et leur activité évaluée par différentes techniques, dont la voltammétrie cyclique et l'électrolyse couplé à une GC, qui nous ont permis d'évaluer l'activité de nos catalyseurs (TON, TOF, surtension). Un des catalyseurs actifs a été utilisé comme support pour des simulations en DFT qui nous ont aidés à mieux comprendre le mécanisme catalytique de production d'hydrogène. / The energy supply sources are mainly based on fossil materials which are growing scarce and release pollutants and greenhouse gases.In this context, an energy vector appears as the future to feed the energetic needs of the planet: the Hydrogen; but its current production costs remain very high.Nature has deviced enzymes, hydrogenases, able to produce and oxidize hydrogen very efficiently. Nevertheless, the manipulation of these organisms is not easy, notably because of their susceptibility (oxygen inhibition, organic solvents, high temperatures), and their production costs are high.So, scientists have taken this inspiration source in order to design biomimetic and bioinspired models, which would much more robust and cheap catalysts to produce hydrogen.During this thesis, we have drawn our inspiration from [NiFe] hydrogenases, where the active site is a Ni-Fe core coordinated by four thiolate ligands. Our goal has been to design new polythiolate ligands, that gather some of the key hydrogenases [NiFe] properties responsible for their activity: thiolate ligands on the nickel, among them two brinding with the second metal, nickel tetraedric geometry.The synthesised complexes have been characterized and their activity tested (TON, TOF, overvoltage) by different techniques, among them cyclic voltammetry and electrolysis coupled to a GC.Finally, the bests have been tested further, thank to bulk electrolysis, which, coupled to a GC system, has enabled us to qualify and quantify the hydrogen production.One of our most active catalysts has been used as a support for DFT calculations, helping us to better undersand the catalytic hydrogen evolving mechanism.

Carbonyl complexes of Ni(0) incorporating two N-heterocyclic carbenes of the type Ni(CO)2(NHC)2 (NHC = ICy [N, N'-bis(cyclohexylimidazol)-2-ylidene], IMes [N, N'- bis(2, 4, 6-trimethylphenyl)-imidazol)-2-ylidene]) have been prepared. The complexes Ni(CO)2(ICy)2 (8) and Ni(CO)2(IMes)2 (9) have been synthesized and characterized by single crystal X-ray diffraction. The enthalpy of substitution reactions of Ni(CO)2(NHC) (NHC = ItBu [N, N'-bis(tert-butylimidazol)-2-ylidene], IAd [N, N'-bis(1- adamentylimidazol)-2-ylidene]) with NHC and tertiary phosphine ligands leading to the formation of Ni(CO)2(L)2 (L = NHC, PR3) complexes have been determined. The solution calorimetric investigations reiterate the greater electron donating property of the NHC ligands compared to tertiary phosphines. Thermochemical studies of the substitution reactions of Ni(CO)2(NHC) (NHC = ItBu, IAd) forming complexes (8) and (9) led to the determination of average bond dissociation energy of Ni-NHC (NHC = ICy, IMes) and Ni-P (P = PCy3, PPh3, P(p-Tol)3, P(m-Tol)3).

Foram feitos estudos das propriedades magnéticas e estruturais em nanofios de níquel em uma lâmina de alumínio. As amostras foram obtidas através da anodização em duas etapas, seguida de uma eletrodeposição AC. Foi verificado que o aumento do potencial usado nas anodizações acarretam em um aumento do tamanho dos grãos cristalinos de níquel e dos diâmetros dos nanofios. O tamanho dos grãos de níquel e dos diâmetros dos nanofios variaram, respectivamente, entre 10 a 20 nm e 30 a 50 nm. As amostras apresentam alta anisotropia de forma, com coercividade entre 565 a 725 Oe. As interações magnéticas foram estudadas através das curvas `delta´M, estas mostraram que as interações desmagnetizantes são dominantes nestes sistemas. O modelo de Stoner-Wohlfarth, acréscido de um termo de interação foi utilizado para simular e interpretar o comportamento magnético dos nanofios. Através dos resultados numéricos e experimentais foi verificado que a componente reversível (Mrev) da magnetização independe do estado inicial do sistema, diferentemente do comportamento para a componente irreversível (Mirr). Através da análise das curvas de Mrev(Mirr)Hi , provenientes dos resultados numéricos e experimentais, foi verificado que existe um forte indicativo quanto ao modo de inversão da magnetização por curling, para nanofios / Studies of magnetic and structural properties of nickel nanowires deposited on nanoporous alumina membranes were carried out. The samples were obtained by a two-step anodization, followed by an AC electrodeposition. It was noted that the diameters of the nanowires and the crystalline grain size of the deposited nickel increase with the anodization voltage. The mean diameters and the grain sizes varied from 10 to 20 nm and from 30 to 50 nm, respectively. The samples exhibited a strong shape anisotropy, with coercivities between 565 and 725 Oe. Magnetic interactions were studied via `delta´M curves, which showed that the dominant interactions are rather demagnetizing in these systems. An interacting Stoner-Wohlfarth model was developed to simulate and reproduce the magnetic behavior of the nanowires. From the comparison between numerical and experimental results (which exhibit excellent agreement), it was noted that reversible components of magnetization (Mrev) do not depend on the initial state of the system, whereas irreversible components (Mirr) do. From the analysis of Mrev(Mirr)Hi curves of numerical and experimental results, it was noted that there is strong evidence for the curling magnetization reversal mode for these systems

Este projeto faz parte de uma Rede Interdisciplinar de Pesquisa em Superligas no Brasil (Projeto Pró-Engenharias - CAPES), que tem como objetivo o desenvolvimento técnico e científico do Brasil nesta classe de materiais. A rede é composta por especialistas de estabelecida competência em assuntos fundamentais para o desenvolvimento de materiais estruturais, tais como: fusão em vácuo, solidificação direcional, relações orientação-propriedade, tratamentos térmicos, fluência, fadiga em alta temperatura, oxidação e corrosão a quente. Assim, na parte que compete a este pesquisador, foram estudadas as propriedades de fadiga em altas temperaturas da liga MAR-M247 e de uma nova liga, a liga MAR-M247 modificada pela substituição do Ta pelo Nb, e sendo doravante denominada MAR-M247(Nb). Foram desenvolvidos estudos correlacionando parâmetros intrínsecos do material, como composição química e microestrutura adicionalmente a parâmetros extrínsecos, tais como: temperatura, estudo de oxidação, propriedades de fadiga, ensaios de tração em temperatura ambiente, 250, 500, 700, 800, 900 e 1000ºC, conforme as normas AMERICAN SOCIETY FOR TESTING AND MATERIALS (ASTM) E 8M-00 e ASTM E 21-00. Em relação aos ensaios de fadiga foram realizados ensaios de nucleação de trincas , conforme a norma ASTM E466-07 e os resultados foram apresentados na forma de curvas S-N e analisados estatisticamente segunda a norma ASTM E739-10. Para auxiliar na definição dos micromecanismos de fadiga, as superfícies de fratura foram analisadas utilizando o microscópio eletrônico de varredura (MEV) e microscópio ótico estereoscópico (MO). Foi realizado ensaio de oxidação para verificar a susceptibilidade a oxidação das ligas, sendo este um dos fatores que afetam a vida em fadiga em alta temperatura. / This project is part of an interdisciplinary network of Research in Super League in Brazil (Project Pro-Engineering - CAPES), which aims to technical and scientific development of Brazil in this class of materials. The network is composed of experts of established competence in matters fundamental to the development of structural materials, such as: vacuum melting, directional solidification, relationships property-oriented, heat treatment, creep, fatigue in high temperature oxidation and hot corrosion. Thus, at the racing this researcher, were studied the fatigue properties at high temperatures MAR-M247 alloy and a new league, which in reality is the MAR-M247 alloy modified by replacing the Ta by Nb, and being hereinafter referred to as MAR-M247 (Nb). Were designed studies correlating parameters intrinsic material, such as chemical composition and microstructure, with extrinsic parameters such as: temperature and type of loading, with the properties fatigue. Thus, tensile tests at room temperature environment, 250, 500, 700 and 900ºC, and tests for compression at temperatures of 700 and 900ºC were performed to determine the elastic behavior and elastoplastic material, according to the ASTM E-8M 00, ASTM E 21-00 and ASTM E209-00. Were also conducted testing of fatigue crack nucleation, as ASTM E466-07. The results were presented at form of SN curves and statistically analyzed the second ASTM E739-10. To assist in the definition of micromechanics of fatigue, the fracture surfaces were examined in a scanning electron microscope (SEM) and stereoscopic optical microscope (OM). Was oxidation test performed to check susceptibility to oxidation of the alloy, which is the factor affecting the fatigue life.

Neste trabalho foi estudado as ligas La0,7-xMgx Pr0,3Al0,3Mn0,4Co0,5Ni3,8 (x = 0 a 0,7) como eletrodo negativo de baterias de níquel - hidreto metálico. A hidrogenação das ligas foi realizada com duas pressões de H2 (2 bar e 10 bar) e temperaturas (ambiente e 500°C). A capacidade de descarga das ba terias de níquel hidreto metálico foram analisadas pelo equipamento de testes elétricos ARBIN BT-4. As ligas, no estado bruto de fusão, foram analisadas por microscopia eletrônica de varredura (MEV), espectroscopia de energia dispersiva (EDS) e difração de Raios-X. Com o aumento da concentração de Mg nas ligas aumenta-se a capacidade de descarga, porém nota-se a diminuição a estabilidade cíclica das baterias. A capacidade de descarga máxima obtida foi para a liga Mg0,7Pr0,3Al0,3Mn0,4Co0,5Ni3,8 (60 mAh) e a bateria que apresentou a melhor performance foi La0,4Mg0,3Pr0,3Al0,3Mn0,4Co0,5Ni3,8 (53 mAh e 150 ciclos). A capacidade de absorção de hidrogênio diminui quando se adiciona Mg, não ocorrendo tal efeito para a liga Mg0,7Pr0,3Al0,3Mn0,4Co0,5Ni3,8. / In this work were studied of La0.7-xMgx Pr0.3Al0.3Mn0.4Co0.5Ni3.8 (x = 0 and 0.7) alloys for negative electrodes of the nickel-metal hydride batteries. The hydrogenation of the alloys was performed varying pressing of H2 (2 and 10 bar) and temperature (room and 500°C). The discharge capacity of the nic kel-metal hydride batteries were analyzed in ARBIN BT- 4 electrical test equipment. The as-cast alloys were analyzed by scanning electron microscopy (SEM), energy disperse spectroscopy (EDX) and X-Ray diffraction. The increasing Mg addition in the alloy increases maximum discharge capacity but decrease cycle life of the batteries. The maximum discharge capacity was obtained with the Mg0.7Pr0.3Al0.3Mn0.4Co0.5Ni3.8 alloy (60 mAh) and the battery which presented the best performance was La0.4Mg0.3Pr0.3Al0.3Mn0.4Co0.5Ni3.8 alloy (53 mAh and 150 cycles). The H2 capability of absorption was diminished for increased Mg addition and no such effect occurs for Mg0.7Pr0.3Al0.3Mn0.4Co0.5Ni3.8 alloy.

Neste trabalho são apresentados estudos referentes a dois grupos de sistemas contendo dióxido de enxofre como principal foco, tendo em vista a importância desta molécula em sistemas ambientais e sua caracteristicas químicas interessantes como seu caráter anfotérico e sua capacidade de interação com sistemas inorgânicos via oxigênio ou enxofre. Tendo como principais feramentas as espectroscopias vibracionais (espalhamento Raman e absorção no Infravermelho), eletrônica (UV-VIS) e Ressonância Magnética Nuclear (RMN) investigou-se as interações inter e intramoleculares dos sistemas de interesse. Primeiramente foi investigada a interação do SO2 com aminoálcoois, sendo que estes sistemas apresentam boa capacidade de absorção do SO2. Destaca-se a formação de zwitteríons pela interação do SO2 com o grupamento alcoólico da molécula, observado apenas quando da presença de grupo amino para estabilização da separação de cargas gerada, mostou-se que o poduto fomado é mais estavél quanto menor a separação das cargas e menor o impedimento estérico na amina. Este sistema foi investigado quanto a sua revesibilidade, que foi observada sempre acompanhada de degradação do aminoálcool. O segundo sistema refere-se a interação do dióxido de enxofre com complexos de níquel em dois estados de oxidação (II/III) com ligante macrocíclico cyclam (1,4,8,11- Tetraazaciclotetradecano); o diferencial deste estudo frente a outros apresentados na literatura é a análise das reações em meio anidro. Nos experimentos em meio livre de O2 obseva-se a redução do complexo de Ni (III) a Ni(II) e em meio contendo O2 observa-se a oxidação do complexo de Ni(II) a Ni(III), mostrando a importância do O2 para a manutenção de um ciclo catalítico capaz de oxidar SO2 a SO42-. Os resultados aqui apresentados indicam que os mecanismos em meio anidro são bastante semelhantes aos observados em meio aquoso. / In this work we focus on two sulfur dioxide containing systems due to the relevance of this molecule in environmental science and its interesting physico-chemical properties as its amphoteric characteristic and ability to interact with inorganic systems through oxygen or sulfur atoms. The main tools for investigation was vibrational spectroscopy (Raman scattering and Infrared absorption), electronic spectroscopy (UV-VIS) and Nuclear Magnetic Resonance (NMR), whereby the intra and intermolecular interactions were probed. The first subject of investigation was the study of interactions between SO2 and amino alcohol. This system shows great ability to capture SO2, highlighting the zwitterionic formation due to the bonding of SO2 via the alcoholic part of the amino alcohol molecule, what is only possible due to the presence of the amino group to stabilize the charge separation, the stability of the poduct depends on the steric hindrance and on the charge separation. The reversibility of the system was investigated and it was always accompanied by degradation of the amino alcohol. The second system consists in the investigation of interactions between SO2 and two nickel-cyclam (1,4,8,11-Tetraazacyclotetradecane) complexes, where the metal is in different oxidation states (II/III). This work is different from previous in the sense that the analyses are carried out in anhydrous environment. In O2 free environment we were able to see the reduction of Ni(III) to Ni(II) complex, and in presence of O2 the oxidation of Ni(II) to Ni(III) complex occurs, showing the relevance of O2 to catalytic cicle that is able to transform SO2 to SO42-. Our results suggest that the mechanisms in aqueous and nonaqueous environments are very similar.

Neste trabalho são apresentados estudos referentes a dois grupos de sistemas contendo dióxido de enxofre como principal foco, tendo em vista a importância desta molécula em sistemas ambientais e sua caracteristicas químicas interessantes como seu caráter anfotérico e sua capacidade de interação com sistemas inorgânicos via oxigênio ou enxofre. Tendo como principais feramentas as espectroscopias vibracionais (espalhamento Raman e absorção no Infravermelho), eletrônica (UV-VIS) e Ressonância Magnética Nuclear (RMN) investigou-se as interações inter e intramoleculares dos sistemas de interesse. Primeiramente foi investigada a interação do SO2 com aminoálcoois, sendo que estes sistemas apresentam boa capacidade de absorção do SO2. Destaca-se a formação de zwitteríons pela interação do SO2 com o grupamento alcoólico da molécula, observado apenas quando da presença de grupo amino para estabilização da separação de cargas gerada, mostou-se que o poduto fomado é mais estavél quanto menor a separação das cargas e menor o impedimento estérico na amina. Este sistema foi investigado quanto a sua revesibilidade, que foi observada sempre acompanhada de degradação do aminoálcool. O segundo sistema refere-se a interação do dióxido de enxofre com complexos de níquel em dois estados de oxidação (II/III) com ligante macrocíclico cyclam (1,4,8,11- Tetraazaciclotetradecano); o diferencial deste estudo frente a outros apresentados na literatura é a análise das reações em meio anidro. Nos experimentos em meio livre de O2 obseva-se a redução do complexo de Ni (III) a Ni(II) e em meio contendo O2 observa-se a oxidação do complexo de Ni(II) a Ni(III), mostrando a importância do O2 para a manutenção de um ciclo catalítico capaz de oxidar SO2 a SO42-. Os resultados aqui apresentados indicam que os mecanismos em meio anidro são bastante semelhantes aos observados em meio aquoso. / In this work we focus on two sulfur dioxide containing systems due to the relevance of this molecule in environmental science and its interesting physico-chemical properties as its amphoteric characteristic and ability to interact with inorganic systems through oxygen or sulfur atoms. The main tools for investigation was vibrational spectroscopy (Raman scattering and Infrared absorption), electronic spectroscopy (UV-VIS) and Nuclear Magnetic Resonance (NMR), whereby the intra and intermolecular interactions were probed. The first subject of investigation was the study of interactions between SO2 and amino alcohol. This system shows great ability to capture SO2, highlighting the zwitterionic formation due to the bonding of SO2 via the alcoholic part of the amino alcohol molecule, what is only possible due to the presence of the amino group to stabilize the charge separation, the stability of the poduct depends on the steric hindrance and on the charge separation. The reversibility of the system was investigated and it was always accompanied by degradation of the amino alcohol. The second system consists in the investigation of interactions between SO2 and two nickel-cyclam (1,4,8,11-Tetraazacyclotetradecane) complexes, where the metal is in different oxidation states (II/III). This work is different from previous in the sense that the analyses are carried out in anhydrous environment. In O2 free environment we were able to see the reduction of Ni(III) to Ni(II) complex, and in presence of O2 the oxidation of Ni(II) to Ni(III) complex occurs, showing the relevance of O2 to catalytic cicle that is able to transform SO2 to SO42-. Our results suggest that the mechanisms in aqueous and nonaqueous environments are very similar.

A castable alloy, i.e., one that flows easily to fill the entire mold cavity and also has resistance to hot tearing during solidification, must invariably contain a sufficient amount of a eutectic structure. For this reason, most traditional aluminum casting alloys contain silicon because the aluminum-silicon eutectic imparts to the alloy excellent casting characteristics. However, the solidus temperature in the Al-Si system does not exceed 577°C, and the major alloying elements (i.e., zinc, magnesium, and copper) used with silicon in these alloys further lower the solidus temperature. Also, these elements have high diffusivity in aluminum and so, while they enhance the room temperature strength of the alloy, they are not useful at elevated temperatures. Considering nickel-base super alloys, whose mechanical properties are retained up to temperatures that approach 75% of their melting point, it is conceivable that castable aluminum alloys can be developed on the same basis so that they are useful at temperatures approaching 350C. A castable aluminum alloy intended for high temperature applications must contain a eutectic structure that is stable at temperatures higher than 600°C, and must contain second phase precipitate particles that are thermodynamically stable at the service temperature. Transition metal trialuminides with the general chemical formula AlxTMy in which TM is a transition metal, are excellent candidates for both the eutectic structure and the precipitate particles. In this research, the use of transition metals in the constitution of aluminum casting alloys is investigated with emphasis on the morphology, crystallography, and mechanisms of formation of the various phases.

Dans le cadre de ce projet de thèse, des microstructures innovantes « composites » Ni-W constituées d’amas de Tungstène multi-cristallins (à grains fins) immergés dans une matrice de la solution solide Ni(W) cfc ont été élaborées par frittage flash (Spark Plasma Sintering (SPS)). Différents alliages ont ainsi été fabriqués en contrôlant de manière très précise les fractions volumiques respectives des deux élément Ni et W. En outre, le fait que le Ni soit un matériau particulièrement ductile contrairement au W plus résistant, peut conférer au matériau un bon compromis ductilité/résistance mécanique. Ainsi, en ajustant les taux respectifs de Ni et/ou de W, nous avons réussi à faire cohabiter dans un même matériau les micro-mécanismes de déformation propres à chaque phase, dont les caractéristiques et les évolutions sont ensuite analysées lors de sollicitations mécaniques conventionnelles ou in situ sous Synchrotron. Ainsi, nous avons mis en évidence le rôle de chacune des phases constituant la microstructure vis-à-vis du comportement macroscopique. Il est clairement montré que la proportion et l’arrangement spatial de la phase de W sont des facteurs influents sur la fragilité d’ensemble ainsi que sur les transferts de charge entre phases. Concernant la phase ductile, nous avons pu mesurer des déformations du réseau cristallin d’amplitude inhabituelle, que nous avons reliées à la densité initiale importante de joints de type ∑3, densité qui ensuite diminue fortement sous sollicitation mécanique. / As part of this thesis project, innovative “composites” microstructures Ni-W composed by clusters of multi crystallized (ultra fine grain) W embedded in a matrix of a cfc Ni(W) solid solution were elaborated by spark plasma sintering (SPS). Several alloys were processed by controlling precisely the respective volume fractions of the two elements Ni and W. In addition, Ni is a particularly ductile material unlike the more resistant W. So, it may give to the material a good compromise between ductility and mechanical resistance. Thus, by adjusting the respective fractions of Ni and/or W, we obtained in the same material the specific deformation micro-mechanisms of each phase, the characteristics and evolutions of those deformations were after analyzed during conventional mechanical stresses or under in situ Synchrotron. Thus, we have highlighted the role of each phase constituting the microstructure regarding the macroscopic behavior. It is clearly shown that the proportion and spatial distribution of the W phase are key factors on the overall brittleness as well as on the load transfer between the phases. Concerning the ductile phase, we underscored deformations of unusual amplitude, which are connected to the high initial density of ∑3 boundary grains, which then decreases sharply under mechanical stress.