[pt] O principal objetivo deste trabalho foi avaliar a evolução microestrutural de dois tipos de nanocompósitos metal/cerâmico: Cu-10(por cento)Ni-1(por cento)Al2O3 (Cu-rich) e Ni-10(por cento)Cu-1(por cento)Al2O3 (Ni-rich) consolidadas em forma de fitas. A obtenção de nanoparticulas precursoras às fitas se deu por uma rota química, (que compreende a decomposição térmica de nitratos metálicos, originando óxidos coformados (CuO-NiO-Al2O3), seguido da redução seletiva destes por hidrogênio). O pó constituído de nanopartículas metálicas CuNi de 20nm a 100nm, com dispersão de nanopartículas ainda mais finas de Al2O3, foi submetido a pressão uniaxial a frio, em forma de pastilhas, e posteriormente sinterizado por 30 minutos. As pastilhas foram laminadas a frio com redução de espessura em 40, 60 e 80 por cento. As fitas assim produzidas foram recozidas a 600 graus Celsius nas amostras Cu-rich e a 900 graus Celsius nas Ni-rich, durante 5, 30 e 300 minutos, gerando diferentes estados microestruturais em virtude de fenômenos de recuperação, recristalização e crescimento de grão, na presença do Al2O3 na matriz metálica. O estudo detalhado da evolução microestrutural foi realizado por Microscopia Eletrônica de Varredura, Feixe de Íons Focalizado e Microscopia Eletrônica de Transmissão (MET), nos modos convencional e transmissão varredura (STEM), e em alta resolução (HRTEM). Tanto no MEV como no MET/STEM analises composicionais foram sistematicamente conduzidas por espectroscopia de dispersão de energia característica de raios x (EDXS). A preparação das amostras para MEV foi realizada por metodos metalogarficos convencionais e também submetidas a polimento por feixe de íons no instrumento MEV/FIB, quando necessário. As amostras transparentes ao feixe de elétrons para MET foram preparadas por métodos eletrolíticos convencionais e seletivos como o denominado jato duplo, assim como por feixe de íons no instrumento de precisão (PIPS) e em regiões especificas selecionadas extraindo lamelas através do FIB. Foi observado que as partículas cerâmicas não se dispersam homogeneamente na matriz metálica policristalina, mas se auto segregam em finos aglomerados seguindo o sentido da laminação e servindo como sítios preferenciais para a nucleação heterogênea de novos grãos, durante o fenômeno de recristalização no recozimento. Observa-se que nos lugares que o Al2O3 está presente o tamanho de grão, TG, é bem menor quando comparado com os lugares em ausência de Al2O3. De fato, observou-se sistematicamente que, principalmente nas amostras com alto grão de deformação ocorreram recristalização e crescimento de grão, gerando microestruturas bastante heterogêneas em quanto ao tamanho de grão, dando lugar a regiões da mostra com TG variando de 10nm a 100nm e regiões vizinhas na amostra com TG entre 1 um e 10 um. Medidas de microdureza comprovaram que as nanopartículas de Al2O3 agem como eficiente reforço, pois aumentou em até 100 porcento a dureza do material, quando comparado ao mesmo sem Al2O3. / [en] In this work it is evaluated the microstructural evolution of two types of metal/ceramic nanocomposites, Cu-10(percent)wt(percent)Ni-1(percent)Al2O3 (Cu-rich) and Ni-10Cu-1(percent)Al2O3 (Ni-rich), consolidated in ribbons. Initially, the precursor nanoparticles were obtained by a chemical route synthesis based on the thermal decomposition of Cu and Ni metal nitrates solution, as it generates co-formed oxides (CuO-NiOAl2O3). This material was selectively reduced by hydrogen in order to produce the nanocomposites. The CuNi matrix with particle size of about 20-100 nm containing a dispersion of even finer Al2O3 was uniaxially cold pressed into pellets and then aggregated by heating for 30 minutes. The treated pellets were cold rolled aiming a thickness reduction of 40, 60 and 80 (percent). The produced ribbons were then annealed at 600 degrees Celsius for Cu-rich samples and at 900 degrees Celsius for Nirich samples for periods of 5, 30 and 300 minutes. This step has produced different microstructural states due to phenomena of recovery, recrystallization and grain growth. The microstructural analysis was performed by Scanning Electron Microscopy (MEV), Focused Ion Beam (FIB), and Transmission Electron Microscopy (MET). All of the studies included the conventional and scanning (STEM) modes and high resolution (HRTEM). Particularly, the SEM and TEM / STEM compositional analyzes were conducted by x-ray energy dispersive spectroscopy (EDXS). The preparation of the samples for MEV was performed by conventional metallography, if required, the samples were subject to ion beam polishing in the MEV / FIB instrument. Electron transparent samples were prepared by conventional double jet electropolishing of thin foils, ion milling in precision instrument (PIPS) as well as selected lamellae prepared by Focus Ion Beam (FIB).These studies indicate that the ceramic particles are not homogeneously disperse in the polycrystalline metal matrix, but they selfsegregate in fine agglomerates following the direction of the cold rolled, and serve as preferential sites for the heterogeneous nucleation of new grains, due to recrystallization phenomenon, during annealing. It has also been observed that in the regions with the presence of Al2O3 the grain size of the nanoparticles is smaller. Actually, in the samples with high grain of deformation, recrystallization and grain growth occurred, generating highly heterogeneous size for the microstructures (range about 50nm to 10um). Microhardness measurements have showed that Al2O3 is a good reinforcement, as it increased the hardness of the material by up to 100 percent when compared with the same material without Al2O3.

Aluminas have had some form of chemical and industrial use throughout history. For little over a century corundum (α-Al2O3) has been the most widely used and known of the aluminas. The emerging metastable aluminas, including the γ, δ, η, θ, κ, β, and χ polymorphs, have been growing in importance. In particular, γ-Al2O3 has received wide attention, with established use as a catalyst and catalyst support, and growing application in wear abrasives, structural composites, and as part of burner systems in miniature power supplies. It is also growing in importance as part of the feedstock for aluminium production in order to affect both the adsorption of hydrogen fluoride and the feedstock solubility in the electrolytic solution. However, much ambiguity surrounds the precise structure of γ-Al2O3. Without proper knowledge of the structure, understanding the properties, dynamics and applications will always be less than optimal. The aim of this research was to contribute towards settling this ambiguity. This work was achieved through extensive computer simulations of the structure, based on interatomic potentials with refinements of promising structures using density functional theory (DFT), and a wide range of supporting experiments. In addition to providing a more realistic representation of the structure, this research has also served to advance knowledge of the evolution of the structure with changing temperature and make new insights regarding the location of hydrogen in γ-Al2O3. / Both the molecular modelling and Rietveld refinements of neutron diffraction data showed that the traditional cubic spinel-based structure models, based on m Fd3 space group symmetry, do not accurately describe the defect structure of γ-Al2O3. A more accurate description of the structure was provided using supercells of the cubic and tetragonal unit cells with a significant number of cations on c symmetry positions. These c symmetry based structures exhibited diffraction patterns that were characteristic of γ-Al2O3. The first three chapters of this Thesis provide a review of the literature. Chapter One provides a general introduction, describing the uses and importance of the aluminas and the problems associated with determining the structure of γ-Al2O3. Chapter Two details the research that has been conducted on the structure of vi γ-Al2O3 historically. Chapter Three describes the major principles behind the computational methods employed in this research. In Chapter Four, the specific experimental and computational techniques used to investigate the structure of γ-Al2O3 are described. All preparation conditions and parameters used are provided. Chapter Five describes the methodology employed in computational and experimental research. The examination of the ~ 1.47 billion spinel-based structural possibilities of γ-Al2O3, described using supercells, and the selection of ~ 122,000 candidates for computer simulation, is detailed. This chapter also contains a case study of the structure of κ-Al2O3, used to investigate the applicability of applying interatomic potentials to solving complex structures, where many possibilities are involved, and to develop a systematic procedure of computational investigation that could be applied to γ-Al2O3. Chapters Six to Nine present and discuss the results from the experimental studies. / Preliminary heating trials, performed to determine the appropriate preparation conditions for obtaining a highly crystalline boehmite precursor and an appropriate calcination procedure for the systematic study of γ-Al2O3, were presented in Chapter Six. Chapter Seven details the investigation of the structure from a singletemperature case. Several known structural models were investigated, including the possibility of a dual-phase model and the inclusion of hydrogen in the structure. It was demonstrated that an accurate structural model cannot be achieved for γ-Al2O3 if the cations are restricted to spinel positions. It was also found that electron diffraction patterns, typical for γ-Al2O3, could be indexed according to the I41/amd space group, which is a maximal subgroup of m Fd3 . Two models were presented which describe the structure more accurately; Cubic-16c, which describes cubic γ-Al2O3 and Tetragonal-8c, which describes tetragonal γ-Al2O3. The latter model was found to be a better description for the γ-Al2O3 samples studied. Chapter Eight describes the evolution of the structure with changing calcination temperature. Tetragonal γ-Al2O3 was found to be present between 450 and 750 °C. The structure showed a reduction in the tetragonal distortion with increasing temperature but at no stage was cubic γ-Al2O3 obtained. Examination of the progress of cation migration indicates the reduction in the tetragonal nature is due to ordering within inter-skeletal oxygen layers of the unit cell, left over from the breakdown of the hydroxide layers of boehmite when the transformation to γ-Al2O3 occurred. Above 750 °C, δ-Al2O3 was not observed, but a new phase was identified and designated γ.-Al2O3. / The structure of this phase was determined to be a triple cell of γ-Al2O3 and is herein described using the 2 4m P space group. Chapter Nine investigates the presence of hydrogen in the structure of γ-Al2O3. It was concluded that γ-Al2O3 derived from highly crystalline boehmite has a relatively well ordered bulk crystalline structure which contains no interstitial hydrogen and that hydrogen-containing species are located at the surface and within amorphous regions, which are located in the vicinity of pores. Expectedly, the specific surface area was found to decrease with increasing calcination temperature. This trend occurred concurrently with an increase in the mean pore and crystallite size and a reduction in the amount of hydrogen-containing species within the structure. It was also demonstrated that γ-Al2O3 derived from highly crystalline boehmite has a significantly higher surface area than expected, attributed to the presence of nano-pores and closed porosity. The results from the computational study are presented and discussed in Chapter Ten. Optimisation of the spinel-based structural models showed that structures with some non-spinel site occupancy were more energetically favourable. However, none of the structural models exhibited a configuration close to those determined from the experimental studies. Nor did any of the theoretical structures yield a diffraction pattern that was characteristic of γ-Al2O3. This discrepancy between the simulated and real structures means that the spinel-based starting structure models are not close enough to the true structure of γ-Al2O3 to facilitate the derivation of its representative configuration. / Large numbers of structures demonstrate migration of cations to c symmetry positions, providing strong evidence that c symmetry positions are inherent in the structure. This supports the Cubic-16c and Tetragonal-8c structure models presented in Chapter Seven and suggests that these models are universal for crystalline γ-Al2O3. Optimisation of c symmetry based structures, with starting configurations based on the experimental findings, resulted in simulated diffraction patterns that were characteristic of γ-Al2O3.

Petrologic, structural and age investigations of the Lolotoi Complex of East Timor indicate that it is part of a group of thin metamorphic klippen found throughout the region that were detached from the Banda forearc and accreted to the NW Australian continental margin during Late Miocene to Present arc-continent collision. Metamorphic rock types are dominated by (in order of greatest to least abundance), greenschist, graphitic phyllite, quartz-mica schist, amphibolite and pelitic schist. Mineral, whole rock, and trace element geochemical analyses of metabasites indicate that protolith compositions are consistent with tholeiitic basalt and basaltic andesite with mixed MORB and oceanic arc affinities. Metapelitic schist compositions are consistent with mafic to intermediate oceanic to continental arc provenance. Geothermobarometric calculations show peak metamorphic temperatures in pelitic rocks range from 530°C to 610°C for garnet-biotite pairs and peak pressures of 5 to 8 kbar for garnet-aluminosilicate-quartz-plagioclase assemblages. Analyses of amphibole in amphibolites yield temperatures of 550°C to 650°C and pressures of 6 to 7 kbar. Lu-Hf analyses performed on garnet samples from two massifs in East Timor yielded four ages with a mean of 45.36 ± 0.63 Ma, which is interpreted to represent the approximate age of peak metamorphism. Detrital zircons from one amphibolite sample in East Timor yields a bimodal U-Pb age distribution of 560 Ma and 80 Ma, indicating deposition occurred after the 80 Ma closure of the zircon grains. The sequence of deformation as indicated by field measurements is similar to that reported from other klippen throughout the Timor region. Contact relationships with adjacent units indicate that the metamorphic terrane is in thrust contact with underlying Gondwana Sequence rocks. Overlying the metamorphic rocks are Asian affinity volcanic and sedimentary cover units found mostly in normal fault contact on the edges of Lolotoi Complex klippen. Geochemical, age, petrological and structural data imply the Lolotoi Complex formed part of the eastern Great Indonesian arc, which began to collapse in the Eocene, was incorporated into the Banda arc in the Miocene, and accreted to the Austrailian continental margin from Pliocene to Present.

Ce travail porte sur la synthèse, la mise en forme et la caractérisation desolutions solides de type tysonite RE1-xMxF3-x (RE = La, Sm, Ce et M = Ba, Ca, Sr). Dans unpremier temps, une démarche d’étude rigoureuse est mise en place pour la solution solide ditede référence, La1-xBaxF3-x. Les synthèses menées à l’état solide aboutissent à une maîtrise dela composition chimique et à l'établissement de lois de variations des paramètres structuraux.Une meilleure compréhension de l’influence de la structure sur la mobilité des ions F- estégalement acquise. L’influence du frittage dans l’obtention de bonnes valeurs de conductivitéionique est également à souligner. Dans un second temps, les effets de la nanostructurationpar mécanobroyage sur les propriétés de conductivité sont évalués. L’utilisation de laméthodologie des plans d’expériences mène à la mise au point des réglages optimums debroyage. Il apparaît alors que la synthèse des électrolytes peut être accélérée et mise àl’échelle tout en gardant des valeurs optimales de conductivité. Enfin, la démarche déterminéeest appliquée à d'autres solutions solides de type tysonite et à la recherche du conducteurionique le plus performant. Si les composés issus de la substitution Ce/Sr ou encore Sm/Casemblent les plus prometteurs, la plus grande stabilité chimique de la solution solide La1-xSrxF3-x est le compromis idéal pour l'utiliser comme électrolyte solide lors des mesuresélectrochimiques des batteries. / This work deals with the synthesis, shaping and characterization of RE1-xMxF3-x (RE = La, Sm, Ce et M = Ba, Ca, Sr) tysonite-type solid solutions. In a first part, onemeticulous approach has been set up for La1-xBaxF3-x solid solution, chosen as a reference.The solid-state synthesis of these materials led to a better knowledge of their chemicalcomposition (Vegard’s laws) and of the structure-ionic mobility correlations. The impact ofthe sintering process on the ionic conductivity is also highlighted. In a second part, the effectsof the nanostructuration conducted by ball-milling of the microcrystalline samples areevaluated. The use of the Design of Experiments methodology led to identify the optimummilling conditions. It appears that the synthesis of electrolytes can be sped- and scaled-up,while keeping high ionic conductivity properties. At last, this approach is applied on othertysonite-type solid solutions, to look for the best electrolyte. The Ce/Sr and Sm/Casubstitutions generate very promising ionic conductors but not really (electro)chemicallystable compounds. A compromise has been found with the choice of the La1-xSrxF3-x solidsolution as the FIB electrolyte for the electrochemical performances tests, regarding its higherchemical stability.

Cette thèse est centrée sur la ceinture orogénique Attico-Cycladique formée durant l'orogénèse Alpine. Par une approche multi-méthodes et multi-échelles combinant géologie structurale, pétrographie, thermobarométrie des assemblages minéraux, géochimie élémentaire et isotopique, et données PVTX des inclusions fluides associées, ce travail vise à caractériser et comprendre les relations entre circulations fluides, interactions fluides/roches, déformation, et mobilisation-transport-dépôt des métaux. Les marbres et schistes de la péninsule du Lavrion et de l'île d'Eubée témoignent d'une évolution orogénique complexe marquée par une phase d'enfouissement à l'Eocène suivie par deux phases d'exhumation successives syn-et post-orogéniques. Les minéralisations de type Cu-Pb-Zn-Fe-Ag de la région du Lavrion sont synchrones de l’activation du détachement post-orogénique et de la mise en place de plutons de granodiorite. Leurs positions structurales témoignent d’un piégeage depuis un régime de déformation ductile jusqu'à fragile. Les minéralisations mises en place durant le régime de déformation ductile à ductile-fragile (skarn et remplacement de carbonate) sont associées à la décarbonatation des niveaux de marbres et à la circulation des fluides magmatiques. L'exhumation progressive de la racine orogénique se traduit par la transition des roches depuis une déformation ductile vers un régime fragile associé à l’ouverture du système aux fluides de surface et notamment aux fluides météoriques. Cette circulation est responsable d’une remobilisation des métaux des minéralisations primaires permettant alors une seconde phase de précipitation dans un régime cassant (veines épithermales) / This thesis is focused on the Attico-Cycladic orogenic wedge formed during the Alpine orogeny. From a multi-method and multi-scale approach using structural geology, petrography, mineral thermobarometry, element and isotope geochemistry, and PVTX data of associated fluid inclusions, this study deciphers the relationships between fluid circulation, fluid-rock interactions and mobilisation-transport-deposits of metals. Marbles and schists from the Evia Island and the Lavrion peninsula testify to a complex orogenic history marked by an Eocene burial phase followed by syn- and post-orogenic exhumation. Cu-Pb-Zn-Fe-Ag mineralisations from the Lavrion area are synchronous with the formation of the low-angle post-orogenic detachment and the emplacement of granodioritic magmas. The structural position of the deposits attests of an emplacement during ductile to brittle deformation conditions. Deposits associated with ductile to ductile-brittle deformation (skarn, carbonate replacement) are related to a marble decarbonation and magmatic fluid circulation. The progressive exhumation of the orogenic wedge allows the transition toward brittle conditions and opens the system to surficial meteoritic fluids. This meteoritic fluid circulation is responsible to remobilisation of metals from primary deposits allowing thus a second phase of deposition in a pure brittle deformation (epithermal veins)