Uma nova rota de síntese via metodo sol-gel para óxido de titânio (titânia) e óxido misto titânio/zircônio (zircônia) é proposta neste trabalho. As amostras foram submetidas ao tratamento hidrotérmico e obteve-se compostos mesoestruturados e de elevada área superficial. Algumas amostras foram submetidas à calcinação a 450°C para a verificação da estabilidade a altas temperaturas. As amostras foram analisadas por difratometria de raios-x (DRX), espalhamento de raios-x de baixo ângulo (SAXS), área superficial através do método BET, por microscopia eletrônica de varredura por emissão de campo (FE-SEM), além de serem testadas na fotodegradação de corantes. Foram testados diferentes alcóxidos precursores, isopropóxido de titânio e n-butóxido de titânio; ácidos, clorídrico e nítrico; e surfactantes, Pluronic® P123, Brij® 700 e Brij® 98; e também variadas as quantidades de surfactantes utilizadas, para que fosse possível analisar como estas variações afetam a síntese dos compostos e se estabelecer uma nova rota padronizada utilizando-se os melhores precursores em quantidades ideais. Para efeito de comparação, foi testada uma rota alcalina de síntese, que levou ao material com área superficial mais elevada. Como resultado deste trabalho, foi desenvolvida uma nova rota de síntese para óxidos mesoestruturados de titânio e titânio/zircônio corn elevada área superficial, na qual a etapa de calcinação para remoção do surfactante foi eliminada. Algunas dos materiais preparados mostraram excelente desempenho na degradação fotocatalítica de um corante comercial. / A new sol-gel based synthetic route for titania and mixed titania-zirconia ceramic powders is proposed in this contribution. This route combines a surfactant-template strategy with hydrothermal treatment, yielding mesostructured compoundes with a high surface area. Some samples were calcined at 450 °C in order to verify the stability of the structures at these temperatures. The materials were characterized by x-ray diffraction (XRD), small angle x-ray scattering (SAXS), surface area (BET method), field emission scanning electron microscopy (FE-SEM), and were also tested in the photocatalytic degradation of selected dyes. Different precursor alcóxidos were used: titanium isopropoxide and titanium n-butoxide. Two different acids were used to catalyze the hydrolysis reaction, HCl and HNO3. Three surfactants were used as templating agents: Pluronic P123®, Brij 700®, and Brij 98®. The amount of surfactant was also changed in order to verify how these variations affect the surface area and morphology of the resulting compounds. For comparison, an alkaline route was also tested, in which the highest surface area was observed. As a result of this work, a new synthetic route for mesostructured titania and titania-zirconia mixed oxides was developed, in which the surfactant is removed without a calcinations step, resulting in compounds with high surface areas and, in some cases, excellent photocatalytic properties for the degradation of a dye.

O objetivo principal desse trabalho é investigar a aplicação de cerâmica á base de Zirconia em ferramentas de corte na usinagem de aço temperado (VND) utilizando um torno de ultraprecisão. Foram analisados dois tipos de composições de cerâmicas com estrutura cristalina diferentes, sendo elas: monoclínica e tetragonal. A diferença destas estruturas é devido à adição de Ytria. A fase monoclínica não contém Ytria em sua composição, enquanto, a fase tetragonal é obtida com Ytria (\'Y IND.3\') (chamada zirconia parcialmente estabilizada com Ytria). A fase tetragonal apresenta uma resistência elevada ao impacto junto com alta dureza (1800 kgf/\'MM POT.2\') quando comparada com a fase monoclínica que apresenta alta dureza mas menor tenacidade. Devido a este fato, esses materiais têm chamado à atenção dos pesquisadores para a usinagem de aços endurecidos. A geração de superfície é influenciada por diversos fatores, sendo eles: material peça, condições de corte, erros macro geométrico, erros de micro geometricos e do estado da aresta da ferramenta. Na usinagem de ultraprecisão a alta rigidez e vibração/trepidação máquina ferramenta é usada para evitar erros de micro geometria e macro geometria que conseqüentemente são transferidos para superfície da peça. Neste trabalho, devido ao fato de se usar um torno de ultraprecisão é possível afirmar que o perfil da rugosidade é gerado pela replicação do perfil da aresta da ferramenta de corte para a superfície da peça. A rugosidade da superfície foi medida com um perfilometro óptico com resolução de 0,1 nm. Os resultados mostraram que a rugosidade da superfície obtida após os testes de usinagem com as ferramantas de cerâmicas chegou á valores em torno de 0,140 microns, o que equivale ao acabamento com processo de retificação. Outro aspecto importante refere-se ao desgaste das ferramentas que, conseqüentemente, tem uma grande influência nos resultados obtidos. As ferramentas de corte foram analisadas antes e depois da usinagem por microscópio eletrônico de varredura. Verificou-se que as ferramentas de corte na fase tetragonal apresentaram desgaste do tipo cratera na aresta da ferramenta enquanto a aresta da ferramenta monoclínica apresentou desgaste do tipo lascamento. / The main objective of this work is to investigate the application of a ceramic composite of Alumina-Zirconia cutting tools inserts in the machining of hardened steel (VND) in an ultraprecision lathe. Two different ceramic compositions with different crystalline structure were tested, to know: monoclinic and tetragonal. The difference in these structures is due the addition of Yttrium. The monoclinic phase has no Yttrium in its composition while the tetragonal phase is obtained with Ytrium (\'Y IND.3\') (named partially stabilized zirconium). The tetragonal phase presents a high impact toughness along with high hardness (1800 kgf/\'MM POT.2\') when compared to the monoclinic phase which presents high hardness but lower toughness. Due to this fact, these materials have draw attention of researchers in the field of machining of hardened steels. The surface generation is influenced by several factors, to know: workpiece material, cutting conditions, macro geometry errors, micro geometry errors and the sharpness of the cutting edge. In ultraprecision machining, a high stiffness and chatter/vibration free machine tool is used in order to avoid common macro and micro geometry errors replicated into the workpiece surface. In this case, it is possible to assert that the roughness profile is generated by the replication of the cutting tool edge profile to the workpiece surface. The surface roughness was measured by an optical profiler with resolution of 0,1 nm. The results showed that the surface roughness obtained after machining tests with these ceramic inserts were in the range of 0,140 micrometers, which is in the same range of roughness obtained by the grinding process. Another important aspect refers to the wear of the ceramic inserts which has direct influence in the performance as a cutting tool material. The cutting inserts were evaluated before and after machining by scanning electron microscope. It was found that the tetragonal phase cutting tools presented crater wear on the rake face while the monoclinic phase presented cutting edge chipping as the main main type of wear.

Due to the increasing demand from patients and dentists for highly aesthetic and strong, metal-free restorations there has been a rapid increase in research into dental CAD CAM technique and zirconia based restorations over the last decade. Such new technology has the potential to take the place of conventional techniques and materials for fabricating indirect dental restorations in the future. In this PhD thesis, five laboratory studies were designed to investigate zirconia bridges constructed using dental CAD CAM. The studies concentrated on: 1. Ideal force applied by dentists for cementing zirconia bridges and the impact on seating. 2. The effect of firing cycles and zirconia thickness on the fit of zirconia bridges. 3. The effect of span length on the fit of three and four unit all zirconia bridges. 4. The effect of veneering on the strength of three unit zirconia bridges. 5. The fit of three unit all zirconia bridges produced by digital and conventional techniques. For these laboratory studies an ideal three unit (and four unit for study 3) fixed-fixed all ceramic bridge preparation was carried out on two plastic teeth and all SLA models and zirconia based bridges were made using the Lava COS and Lava™ CAD CAM system (3M, ESPE). In addition to the laboratory studies, a clinical audit was carried out to assess satisfaction (dentist, dental technician and patient) with zirconia based restorations (through a xvi series of questionnaires) made and fitted at Dundee Dental Hospital and School. In addition, as part of this audit a simple cost analysis was carried out to explore the differences in cost between zirconia based restorations and high fusing gold alloy based metal ceramic restorations. Four of the studies (studies 1, 2, 3 and 5) investigated the internal and marginal fit of the zirconia based restorations under differing laboratory and clinical procedures and conditions. It was found that the seating force used to cement a zirconia based bridge had no impact upon fit (Study 1). Whilst the thickness of zirconia (all-zirconia bridge and un-veneered zirconia framework) did not affect the fit of the restoration, veneering the framework did lead to a statistically significant deterioration in fit (Study 2). Although leading to a poorer fit veneering did have a positive effect in strengthening the zirconia framework, but neither un-veneered nor veneered frameworks were as strong as monolithic/all zirconia bridges (Study 4). Despite the high shrinkage during post milling sintering and the potential for greater distortion on longer span bridges, the longer span bridges investigated in Study 3 did not impact upon fit. In study 1, 2, 3 and 4 the Lava COS intra-oral scanner was used to create a digital impression of the tooth preparations and study 5 confirmed that the fit of bridges made from these impressions were better than those made using conventional addition cured silicone putty and wash impressions (Study 5). The results of the questionnaires used in the audit revealed high satisfaction rates with all stake holders and the cost analysis showed that producing zirconia based restorations can be five to six times cheaper than conventional gold based restorations. Despite the variations in fit which were found in Studies 2 and 5, all bridges produced were within what would be regarded as clinically acceptable and comparable to those produced with more traditional techniques.

Este estudo se propôs a analisar os efeitos das diferentes larguras temporais de pulso do laser de Er:YAG na rugosidade superficial, na perda de volume do material e na altura do degrau formado em uma Y-TZP (Yttrium-stabilized Tetragonal Zirconia Polycrystal) pré-sinterizada. Foram utilizados 5 blocos de Y-TZP pré-sinterizados destinados ao uso CAD/CAM que foram seccionados, obtendo-se 63 espécimes padronizados. Em seguida, esses espécimes foram lixados com uma sequência decrescente de lixas para padronização da superfície. Os grupos experimentais foram compostos a partir de 1 fator de variação - o tratamento de superfície. Os espécimes foram irradiados com o laser de Er:YAG (Fidelis III Fotona, Eslovênia) - 2,94 ?m, 100 mJ, 15,87J/cm2, 10 Hz, 1W, 7 mm, 60% água/40% ar. Assim formaram-se 7 grupos experimentais (n=9): G1 (50 ?s); G2 (100 ?s); G3 (300 ?s); G4 (600 ?s); G5 (1000 ?s); G6 (Abrasão triboquímica com partículas de 30 ?m); G7 (Sem tratamento). Após os tratamentos de superfície, os espécimes foram sinterizados em forno específico, de acordo com as recomendações do fabricante. Foram capturadas imagens em Microscópio Confocal a Laser 3D de cada espécime e avaliadas por meio de um software. A análise dos grupos irradiados revelou um aumento da rugosidade nos grupos G1, G2, G3 e G4 quando comparados aos grupos G6 e G7. O grupo G5 apresentou superfície totalmente plana e desfavorável para retenção. No que se refere à perda de volume e formação de degrau, os grupos G1, G2 e G3 demonstraram grande perda de volume e grande altura de degrau formado, o que pode levar a uma desadaptação da peça protética. No grupo G4 foram observados valores de rugosidade satisfatórios com pouca perda de volume e pequena altura de degrau formado, semelhante ao que foi notado para a abrasão trioboquímica (G6), podendo ser indicada para tratamento de superfície de Y-TZP pré-sinterizada. A irradiação com o laser de Er:YAG promoveu um padrão morfológico com muitas irregularidades, característico de ablação para os grupos G1, G2, G3 e G4 e, para todos os protocolos utilizados, não foi observada a presença de trincas ou carbonização. Sugere-se que a largura temporal de 600 ?s (G4) seja a mais indicada como alternativa para tratamento de superfície, objetivando a criação de micro-retenções superficiais, com pouca perda de volume de material e que, ao mesmo tempo, não provoque danos à estrutura da cerâmica policristalina. / This study evaluated the effects of different Er:YAG laser pulse width protocols on surface roughness, loss of volume of the material and the step height formed of pre-sintered Yttrium-stabilized tetragonal Zirconia Polycrystal (Y-TZP) by three-dimensional profilometric assessment. Blocks of pre-sintered Y-TZP were cut providing 63 standard 5mm thick samples which were divided by surface treatment, as follows (n=9): G1 (50?s); G2 (100?s); G3 (300?s); G4 (600?s); G5 (1000?s); G6 (tribochemical silica coating); G7 (Untreated). Laser settings: The Er:YAG laser (Fidelis III; Fotona, Ljubljana, Slovenia) 100mJ, 15,87J/cm2, 10Hz, 1W, (60%) and air (40%) cooling. After treated or not, samples were sintered according to the manufacturer\'s recommendations. Roughness, volume loss and step and were analyzed by 3D profilometric assessment with confocal laser microscopy. Irradiated groups showed an increased roughness in the groups G1, G2, G3 and G4 when compared to G6 and G7 groups. The G5 group showed a completely flat and unfavorable surface for retention. The groups G1, G2 and G3 shown great loss of volume and the step height formed, which can lead to a gap on the crowns. In G4 were observed satisfactory roughness with little loss of volume and the step height formed similar to G6. Irrespective of laser protocol, any of the specimens showed presence of cracks and carbonization. It is suggested that the pulse width 600?s (G4) is the most suitable pulse width protocol as an alternative surface treatment, promoting micro-retention, with little loss of volume of material, comparable to gold standard treatment.

Objetivos: aprofundar na interpretação dos dados obtidos pelo teste de lascamento da aresta, com espécime em formato de barra ou de coroa, para verificar se o ensaio é capaz de reproduzir o resultado já conhecido na clínica de que porcelana sobre zircônia apresenta maior facilidade de lascamento do que porcelana sobre metal, quando o resfriamento rápido é adotado. Material e método: o teste de lascamento da aresta foi aplicado em espécimes com dois formatos: barras (monolíticas: de VM13, VM9 ou zircônia; ou em duas camadas: de VM13-metal ou VM9-zircônia) e coroas (sempre com duas camadas). Nas barras monolíticas (5 mm x 32 mm x 2,5 mm) foi realizada uma análise da microestrutura para avaliar eventuais diferenças entre a VM13 e a VM9, que poderiam interferir na interpretação de diferenças encontradas nos espécimes de duas camadas. As barras com duas camadas (5 mm x 32 mm x 2,2 mm, com infraestrutura de 0,7 mm e porcelana de 1,5) receberam dois protocolos de resfriamento (lento e rápido) e foram testadas em duas direções de carregamento (paralela ou perpendicular à interface). Para estes espécimes foram avaliadas as tensões térmicas residuais por análise por elementos finitos. Para as coroas (correspondentes ao primeiro molar inferior, com infraestrutura de 0,7 mm de espessura), foram utilizados os mesmos protocolos de resfriamento das barras de duas camadas. As superfícies de fraturas de todos os espécimes foram analisadas em estereomicroscópio com um aumento de 20x a 50x. Os dados de lascamento foram analisados através de diferentes abordagens apresentadas na literatura, sendo o parâmetro ReA (resistência ao lascamento), correspondente à média de todas as razões de força necessária para criar a lasca pela distância da aresta (N/mm), o escolhido para comparar os vários grupos experimentais. Resultados: não foram encontradas diferenças estatisticamente significantes entre as resistências ao lascamento das porcelanas, apesar da VM13 apresentar maior fração de área de leucita. Nas barras de duas camadas resfriadas lentamente e carregadas na direção perpendicular à interface, a zircônia proporcionou resistência ao lascamento da porcelana estatisticamente superior à proporcionada pelo metal. Quando o resfriamento rápido foi utilizado ou quando o carregamento foi paralelo à interface, o teste não foi capaz de evidenciar diferenças entre os grupos. Nas coroas submetidas ao resfriamento rápido, o metal proporcionou resistência ao lascamento da porcelana estatisticamente superior à proporcionada pela zircônia. Quando o resfriamento lento foi utilizado, o teste não foi capaz de evidenciar diferenças entre grupos com materiais de infraestrutura distintos. Conclusão: O ensaio de lascamento em coroas reproduziu melhor que o ensaio de lascamento em barras a resistência ao lascamento relatada na clínica. Assim, esforços em aprimorar o teste utilizando espécimes com geometria mais semelhante à da coroa são importantes. / Aim: To deepen the investigation of the edge chipping method when using either bar or crown-shaped specimens, to verify whether the test is able to reproduce the well-known clinical outcome that veneered zirconia is more prone to chipping than porcelain-fused-to-metal when the fast cooling protocol is used. Materials and methods: edge chipping test was conducted with different shaped specimens: bars (monolithic: VM13, VM9 or zirconia; or bilayers: VM13-metal and VM9-zirconia) and bi-layer crowns. A microstructure analysis was performed on the monolithic bars (5 mm x 32 mm x 2.5 mm) to evaluate possible differences between VM13 and VM9, that could account for differences on bilayer specimens data. The bilayer bars (5 mm x 32 mm x 2.2 mm, 0.7 mm and 1.5 porcelain infrastructure) were subjected to two cooling protocols (slow and fast) and load was applied in two directions (parallel or perpendicular to the interface). For bilayer bars, residual thermal stresses were evaluated using finite element analysis. For crown-shaped specimens (corresponding to the first molar, with 0.7 mm framework thickness), the cooling protocol was the same employed for bilayer bars. The fractured surfaces of all specimens were examined utilizing a stereomicroscope at a magnification from 20x up to 50x. The edge chipping data were analyzed by several approaches presented in the literature, the ReA parameter (chipping resistance), corresponding to the average of force versus distance data collected over a broad range (N / mm), was chosen to compare the different experimental groups. Results: There was no significant difference between the veneers for chipping resistance, despite that VM13 presented the highest leucite content. On bilayer bars with slow cooling protocol and loading perpendicular to the interface, zirconia provided significantly higher chipping resistance than metal-based specimens. Edge chipping test was not able to detect differences between groups when fast cooling was used or loading was applied parallel to the interface. When crowns were subject to fast cooling, results revealed that metal framework has significantly higher veneer chipping resistance than zirconia. When the slow cooling protocol was used, differences between groups with different frameworks were not observed using edge chipping test. Conclusion: The chipping test on crowns reproduced the chipping resistance reported clinically better than bar-shaped specimens. Thus, efforts to improve the test using specimens more similar to the crown geometry are important.

Uma nova rota de síntese via metodo sol-gel para óxido de titânio (titânia) e óxido misto titânio/zircônio (zircônia) é proposta neste trabalho. As amostras foram submetidas ao tratamento hidrotérmico e obteve-se compostos mesoestruturados e de elevada área superficial. Algumas amostras foram submetidas à calcinação a 450°C para a verificação da estabilidade a altas temperaturas. As amostras foram analisadas por difratometria de raios-x (DRX), espalhamento de raios-x de baixo ângulo (SAXS), área superficial através do método BET, por microscopia eletrônica de varredura por emissão de campo (FE-SEM), além de serem testadas na fotodegradação de corantes. Foram testados diferentes alcóxidos precursores, isopropóxido de titânio e n-butóxido de titânio; ácidos, clorídrico e nítrico; e surfactantes, Pluronic® P123, Brij® 700 e Brij® 98; e também variadas as quantidades de surfactantes utilizadas, para que fosse possível analisar como estas variações afetam a síntese dos compostos e se estabelecer uma nova rota padronizada utilizando-se os melhores precursores em quantidades ideais. Para efeito de comparação, foi testada uma rota alcalina de síntese, que levou ao material com área superficial mais elevada. Como resultado deste trabalho, foi desenvolvida uma nova rota de síntese para óxidos mesoestruturados de titânio e titânio/zircônio corn elevada área superficial, na qual a etapa de calcinação para remoção do surfactante foi eliminada. Algunas dos materiais preparados mostraram excelente desempenho na degradação fotocatalítica de um corante comercial. / A new sol-gel based synthetic route for titania and mixed titania-zirconia ceramic powders is proposed in this contribution. This route combines a surfactant-template strategy with hydrothermal treatment, yielding mesostructured compoundes with a high surface area. Some samples were calcined at 450 °C in order to verify the stability of the structures at these temperatures. The materials were characterized by x-ray diffraction (XRD), small angle x-ray scattering (SAXS), surface area (BET method), field emission scanning electron microscopy (FE-SEM), and were also tested in the photocatalytic degradation of selected dyes. Different precursor alcóxidos were used: titanium isopropoxide and titanium n-butoxide. Two different acids were used to catalyze the hydrolysis reaction, HCl and HNO3. Three surfactants were used as templating agents: Pluronic P123®, Brij 700®, and Brij 98®. The amount of surfactant was also changed in order to verify how these variations affect the surface area and morphology of the resulting compounds. For comparison, an alkaline route was also tested, in which the highest surface area was observed. As a result of this work, a new synthetic route for mesostructured titania and titania-zirconia mixed oxides was developed, in which the surfactant is removed without a calcinations step, resulting in compounds with high surface areas and, in some cases, excellent photocatalytic properties for the degradation of a dye.

The yttria-stabilized zirconia (YSZ) system has been extensively studied because of its critical applications, like solid oxide fuel cells (SOFCs), oxygen sensors, and jet engines. However, there are still important questions that need to be answered and significant thermodynamic information that needs to be provided for this system. There is no predictive tool for the ionic conductivity of the cubic-YSZ (c-YSZ), as an electrolyte in SOFCs. In addition, no quantitative diagram is available regarding the oxygen ion mobility in c-YSZ, which is highly effective on its ionic conductivity. Moreover, there is no applicable phase stability diagram for the nano-YSZ, which is applied in oxygen sensors. Phase diagrams are critical tools to design new applications of materials. Furthermore, even after extensive studies on the thermodynamic database of the YSZ system, the zirconia-rich side of the system shows considerable uncertainties regarding the phase equilibria, which can make the application designs unreliable. During this dissertation, the CALPHAD (CALculation of PHase Diagrams) approach was applied to provide a predictive diagram for the ionic conductivity of the c-YSZ system. The oxygen ion mobility, activation energy, and pre-exponential factor were also predicted. In addition, the CALPHAD approach was utilized to predict the Gibbs energy of bulk YSZ at different temperatures. The surface energy of each polymorph was then added to the predicted Gibbs energy of bulk YSZ to obtain the total Gibbs energy of nano-YSZ. Therefore, a 3-D phase stability diagram for the nano-YSZ system was provided, by which the stability range of each polymorph versus temperature and particle size are presented. Re-assessment of the thermodynamic database of the YSZ system was done by applying the CALPHAD approach. All of the available thermochemical and phase equilibria data were evaluated carefully and the most reliable ones were selected for the Gibbs energy optimization process. The results calculated by the optimized thermodynamic database showed good agreement with the selected experimental data, particularly on the zirconia-rich side of the system.

Dans cette étude de doctorat, de la poudre de Y3Al5O12 (YAG) a été synthétisé avec plusieurs méthodes: atomisation, synthèse de réaction et co-précipitation. Le procédé de synthèse le plus prometteur, la co-précipitation, a été optimisé pour obtenir une poudre hautement frittable, présentant une phase pure. Le traitement approprié avant frittage, comprenant calcination, efficace dispersion et séchage homogène, a été réalisé. La poudre de YAG a été dispersée avec plusieurs méthodes, avant frittage. Grâce à la technique Spark Plasma Sintering (SPS) une évaluation très rapide de l'influence des différents traitements a été réalisée. Il a été constaté que, pour une poudre obtenue avec une telle synthèse, la méthode de dispersion est cruciale afin de obtenir une transparence élevée du materiaux fritté. En raison de l'aptitude au frittage de la poudre, du traitement approprié avant frittage et de la basse température du cycle effectué par SPS, un matériau à grains fins a été obtenu. Des mesures de spectroscopie de photoélectrons (XPS) ont été effectuées sur la poudre de YAG et sur le matériaux fritté, et plusieurs differences ont été mises en évidence. Quelques hypothèses ont été faites pour expliquer les differences observées, et certains preuves supplémentaires pour les vérifier ont été mises en avant. Une poudre composite alumine-zircone-YAG a été synthétisé à partir d'une poudre d'alumine commerciale, qui a été fonctionnalisé avec chlorures de yttrium et de zirconium. Les traitements de pré-frittage appropriées ont été effectués, comprenant une calcination à basse température et une calcination "rapide", pour favoriser la germination des petits cristallites. Deux méthodes de mise en forme, coulage et pressage, ont été réalisées. Il a été constaté que le coulage permet la production de matériaux céramiques beaucoup plus homogènes. Une caractérisation mécanique préliminaire a été effectuée. Une caractérisation spectroscopique des poudres d'alumine-YAG, traités à basse et haute température, a été réalisée. Il a été mis en évidence que l'état d'hydratation des poudres varie avec la fonctionnalisation par les chlorures. La présence de sites Y sur la surface des poudres composites a été mise en évidence par XPS et à partir des spectres infrarouges (spectroscopie infrarouge par transformée de Fourier, FTIR) des échantillons soumis à des différentes pressions de monoxide de carbone (CO). / In this PhD study, Yttrium aluminum garnet (Y3Al5O12, YAG) powder was synthesised with several methods, i.e. spray drying, reaction synthesis and co-precipitation. The most promising synthesis method, i.e. co-precipitation, was optimized to obtain a pure phase, highly sinterable powder. The appropriate pre-sintering processing, i.e. calcination treatment, e fficient dispersion, homogeneous drying, were performed. YAG powder was dispersed with several methods, prior to sintering. Through Spark Plasma Sintering (SPS) a very fast assessment of the influence of the various treatments was performed. It was found that, for the synthesised powder, the dispersion method is crucial to obtain a high transparency. Due to the high sinterability of the powder and to the appropriate pre-sintering treatment, a low temperature SPS cycle was performed, and a fine-grained material was obtained. X-ray Photoelectron Spectroscopy (XPS) measurements were performed on YAG powder and on the sintered material, and several di fferences were evidenced. Some hypothesis were made to explain the observed di fferences, and some additional proofs to verify them were put forward. A composite Alumina-YAG-Zirconia powder was synthesized, starting from a commercial alumina powder, which was functionalised with Yttrium and Zirconium chlorides. The appropriate pre-sintering treatments were performed, comprising a low temperature calcination and a "fast" calcination, to favour the germination of small crystallites. Two shaping methods, i.e. slip casting and pressing, were performed. It was found that slip casting allows the production of much more homogeneous ceramic materials. A preliminary mechanical characterization was performed. A spectroscopic characterization of Alumina-YAG powders, heat-treated at low and high temperatures, was performed. It was evidenced that the hydration state of the powders changes with chlorides functionalization. The presence of Y sites on the surface of the composite powders was evidenced by X-ray Photoelectron Spectroscopy and from the di fference spectra of powdered samples subjected to various CO pressures.

La connaissance du comportement et des propriétés des matériaux est d’une grande importance pour optimiser leur mise en forme et adapter leur utilisation. Pour étudier ces propriétés de nombreuses techniques sont couramment utilisées : les essais de traction, la microindentation, la nanoindentation instrumentée… Aujourd’hui, un intérêt particulier est porté sur les nanomatériaux et matériaux nanostructurés car ils présentent souvent des propriétés différentes et plus intéressantes. La nanoindentation instrumentée, notamment, permet de déterminer des paramètres matériaux de manière locale. Cependant, le comportement en temps réel ne peut être observé et l’échantillon ne doit pas être de dimension trop faible (typiquement, l’étude de nanoparticules n’est pas envisageable). Le principal atout de la nanoindentation in situ en Microscopie Electronique en Transmission vis-à-vis des autres techniques existantes est la possibilité d’étudier le comportement de nano-objets ou des comportements très locaux et en temps réel, tout en observant les transformations subies par le matériau. Dans cette étude, nous avons évalué les potentialités de cette nouvelle technique via l’analyse de céramiques très étudiées au laboratoire notamment en tant que biomatériaux : la zircone stabilisée et l’alumine. Dans le cas de la zircone (stabilisée à l’yttrium ou au cérium), le but était de localiser à l’échelle nanométrique les contraintes responsables ou inhérentes à la transformation de phase quadratique-monoclinique, phénomène ayant une très grande influence sur les propriétés du matériau massif. Pour ce faire, après avoir déterminé une technique de préparation adaptée, nous proposons une voie d’étude pour la localisation des contraintes liées à la transformation de phase : le CBED (Convergent Beam Electron Diffraction) couplé à la nanoindentation in situ. Dans le cas de l’alumine, l’objectif était d’étudier le matériau (commercial et non un matériau modèle) dans sa forme originelle à savoir sous forme de nanoparticules d’alumine de transition. L’idée était d’étudier le comportement de ces nanoparticules sous compression. Nous avons notamment constaté que ces particules pouvaient subir une grande déformation plastique à température ambiante. Nous avons pu également, sur quelques particules, obtenir une série d’images en cours de compression ainsi que la courbe de charge-déplacement correspondante. Ces résultats ont ensuite été soumis à une analyse des images couplée à une simulation de type Eléments Finis (réalisées par le LAMCOS). / Knowledge of the behavior and properties of materials is of great importance to optimize their processing and adapt their use. To study these properties, many techniques are commonly used: tensile tests, microindentation, instrumented nanoindentation ... Today, particular interest is focused on nanomaterials and nanostructured materials because they often have different and more interesting properties. Instrumented nanoindentation allow to determine material parameters. However, the real-time behavior can not be observed and the study of nano-objects is difficult (nanoparticles for example). The main advantage of in situ TEM (Transmission Electron Microscopy) nanoindentation is the ability to study the behavior of nano-objects in real time. In this study, we evaluated the potential of this new technique by analyzing ceramics extensively studied in the laboratory such as biomaterials: stabilized zirconia and alumina. In the case of zirconia (stabilized with yttrium or cerium), the goal was to locate at the nanoscale, the constraints responsible for the tetragonal to monoclinic phase transformation. This phenomenon having a great influence on the bulk material properties. To do this, after having determined a suitable preparation method, we suggest a way to study the localization of constraints: the CBED (Convergent Beam Electron Diffraction) coupled with in situ TEM nanoindentation. In the case of alumina, the goal was to study the material in its original form (nano powder of transition alumina). The idea was to study the behavior of these nanoparticles under compression. We particularly observed that these particles could undergo large plastic deformation at room temperature. We have also obtained during compression on few particles, series of images and the corresponding load-displacement curve. These results were then analyzed by image analysis coupled with Finite Element simulations (performed in LAMCOS lab).

L’objectif de cette thèse est le développement de composites dans le système alumine-zircone par une approche d’ingénierie des poudres permettant de façonner les caractéristiques microstructurales et compositionnelles, et, par conséquent, les propriétés des matériaux finaux. Les poudres composites ont été elaborée à travers la modification de la surface des poudres commerciales par un précurseur inorganique de les phases secondaires . Cette approche innovante assure un degré élevé du contrôle de la taille et de la distribution des grains de seconde phase sur la surface du matériau parent. Les poudres composites à base d’alumine contenant 10 vol% de zircone non-stabilisée et des poudres composites à base de zircone triphasique contenant 8 vol% d’alumine et 8 vol% de phase aluminate, ont été développées. Leur propriétés physiques, chimiques et mécaniques a été caractérisé. Dans le cas premier, les materials porous ont été développés à travers le technique gel-casting avec sphères de PE. Les mécanismes de ténacité de la zircone ont été étudiés, révélant aucun influence sur les propriété mécaniques. Les composites poreux présentent des valeurs de résistance à la rupture plus élevées, en comparant à des alumines pures, mais cet amélioration peut être raisonnablement dû à leur microstructure plus fine, celle-ci étant caractérisée par des grains et des pores plus petits. Dans le deuxième cas, a partir de la Ce-TZP, connue pour sa ténacité et sa stabilité importantes, un travail d’optimisation de la microstructure a été réalisé afin d’obtenir une résistance à la rupture maximale. Les matériaux présentés dans cette étude ont été développés afin de répondre au triple objectif de ténacité, résistance et stabilité. Deux composites très prometteurs, avec des résistances à la rupture élevées (environ 900 MPa) et ténacités élevées (environ 10Mpa√m), ont été réalisés. De plus, les composites étudiés ont montré de hautes capacités de transformation et pas de faible température de dégradation en atmosphère humide, dans les temps des applications médicales. Il a été démontré que les propriétés mécanique sont vivement affectées par le degré de stabilisation de la zircone. L’étude de la relation entre les propriétés finales et l’architecture de la composition/microstructure, au but d’obtenir les propriétés désirées, se révèle nécessaire. / The aim of this PhD study is the development of composites in the alumina-zirconia system through a powder engineering approach which allows tailoring the compositional and microstructural features, and, as a consequence, the properties of the final materials. The experimental activities refer to two different projects. The first, named MITOR project, was devoted to the elaboration and mechanical characterization of macro-porous Alumina-Zirconia composites. It dealt with the development of a new method for the elaboration of composite cellular ceramics and with the investigation of the role of zirconia and its toughening mechanisms in porous materials, thus filling a gap in the scientific literature. The latter, a European Project named Longlife, was dedicated to the preparation and characterization of zirconia (stabilized with ceria)-based composites for dental and spine implants. The major aim was to overcome the drawbacks proper of yttria-zirconia-based materials, concerning their stability in moisture atmosphere as well as their low toughness. Ceria-zirconia-based composites should benefit from phase transformation toughening still keeping high strength. In addition, they should not suffering of surface degradation in presence of water. So, materials characterized by high strength, high toughness with a perfect reliability and a lifetime longer than 60 years were investigated. Alumina-based composite powders containing 10 vol% of un-stabilized zirconia as well as tri-phasic zirconia-based composite powders containing 8 vol% of alumina and 8 vol% of an aluminate phase(Srontiuma nd Magnesium hexaxaluminate), were developed and characterized in terms of phase evolution and thermal behaviour. In addition, the adopted elaboration route allowed tailoring the ceria amount inside the zirconia grains: four different zirconia stabilization degree were thus investigated. Two very promising composites with high fracture strength, of about 900 MPa, and high crack resistance were found. Furthermore, the investigated composites showed high transformability and no low temperature degradation in moisture atmosphere in the time-scale of medical applications. It was shown that the deep knowledge of all the involved mechanisms (such as raw powders dispersion, pH suspension, powder thermal treatments) is crucial for achieving a full control of the powders features and, consequelntly, of the final microstructures.