Ce projet de thèse a concerné la recherche et le développement de catalyseurs multifonctionnels efficaces et de procédés catalytiques en une étape (hydrolyse-déshydratation, hydrolyse-oxydation) pour la transformation de la cellulose en produits chimiques à valeur ajoutée (glucose, 5-HMF, acide formique). Ces produits sont également connus sous le nom de molécules plateformes et ils présentent un intérêt dans une large gamme d'applications, par exemple, pour les industries alimentaires et chimiques et pour la production de carburants. Dans ce projet, des recherches systématiques sur la synthèse de l'acide formique en présence de catalyseurs HPA contenant du vanadium ont d'abord été conduites. En particulier, l'influence de la composition du catalyseur et des paramètres du procédé sur le rendement en produit cible a été étudiée. Le rendement en AF obtenu (66%) est supérieur à tous les résultats rapportés dans la littérature à ce jour. Les catalyseurs NbOx / ZrO2 ont été évalués pour la première fois sur la réaction d'hydrolyse-déshydratation de la cellulose microcristalline activée en milieu aqueux. Des rendements élevés en glucose et en 5-HMF (22 et 16%, respectivement) ont été observés. Des catalyseurs carbonés à base du matériau Sibunit modifié ont été utilisés pour la première fois pour l'hydrolyse-déshydratation de la cellulose. Les rendements en glucose (jusqu'à 74% dans un réacteur en continu) et en 5-HMF (jusqu'à 21% dans un réacteur statique) ont été obtenus en présence de Sibunit modifié par sulfonation et / ou oxydation. Ces résultats sont également supérieurs à ceux reportés à ce jour sur les systèmes catalytiques carbonés. La relation entre l'activité sur les réactions d’hydrolyse-déshydratation et la méthode d'activation du carbone a été étudiée en profondeur. L'étude du mécanisme et de la cinétique de la réaction d'hydrolyse-déshydratation de la cellulose en présence de catalyseurs acides solides a également été réalisée. / The PhD project was devoted to search for and to develop effective multifunctional catalysts and catalytic one-stage processes (hydrolysis-dehydration, hydrolysis-oxidation) for transformation of cellulose to valuable chemicals (glucose, 5-HMF, formic acid). These products are also known as platform molecules and they seem to be promising for a wide range of application in food and chemical industries and for fuel production. In this project, systematic investigations of the formic acid synthesis in the presence of vanadium-containing HPA catalysts was first conducted; the influence of the catalyst composition and process parameters on the yield of the target product was studied. The obtained FA yield (66 %) was superior to all the results reported in literature. The NbOx/ZrO2 catalysts were applied for the first time for hydrolysis-dehydration of activated microcrystalline cellulose in pure water. High yields of glucose and 5-HMF (22 and 16 %, respectively) were observed. Carbon catalysts based on modified Sibunit material was used for the first time for cellulose hydrolysis-dehydration. The yields of glucose (up to 74 % in a flow reactor) and 5-HMF (up to 21 % in a static reactor) were obtained in the presence of Sibunit modified by sulfation and/or oxidation; these are much superior to the results on carbon catalytic systems reported in literature. The relation between the activity to hydrolysis-dehydration and the method of the carbon activation was thoroughly studied. Investigations of the mechanism and kinetics of cellulose hydrolysis-dehydration in the presence of solid acid catalysts were also carried out.

Ce travail est en relation avec la thématique "Chimie Verte" en particulier, le rôle de la catalyse,l’utilisation des matières premières renouvelables et l’élimination des produits nocifs.- Quatre échantillons commerciaux de zircone tungstatée de Mel-Chemicals.- deux séries de zircone tungstatée préparées par deux méthodes différentes avec une teneuren WO3 de 1 à 20 % en masse.- des oxydes binaires tels que WO3-ZrO2, B2O3-ZrO2, Al2O3-ZrO2, Ga2O3-ZrO2 et In2O3-ZrO2.- des oxydes binaires tels que WO3-Me2O3 (Me = B, Al, Ga et In) et finalement des oxydesternaires WO3/(Me2O3-ZrO2) (Me = B, Al, Ga et In) ont été étudiés et préparés lors de cettethèse.La performance catalytique de ces catalyseurs a été évaluée dans l’hydrolyse de la cellobiose, ladéshydratation du fructose et la réduction catalytique sélective des NOx. Les propriétés acides etredox de surface ont été corrélées aux performances catalytiques. En général, la conversion totale est liée à l’acidité des catalyseurs. Les catalyseurs les plus sélectifs pour la déshydratation du fructose et en deNOx sont ceux présentant une acidité modérée. / This work is related to the subject “Green Chemistry” in particular the role of the catalyst, the useof renewable raw materials and the decrease of hazardous materials.- Four commercial tungstated zirconia provided by Mel-Chemicals.- Two series of tungstated zirconia catalysts prepared by two different methods in a range of(1-20) WO3 wt.% loading- Binary zirconia-based oxides WO3-ZrO2, B2O3-ZrO2, Al2O3-ZrO2, Ga2O3-ZrO2 and In2O3-ZrO2.- Binary oxides WO3-Me2O3 (Me = B, Al, Ga and In) and ternary oxides WO3/(Me2O3-ZrO2)(Me = B, Al, Ga and In) were prepared and studied during my PhD thesis.The catalytic activity of these mixed oxide catalysts was evaluated in cellobiose hydrolysis, fructosedehydration and selective catalytic reduction of NOx. The catalysts were thoroughly characterizedin terms of their acidic and redox properties in order to find correlations between the identifiedactive sites and the catalytic properties. The total conversion is related in general to the acidity ofthe tested catalysts and the most selective catalysts for fructose dehydration and deNOx are thosewith moderate acidity.

As ceramicas a base de zirconia (Y-TZP) apresentam propriedades mecanicas superiores as das demais ceramicas odontologicas. Entretanto, o aumento do conteudo cristalino modificou suas caracteristicas de adesao a cimentos resinosos, tornando necessario o desenvolvimento de metodos mais efetivos de uniao a estes materiais. Este trabalho in vitro pretende, portanto, avaliar a influencia de diferentes tratamentos de superficie e de diferentes agentes de uniao na resistencia ao cisalhamento entre uma zirconia estabilizada por itrio e um agente cimentante autoadesivo (RelyX U100®/3M ESPE). Para tal, cilindros de PROCERA® Allzircon receberam como tratamento de superficie jateamento com oxido de aluminio (Al2O3 - 50 m) ou jateamento com o sistema Rocatec. Sobre a superficie tratada dos cilindros foram aplicados, de acordo com os diferentes grupos experimentais, o sistema adesivo Clearfil SE Bond® (Kuraray Co.), e os primers Metal Zirconia Primer (Ivoclar Vivadent) e Alloy Primer (Kuraray Co.) e, finalmente, o cimento resinoso adotado. Cada especime foi, entao, submetido ao teste de cisalhamento (0,05 mm/min), por meio da acao de uma alca de fio ortodontico passando o mais próximo possivel da interface adesiva. A analise de variancia a um criterios (ANOVA) e o teste de Tukey (p<0,05) mostraram que a realizacao do tratamento de superfície aumentou os valores de resistencia de uniao entre a ceramica e o cimento resinoso. O jateamento com o sistema Rocatec (15,33 MPa) apresentou valores significantemente maiores que o jateamento com Al2O3 (11,93 MPa). A aplicacao dos agentes de uniao resultou em uma maior resistencia adesiva, sendo que o sistema adesivo Clearfill SE Bond (17,07 MPa) teve um comportamento estatisticamente superior aos demais materiais. Entre os primers, o Metal Zirconia Primer (11,26 MPa) apresentou maior valor de resistencia de uniao que o Alloy Primer (10,01 MPa). Portanto, a associacao de um tratamento superficial com um agente de união e valida, ja que promoveu os maiores valores de resistencia adesiva. / Yttrium-stabilized tetragonal zircon polycrystal (Y-TZP) ceramics show better mechanical properties than other dental ceramics. However, the high crystalline content modified their adhesiveness to resin cements, making it extremely necessary to develop a more effective adhesive strategy between them. This in vitro study intends to evaluate the influence of different surface treatments and different bond agents on the shear bond strength between a Y-TZP and self-adhesive resin cement. PROCERA® Allzircon cylinders (3.5 mm in diameter) received a surface airborne abrasion treatment with 50 m aluminum-oxide (Al2O3) particles or with the Rocatec system. According to the experimental groups, the adhesive system Clearfil SE Bond® (Kuraray Co.), and the primers Metal Zirconia Primer (Ivoclar Vivadent) and Alloy Primer (Kuraray Co.) were applied on the treated surface of the cylinders, before the application of the adopted resin cement (RelyX U100®/3M ESPE). Each specimen was submitted to the shear bond strength test (0.5 mm/min), by the action of an orthodontic stainless steel ligature wire (0.5 mm in diameter) loop, wrapped around the resin cement, as close as possible to the adhesive interface. One way-ANOVA and Tukey´s post hoc tests (p<0.05) revealed that surface treatment increased bond strength between the ceramic and the resin cement. Silica coating with the Rocatec system (15.33 MPa) showed significantly higher values than airborne abrasion with Al2O3 (11.93 MPa). Application of all bond agents improved shear bond strength: adhesive system Clearfil SE Bond (17.07 MPa) showed better performance than the other evaluated materials, and Metal Zirconia Primer (11.26 MPa) showed higher bond strength values than Alloy Primer (10.01 MPa). Therefore, the association of a surface treatment with a bond agent is suitable, once it resulted in higher values of adhesive strength.

O objetivo desse trabalho foi desenvolver um compósito cerâmico de zircônia-grafeno para aplicação odontológica. Este estudo avaliou o efeito do pó de partida, concentração de grafeno e da temperatura de sinterização sobre as propriedades mecânicas (dureza e tenacidade à fratura) do compósito desenvolvido. Para isto foram sintetizados os pós de Y-TZP a partir de soluções de óxido-cloreto de zircônio e cloreto de ítrio na proporção desejada de 3mol% através da rota de co-precipitação em solução de hidróxido de amônio seguido por uma série de lavagens em água, etanol e butanol com posterior destilação azeotrópica, secagem, moagem e calcinação. O grafeno foi obtido a partir da exfoliação química de grafite pelo método de Hummers [40] modificado por Marcano [39], o que resultou em um gel acastanhado que foi submetido a lavagem por centrifugação, secagem e desaglomeração em almofariz de ágata, resultando, por fim, no óxido de grafeno. Uma segunda etapa foi o processo de redução química com ácido ascórbico para obtenção de óxido de grafeno reduzido, um pó de coloração escura que foi adicionado à Y-TZP para a obtenção do compósito nas diversas concentrações (em mol%) que foram estudadas: (0,01%, 0,05%, 0,10%, 0,50%, 1,00% e 2,00%). Os pós foram caracterizados por termogravimetria, difração de raios X e espectroscopia (FT-IR). Os espécimes foram confeccionados em matriz metálica cilíndrica e sinterizados em forno tubular em atmosfera inerte. Outros espécimes foram confeccionados em matriz de grafite de alta densidade e sinterizados por Spark Plasma Sintering (SPS). Todas as amostras foram caracterizadas por meio de ensaios de densidade, dureza Vickers, tenacidade à fratura e microscopia eletrônica de varredura. Os maiores valores de densidade relativa foram observados para as amostras sinterizadas em SPS, sendo que se obteve valor de densidade relativa de 98,7 % para a concentração de 0,50% de grafeno e 98,4% para a Y-TZP pura. Por outro lado, o maior valor encontrado em sinterização em atmosfera a 1400°C sem a presença de H2 para Y-TZP pura foi da ordem de 96,76%. Os valores de dureza foram maiores nas amostras sinterizadas em SPS, no entanto a tenacidade à fratura mostrou não se alterar em função do conteúdo de grafeno. As fotomicrografias de MEV mostraram que houve uma variação de tamanho de grão de acordo com a presença do grafeno e do método de sinterização. De acordo com os resultados obtidos neste trabalho foi possível concluir que o processamento desenvolvido permitiu a criação de um compósito cerâmico zircônia-grafeno que pôde ser caracterizado por diversos métodos analíticos. A densidade teórica do compósito desenvolvido não foi alcançada por meio de nenhum dos métodos de sinterização utilizados (Tubular ou SPS) e nem variando-se a temperatura. Para espécimes sinterizados em atmosfera inerte, a maior temperatura de sinterização (1400°C) e a presença do gás H2 não melhorou a densificação. Além disso, esses espécimes tiveram aumento da dureza com o aumento da concentração de grafeno, entretanto, a sua tenacidade à fratura não foi afetada pelo teor de grafeno. Para espécimes sinterizados por meio de SPS, a temperatura de sinterização de 1350°C resultou em melhores valores de densificação. Além disso, para este tipo de sinterização, tanto a dureza como a tenacidade à fratura foram afetadas pelo teor de grafeno. / The objective of this work was to develop a zirconia-graphene ceramic composite for dental application. The study evaluated the effect of the starting powder effect, graphene concentration and sintering temperature on the mechanical properties of the composite. For this, the Y-TZP powders were synthesized from zirconium chloride and yttrium chloride solutions in the desired ratio of 3 mol% through the co-precipitation route in ammonium hydroxide solution followed by a series of washes in water, ethanol and butanol with subsequent azeotropic distillation, drying, grinding and calcination. Graphene was obtained from the chemical exfoliation of graphite by the method of Humans modified by Marcano, which resulted in a brownish gel that was subjected to washing by centrifugation, drying and deagglomeration in agate mortar, resulting finally in the graphene oxide. A second step was the chemical reduction with ascorbic acid to obtain reduced graphene oxide, a dark-colored powder that was added to the Y-TZP to obtain the composite in the various concentrations (in mol%) that were studied (0, 01%, 0.05%, 0.10%, 0.50%, 1.00% and 2.00%). The powders were characterized by thermogravimetry, X-ray diffraction and spectroscopy (FT-IR). The specimens were made in cylindrical metallic matrix and sintered in a tubular oven. Other samples were made in high density graphite matrix and sintered by Spark Plasma Sintering (SPS). All samples were characterized by means of density tests, Vickers hardness, fracture toughness and scanning electron microscopy. The highest values of relative density were observed for the sintered samples in SPS. A relative density of 98.7% was obtained for the 0.50% concentration of graphene and 98.4% for the pure Y-TZP. On the other hand, the highest value found in tubular sintering at 1400 ° C without the presence of H2 for pure Y-TZP was of the order of 96.76%. The hardness values were higher in the sintered samples in SPS, however the fracture toughness showed not to change as a function of the content of graphene. SEM images showed that there was a variation of grain size according to the presence of graphene and the sintering method. According to the results of this study it was concluded that the process developed allowed the creation of a graphene-zirconia ceramic composite which can be characterized by various analytical methods. The theoretical density of the composite developed was not achieved by any of the sintering methods used (tubular or SPS) nor by varying the temperature. For tubular sintered specimens, the higher sintering temperature (1400 ° C) and the presence of H2 gas did not improve densification. In addition, these specimens had increased hardness with increasing graphene concentration, however, their fracture toughness was not affected by graphene content. For sintered specimens by SPS, the sintering temperature of 1350 ° C resulted in better densification values. In addition, for this type of sintering, both hardness and fracture toughness were affected by the content of graphene

Este estudo teve como objetivo principal desenvolver uma técnica para síntese de um nanocompósito de Y-TZP/MWCNT-COOH (Zircônia estabilizada por 3 mol% de ítria reforçada por nanotubos de carbono funcionalizado em -COOH) com propriedades mecânicas e ópticas que permitam a sua futura utilização como infraestrutura de próteses fixas dentárias e pilares protéticos para implantes. Assim, foram avaliados a microestrutura, resistência à flexão, tenacidade à fratura, limite de fadiga e propriedades ópticas do nanocompósito e comparada àquelas medidas para Y-TZP convencional (controle). O material Y-TZP/MWCNT-COOH foi desenvolvido pelo processo de co-precipitação de hidróxidos mistos associado ao tratamento hidrotérmico/solvotérmico e prensagem uniaxial em formato de blocos para sistemas CAD/CAM. O pó de MWCNT-COOH foi caracterizado por meio de MEV-FEG, TEM, TGA, DRX e FRX previamente a sua utilização para desenvolvimento do nanocompósito. Espécimes foram obtidos a partir do material Y-TZP/MWCNT-COOH para caracterização por meio de DRX, MEV-FEG e TEM, e comparação de suas propriedades estruturais (densidade e contração), ópticas, resistência à flexão, tenacidade à fratura e limite de fadiga com a Y-TZP convencional. O MWCNT-COOH apresentou-se em feixes de nanotubos de carbono recobertos por sílica tendo comprimento médio de 5,10 ± 1,34 ?m, com 90% dos comprimentos medidos (D90) estando abaixo de 6,9 ?m. Foi verificado a não possibilidade da utilização de líquidos orgânicos em nenhum passo da fabricação dos compósito Y-TZP/MWCNT-COOH por levar ao escurecimento do compósito, inviabilizando sua futura aplicação clínica. O tratamento hidrotérmico sem uso de líquidos orgânicos mostrou-se eficaz em proporcionar o revestimento do nanotubo de carbono por partículas de óxido de zircônio e ítrio. Entretanto, ocasionou a formação de aglomerados e partículas de Y-TZP com tamanho maiores que 5 ?m. Uma densidade relativa de 97,4% foi alcançada para o compósito experimental de Y-TZP contendo MWCNT-COOH, tendo uma razão de contraste de 0.9929 ± 0.0012 e um valor de diferença de cor da Y-TZP convencional de 6,1 ± 3,1 ( ?E). As propriedades mecânicas da Y-TZP/MWCNT-COOH, dureza Vickers (10,14 ± 1,27 GPa; p=0,25) e tenacidade à fratura (4,98 ± 0,30 MPa.m1/2; p=0,39), não apresentaram diferença significativa da Y-TZP convencional (dureza: 8,87 ± 0,89; tenacidade à fratura: 4,98 ± 0,30 MPa.m1/2). Entretanto, para a resistência à flexão (p=0,003) e limite de fadiga cíclica (LFC) foram obtidos valores inferiores para o material experimental Y-TZP/MWCNT-COOH (resistência à flexão: 299,4 ± 30,5 MPa; LFC: 179,4 ± 22,5 MPa) quando comparado à Y-TZP controle (resistência à flexão: 623,7 ± 108,8 MPa; LFC: 439,0 ± 56,4 MPa). Com base nos resultados apresentados, é possível concluir que a síntese de um nanocompósito de Y-TZP/MWCNT-COOH com propriedades ópticas adequadas para aplicação na odontologia restauradora foi possível por meio dos métodos descritos, entretanto algumas adequações nos métodos de síntese e processamento para criação do nanocompósito devem ser realizadas para se evitar a acentuada diminuição de importantes propriedades mecânicas do material. / This study aim was to develop a technique for synthetize nanocomposite of Y-TZP/MWCNT-COOH (3 mol% Yttria-Stabilized Tetragonal Zirconia reinforced with COOH functionalized carbon nanotubes) with mechanical and optical properties that allow their future use as fixed dental prosthesis infrastructure and implant abutments. Thus, the following properties of the nanocomposite were investigated and compared to those measured for conventional Y-TZP (control): microstructure, flexural strength, fracture toughness, fatigue limit and optical properties. Y-TZP/MWCNT-COOH material was developed by the co-precipitation of mixed hydroxides associated with the hydrothermal/solvothermal treatment and uniaxial pressing to form blocks for CAD/CAM systems. The MWCNT-COOH powder was characterized by SEM-FEG, TEM, TGA, XRD and XRF prior to its use for the development of nanocomposite. Specimens were obtained from the Y-TZP/MWCNT-COOH material and characterized by XRD, SEM-FEG and TEM. After characterization, the material had their structural properties (density and contraction), optical, flexural strength, fracture toughness and fatigue limit compared to a conventional Y-TZP. The MWCNT-COOH material was observed to be a bundle formation of carbon nanotube covered with silica with an average length of 5.10 ± 1.34 ?m, with 90% of the measured lengths (D90) being below 6.9 ?m. It has been found to be not possible to use organic liquids on any step of the Y-TZP/MWCNT-COOH manufacturing process due to darkening of the composite, making it unfeasible to future clinical application. The hydrothermal treatment without the use of organic liquids was effective in providing the carbon nanotube coating by zirconium and yttrium oxide particles. However, this treatment led to the formation of agglomerates and particles of Y-TZP with larger than 5 ?m. A relative density of 97.4% was achieved for the Y-TZP/MWCNT-COOH composite, having a contrast ratio of 0.9929 ± 0.0012, and a color difference value from the conventional Y-TZP of 6.1 ± 3.1 (?E). The mechanical properties of Y-TZP/MWCNT-COOH, Vickers hardness (10.14 ± 1.27 GPa; p = 0.25) and fracture toughness (4.98 ± 0.30 MPa.m1/2; p = 0.39), showed no significant difference from the conventional Y-TZP (hardness: 8.87 ± 0.89; fracture toughness: 4.98 ± 0.30 MPa.m1/2). However, flexural strength (p = 0.003) and cyclic fatigue limit (CFL) showed lower values for the experimental material Y-TZP/MWCNT-COOH (flexural strength: 299.4 ± 30.5 MPa; CFL: 179.4 ± 22.5 MPa) compared to Y-TZP control (flexural strength: 623.7 ± 108.8 MPa; CFL: 439.0 ± 56.4 MPa). Based on the results presented, it could be conclude that the synthesis of a nanocomposite of Y-TZP/MWCNT-COOH with optical properties suitable for application in restorative dentistry was made possible by the described methods, however some adjustments in synthesis and processing methods for the nanocomposite creation should be taken; to avoid the sharp decrease of important mechanical properties of the material.

Considerando a crescente exigência estética, o desenvolvimento da zircônia e o incremento da tecnologia CAD/CAM o objetivo deste trabalho foi avaliar a adaptação marginal e interna, as tensões nos implantes e a resistência à fratura após prensagem da porcelana e termociclagem mecânica em próteses parciais fixas sobre implantes com pilares e infraestrutura em zircônia com dois sistemas CAD/CAM (Neodent digital - Neodent e Lava - 3M ESPE) comparados com o método convencional (n=10). A adaptação marginal e interna foi analisada por meio de um microtomógrafo computadorizado (microCT). Cada prótese foi digitalizada e os arquivos foram processadas utilizando o software NRecon e CTAN. Foi utilizado o programa Dataview para aferição das medidas. Para a realização da ciclagem termomecânica as próteses foram posicionadas na máquina de fadiga mecânica por mastigação e foi aplicada a carga de 120 N com uma ponta que simula a oclusão antagonista simulando 2.000.000 ciclos. Durante o ensaio, as próteses foram mantidas em água destilada e termocicladas com variação de temperatura entre 5º-55º C. Para a verificação das tensões geradas pelas próteses parciais fixas em torno dos implantes foi realizada a análise por correlação de imagens digitais. Foram selecionados cinco modelos de cada um dos sistemas CAD/CAM e um antagonista e aplicada uma carga de 250 N, com velocidade de 0,1 mm/min, em máquina universal de ensaios. Para avaliação da resistência à fratura foi aplicada uma força perpendicular ao longo eixo da peça protética, no pôntico, até que devido à fratura não houvesse mais resistência. Após esse teste foi avaliado o relacionamento entre os componentes da prótese em microscópio eletrônico de varredura (MEV). A análise estatística mostrou que houve diferença significativa na adaptação pilar-implante dos molares entre os grupos Lava e ZirNeo, Lava e Controle (p=0,008). Para a desadaptação vertical e horizontal antes e após a prensagem e ciclagem não houve diferença significante (p>0,005). A desadaptação interna axial mostrou diferença significante antes e após para os molares dos grupos Lava e ZirNeo (p<0,001). A desadaptação interna oclusal mostrou diferença significante para os PM dos grupos TiNeo e Controle e para os molares dos grupos Lava e Zir Neo (p<0,005). Houve diferença significante de tensão na região cervical dos molares dos grupos ZirNeo e Lava (p=0,015) com maiores valores de tensão para o grupo Lava. O grupo TiNeo teve maior resistência à fratura que os demais (p=0,022). O relacionamento entre os componentes da prótese permaneceu favorável para todos os grupos. Os resultados deste trabalho permitem concluir que a prensagem da porcelana e a termociclagem mecânica não influenciou os resultados da desadaptação marginal e melhorou a desadaptação interna. O grupo usinado pelo sistema Neodent digital em zircônia teve maior concentração de tensão na região cervical podendo ter maior perda óssea nessa região. O grupo TiNeo foi o que mais resistiu à fratura. Entre fresar em zircônia pelo sistema Neodent digital ou Lava, o sistema Lava distribui melhor a tensão ao longo do implante, porém teve maiores valores de desadaptação interna. Entre fresar em titânio ou confeccionar a prótese pelo sistema convencional, melhor fresar. / Considering the growing aesthetic requirements, the development of zirconia and the increase of CAD/CAM technology, the aim of this study was to evaluate the marginal and internal fit, tensions in implants and fracture resistance after pressing porcelain and thermomechanical cycling in FPDs on implants with abutments and infrastructure in zirconia with two CAD/CAM systems (Neodent digital -Neodent and Lava - 3M ESPE) compared with the conventional method (n = 10). The marginal and internal fit was analyzed by a computerized microtomograph (microCT). Each prosthesis was scanned and the files were processed using the NRecon and CTAN software. Dataview program was used for the assessment of the measures. To carry out the thermomechanical cycling, prostheses were placed in mechanical fatigue machine for chewing and 120 N load was applied with a tip that simulates the antagonist occlusion simulating 2,000,000 cycles. During the test, the prostheses were kept in distilled water and thermocycled with temperatures between 5°-55° C. Digital image correlation analysis was performed to check the load transfer by implant-supported restoration. Five models were selected from each of the CAD/CAM systems and an antagonist and a load of 250 N was applied, with 0.1 mm/min speed using a universal testing machine. The fracture resistance was verified with force applied perpendicular to the long axis of the prosthesis, at pontic, until there were no more fracture resistance. After this test was evaluated the relationship between the components of the prosthesis in a scanning electron microscope (SEM). The statistical analysis showed significant difference in abutment-implant fit of molars between Lava and ZirNeo, Lava and control groups (p=.008). For vertical and horizontal fit there was no significant difference (p>.005) before and after pressing and thermomechanical cycling. The axial internal gap was significantly different before and after for molar ZirNeo groups (p<.001). The occlusal internal fit was significantly different to the PM of TiNeo and Control, and the molars of Lava and ZirNeo (p<.005). There were significant difference for tension in the cervical region of the molars of ZirNeo and Lava (p=.015) with higher values for the Lava group. TiNeo group had higher resistance to fracture than others (p=.022). The relationship between the prosthesis components remained positive for all groups. The results of this study showed that the pressing of porcelain and thermomechanical cycling did not influence the results of marginal gap and improved internal fit. The zirconia group machined by Neodent digital system had higher concentration of tension in the cervical and may have greater bone loss in this region. TiNeo group was the most resistant to fracture. Between the zirconia milling by Neodent digital or Lava system, the Lava system distributes better strain throughout the implant, but had greater internal fit values. Between milling titanium or fabricate the prosthesis by the conventional system, better milling.

The densification mechanisms of polycrystalline α-alumina by spark plasma sintering are highly contradictory, with different research groups suggesting diffusion to dislocation controlled mechanisms to be rate controlling. The specific objective of this work was to investigate densification mechanisms of α-alumina during the intermediate and final stages of sintering by SPS, analyze the microstructural development and establish sintering trajectories. In addition, zirconia and yttria were added in different weight percentages to study the effect of solute concentration on the densification kinetics of spark plasma sintered alumina. The present work adopts a different approach from the classical method adopted previously to analyze the sintering kinetics and densification mechanisms of alumina in SPS, although existing models for hot pressing were adopted for the basic analysis. The densification behavior was investigated in the temperature range 1223-1573 K under applied stresses of 25, 50 and 100 MPa and grain sizes between 100 and 250 nm. The SEM micrographs reveal equiaxed grains with no abnormal grain growth in the dense samples. The ‘master sintering curve’ shows grain size to be primarily dependent on density, irrespective of the applied stresses or temperature. The stress exponent of 1 along with an inverse grain size exponent of 3 and activation energy of 320-550 kJ mol-1 suggests Al3+ grain boundary diffusion as the rate controlling densification mechanism in alumina. The densification rates are marginally slower in compositions with 0.1% Y2O3 and ZrO2 content possibly due to the smaller grain sizes used in this study which leads to faster rates compared to earlier reports. However, higher Y2O3 and ZrO2 content led to decrease in densification rate by more than an order of magnitude possibly due to presence of a second phase which increases the effective path length for diffusion, thereby reducing the densification rates. Presence of Y2O3 and ZrO2 in the compositions with 0.1% Y2O3 and ZrO2 were confirmed by TEM studies. The Y3Al5O12 (YAG) phase developed between 1223 and 1273 K and suppressed densification and grain growth in alumina. In spite of higher temperatures required for alumina-YAG and alumina-zirconia composites to attain density ~99%, the alumina grain size in the composites was smaller than that in pure alumina due to the Zener drag effect. The stress exponents obtained for Y2O3 and ZrO2 composites at both the concentrations yield a value of n~ 2, which indicates a change in densification mechanism from pure alumina. The higher stress dependence of these composites could be due to presence of solute and second phase formation, both of which retard densification rates. The inverse grain size exponents obtained are between 1 and 2; both stress exponent and grain size exponent values suggest an interface reaction controlled diffusion mechanism occurring in these composites, independent of the Y2O3 and ZrO2 content. Higher activation energies are obtained with the Y2O3 and ZrO2 composites of higher content, respectively, due to presence of second phase particles at grain boundaries. The presence of solutes at grain boundaries hinders grain boundary diffusion of alumina, leading to interface reaction controlled process; this is confirmed by superimposing standard aluminum grain boundary and lattice diffusion data on to stress-densification rate data obtained in this work. A comparison of stress exponents using current experimental data adopting the present and the classical approaches show a wide difference in their values indicating a change in the rate controlling diffusion path, necessitating a review of the assumptions made on the basic equations used in previous SPS studies.

Le combustible nucléaire des Réacteurs à Eau sous Pression (REP), sous forme de pastilles d’oxyde d’uranium UO2 (ou MOx), est confiné dans un gainage en alliage de zirconium. Ce gainage est très important car il représente la première barrière de confinement contre la dissémination des produits de fission, générés par la réaction nucléaire, vers le milieu extérieur. La corrosion par le milieu primaire des alliages de zirconium, en particulier l’alliage Zircaloy-4, est un des facteurs limitant le temps de séjour en réacteur des crayons combustibles (pastilles UO2 + gainage). Afin de permettre aux exploitants de centrales d’optimiser la gestion des cœurs et de prolonger la durée de vie des crayons combustibles en réacteur, de nouveaux alliages à base de zirconium-niobium (M5®) ont été développés. Or, les mécanismes de corrosion de ces derniers ne sont, en l’état, pas complètement élucidés du fait notamment de la complexité de ces matériaux, de l’environnement de corrosion et de la présence de l'irradiation venant du combustible nucléaire. De ce fait, cette thèse porte spécifiquement sur l’effet de la radiolyse et des défauts induits par l’irradiation aux ions dans la matrice métallique et dans la couche d’oxyde sur la vitesse de corrosion de l’alliage Zircaloy-4 et M5®. L’objectif est de déconvoluer la part de l’influence des dommages d’irradiation subis par la matrice métallique, de celle relative aux défauts créés dans l’oxyde et de celle liée à la radiolyse du milieu primaire sur la vitesse d’oxydation des alliages de zirconium en réacteur.1) Concernant l’effet de l’irradiation de la matrice métallique sur la vitesse d’oxydation : des boucles de dislocation de type <a> apparaissent et entrainent une augmentation de la vitesse d’oxydation des deux alliages. Pour le M5®, en plus de ce premier effet, une précipitation d’aiguilles fines de niobium diminue la concentration en niobium en solution solide dans la matrice métallique et in fine dans l’oxyde, ce qui réduit fortement la vitesse d’oxydation de l’alliage.2) Concernant l’effet de l’irradiation de la couche d’oxyde sur la vitesse d’oxydation : les défauts générés par les cascades de déplacement dans l’oxyde augmentent la vitesse d’oxydation des matériaux. Pour le M5®, la germination de zones enrichies en niobium par irradiation de l’oxyde entraine une également diminution de la concentration en niobium en solution solide dans l’oxyde, ce qui réduit une nouvelle fois, la vitesse d’oxydation de cet alliage.3) Concernant l’effet de la radiolyse de l’eau : nous n’avons pas relevé d’effet considérable de la radiolyse sur la corrosion de l’alliage Zy4 ou M5® dans nos conditions expérimentales. / The nuclear fuel of pressurized water reactors (PWR) in the form of uranium oxide UO2 pellets (or MOX) is confined in a zirconium alloy cladding. This cladding is very important because it represents the first containment barrier against the release of fission products generated by the nuclear reaction to the external environment. Corrosion by the primary medium of zirconium alloys, particularly the Zircaloy-4, is one of the factors limiting the reactor residence time of the fuel rods (UO2 pellets + cladding). To optimize core management and to extend the lifetime of the fuel rods in reactor, new alloys based on zirconium-niobium (M5®) have been developed. However, the corrosion mechanisms of these are not completely understood because of the complexity of these materials, corrosion environment and the presence of radiation from the nuclear fuel. Therefore, this thesis specifically addresses the effects of radiolysis and defects induced by irradiation with ions in the matrix metal and the oxide layer on the corrosion rate of Zircaloy-4 and M5®. The goal is to separate the influence of radiation damage to the metal, that relating to defects created in the oxide and that linked to radiolysis of the primary medium on the oxidation rate of zirconium alloys in reactor.1) Regarding effect of irradiation of the metal on the oxidation rate: <a> type dislocation loops appear and increase the oxidation rate of the two alloys. For M5®, in addition to the first effect, a precipitation of fines needles of niobium reduced the solid solution of niobium concentration in the metal and ultimately in the oxide, which strongly reduces the oxidation rate of the alloy.2) Regarding the effect of irradiation of the oxide layer on the oxidation rate: defects generated by the nuclear cascades in the oxide increase the oxidation rate of the two materials. For M5®, germination of niobium enriched zones in irradiated oxide also causes a decrease of the niobium concentration in solid solution in the oxide, which once again, reduced the oxidation rate of this alloy.3) Regarding the effect of water radiolysis: We did not identify any significant effect of radiolysis on corrosion of the alloys under our experimental conditions.

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Nanokristalle werden beispielsweise für eine Anwendung in Solarzellen, Lichtemittern und nichtflüchtigen Datenspeichern diskutiert. Damit diese Anwendungen funktionieren können, ist eine genaue Kontrolle der Kristallitgröße sowie der Flächendichte und Lage der Kristallite in der Matrix wichtig. Zudem sollte die Matrix amorph sein, da amorphe Matrixmaterialien die Nanokristall-Oberfläche besser passivieren und beständiger gegen Leckströme sind. In dieser Arbeit werden Ge-Nanokristalle in die Hoch-Epsilon-Dielektrika ZrO2 und TaZrOx eingebettet. Im System Ge/ZrO2 kristallisieren die Ge-Cluster und die ZrO2-Matrix bei der gleichen Temperatur. Aufgrund der kristallinen Matrix weicht die Form der Ge-Nanokristalle von einer Kugel ab, worunter unter anderem die Größenkontrolle leidet. Die Beimischung von Ta2O5 stabilisiert die amorphe Phase des ZrO2 und verhindert dadurch die gemeinsame Kristallisation. Dadurch wird es im System Ge/TaZrOx möglich, kugelförmige Ge-Nanokristalle im Größenbereich von 3 nm bis 6 nm positionskontrolliert in eine amorphe Matrix einzubetten. Für die Untersuchung einer möglichen Anwendung des Materialsystems wurden Speicherzellen eines nichtflüchtigen Datenspeichers auf Basis von Ge-Nanokristallen hergestellt. Dabei zeigte sich, dass das System Ge/TaZrOx überdurchschnittlich viele Ladungen speichert und daher für diese Anwendung vielversprechend ist. Zudem stabilisiert die Beimischung von Ta2O5 eine extrem seltene orthorhombische Modifikation des ZrO2. Für ferroelektrische Datenspeicher könnte diese Phase eine aussichtsreiche Alternative zum HfO2 sein.