<p>In this study, the OMCVD method is demonstrated as a powerful, fast, economic and environmental friendly method to produce a set of PGMelectrocatalysts with different supports, metal content and metal alloys in one step and without the multiple processing stages of impregnation, washing, drying, calcinationsand activation.</p>

<p>In this study, the OMCVD method is demonstrated as a powerful, fast, economic and environmental friendly method to produce a set of PGMelectrocatalysts with different supports, metal content and metal alloys in one step and without the multiple processing stages of impregnation, washing, drying, calcinationsand activation.</p>

In this study, the OMCVD method is demonstrated as a powerful, fast, economic and environmental friendly method to produce a set of PGMelectrocatalysts with different supports, metal content and metal alloys in one step and without the multiple processing stages of impregnation, washing, drying, calcinationsand activation.

A fotoelasticidade é um método analítico usado para avaliar e calcular as tensões existentes em qualquer ponto da superfície de um material. É uma ferramenta para análise de tensões bidimensionais, usa luz monocromática polarizada e modelos de resina. O objetivo do presente estudo foi comparar as tensões induzidas na interface osso-implante em diferentes planejamentos de próteses fixas totais implantossuportadas protocolo de Branemark. As variáveis nos modelos foram: número de implantes, tipo de liga, presença ou ausência de cantilever, inclinação dos implantes distais e secção transversal da infraestrutura. Foram confeccionados 32 modelos fotoelásticos e foram realizadas análises qualitativa e quantitativa das tensões induzidas. Os modelos sofreram carga estática no valor de 50 N na porção central e distal da barra. Os implantes central e distal foram analisados sob as cargas central e distal individualmente. Os pilares receberam torque de 20 N.cm e os parafusos protéticos de fixação da barra receberam 10 N.cm. Antes de qualquer avaliação, foi certificado que os modelos fotoelásticos encontravam-se livres de tensões residuais. A tensão (MPa) acumulada nos implantes distais sob carga distal foi aproximadamente 7 vezes maior que nas outras situações de carga. Além disso, 69% de toda tensão acumulada no sistema se manifestou no implante distal sob carga distal. Houve uma clara vantagem para as estruturas fundidas em cobalto-cromo em relação às fundidas em titânio concernente à distribuição de tensões. A análise da secção transversal demonstrou que na comparação entre viga convencional e viga I, houve distribuição aleatória de resultados. Também ficou evidente que o número maior de implantes favorece a uma melhor distribuição de tensões. Já quando foram comparadas barras de protocolo apresentando ou não cantilever, as infraestruturas sem cantilever apresentaram um resultado marcadamente superior àquelas com cantilever. Finalmente, as infraestruturas com implantes distais retos apresentaram uma melhor distribuição de tensões. Com base nos resultados obtidos, pode-se concluir que o método de fotoelasticidade é um método laboratorial apropriado para análise de tensões; próteses tipo protocolo de Branemark com 5 implantes provêm uma melhor condição de distribuição de tensões do que com 4 implantes; a secção transversal da supraestrutura metálica e o tipo de liga utilizado na fundição não apresentaram relação direta com o padrão de distribuição de tensões nos implantes; a distribuição de tensões nos implantes dentários em uma prótese tipo protocolo é mais eficiente com implantes distais retos e sem extensão em cantilever. / Photoelastic analysis is a method used to evaluate and calculate stresses at a material surface. It is a tool for bidimensional stresses analysis. Polarized monochromatic light and resin models for stresses evaluation were used. The purpose of this study was to compare the induced stresses in the bone-implant interface using different implant supporting complete fixed prostheses Branemark protocol. The variables studied in the models were: the number of implants, cast metal alloy, presence or absence of cantilever, angulation of distal implants and superstructure cross-sectional shape. It were prepared thirty-two photoelastic models and perceived quantitative and qualitative analysis of the induced stresses. 50 Newtons static load was exerted on the central and the distal part of the superstructure. Central and distal implants were analyzed under central and distal loads individually. The abutments were tightened with a 20 N.cm torque and the prosthetic screws with a 10 N.cm torque. Before the evaluations took place, it was checked if the implants presented residual stresses. Stresses accumulated in the distal implants under distal load were nine times greater than in the other loading situations and received approximately 69% of all stresses scattered in the whole system. There was a clear advantage for cobalto-chromium cast superstructures over titanium ones about stress transfer. The analysis of the cross-sectional superstructure shape evinced that when comparing conventional beam with i-beam there was an aleatoric results distribution. It was also evident that a superstructure with more implants collaborates to a better stresses distribution. Comparing Branemark protocol bars presenting or not cantilever extension, those with no cantilever presented remarked superior results than those with cantilever. Finally, superstructures with straight implants had a better stress transfer than those with angulated ones. Based upon the obtained results, it was concluded that the photoelastic method is a laboratorial evaluation method suitable for stress transfer analysis. Five implants complete fixed prostheses provide a better stress than those with four implants. Cross-sectional metal superstructure shape and the type of cast alloy demonstrate no direct correlation about the stress transfer pattern over the implants. The stress distribution over dental implants in a Branemark procotol prosthese is more efficient with straight distal implants and a bar with no cantilever extension.

Recently, efforts have been made for self-powering the batteries and portable electronic devices by piezoelectric nanogenerators. The piezoelectric nanogenerators can work as a power source for nano-systems and also as an active sensor. The piezoelectric nanogenerator is a device that converts random mechanical energy into electrical energy by utilizing the semiconducting and piezoelectric properties. Also, the mechanical energy is always available in and around us for powering these nano devices. The aim of the present thesis work is to explore 1D and 2D ZnO nanostructures (nanorods and nanosheets) on metal alloy substrates for the development of piezoelectric nanogenerators in energy harvesting and sensors applications. Hydrothermal synthesis method was adopted for the growth of ZnO nanostructures. The nanogenerators were fabricated by using the optimized synthesis parameters and subsequently studied their performance for power generation and as an active speed sensor. These 1D and 2D nanostructures based nanogenerators have opened up a new window for the energy harvesting applications and sensors development. The thesis is divided into following six chapters. Chapter 1: This chapter gives a general introduction about energy harvesting devices such as nanogenerators, available energy sources, mechanical energy harvesting, ZnO material and the details on hydrothermal synthesis process. A brief literature survey on different applications of piezoelectric nanogenerators is also included. Chapter 2: A novel flexible metal alloy (Phynox) and its properties along with its applications are discussed in this chapter. Details on the synthesis of 1D ZnO nanorods on Phynox alloy substrate by hydrothermal method are presented. Further, the optimization of parameters such as growth temperature, seed layer annealing and substrate temperature effects on the synthesis of ZnO nanorods are discussed in detail. As-synthesized ZnO nanorods have been characterized using XRD, FE-SEM, TEM and XPS. Chapter 3: It reports on the fabrication of piezoelectric nanogenerator on Phynox alloy substrate as power generating device by harvesting the mechanical energy. Initially, the performance of the nanogenerator for power generation due to finger tip impacts was studied and subsequently its switching polarity test was also carried out. Output voltage measurements were carried out using the in-house developed experimental setup. Stability test was also carried out to see the robustness of the nanogenerator. Finally, the output voltage response of the nanogenerator was studied for its use as an active speed sensor. Chapter 4: Synthesis of Al doped 2D ZnO nanorsheets on Aluminum alloy (AA-6061) substrate by hydrothermal method is reported in this chapter. The optimized parameters such as growth temperature and growth time effects on the synthesis of ZnO nanosheets are discussed. As-synthesized ZnO nanosheets were characterized using XRD, FE-SEM, TEM and XPS. The Al doping in ZnO is confirmed by EDXS and XPS analysis. Chapter 5: Cost effective fabrication of Al doped 2D ZnO nanosheets based nanogenerator for direct current (DC) power generation is reported in this chapter. The performance of the nanogenerator for DC power generation due to finger tip impacts was studied and subsequently its switching polarity test was also carried out. Output voltage measurements were carried out using the in-house developed experimental setup. Stability test was also carried out to see the robustness of the nanogenerator. Finally, the DC output voltage response of the nanogenerator was studied for its use as an active speed sensor. Chapter 6: The first section summarizes the significant features of the work presented in this thesis. In the second section the scope for carrying out the further work is given.

Philosophiae Doctor - PhD / In this study, the OMCVD method is demonstrated as a powerful, fast, economic and environmental friendly method to produce a set of PGMelectrocatalysts with different supports, metal content and metal alloys in one step and without the multiple processing stages of impregnation, washing, drying, calcinationsand activation. / South Africa

L’objectif de cette étude était d’évaluer et de comparer la force d’adhésion de deux résines de collage: le ClearfilTM Esthetic Cement & DC Bond Kit (C) et le RelyXTM Unicem (R), sur trois adhérents différents : une surface d’émail, un alliage de métaux non précieux (Np) et un alliage de métaux semi-précieux (Sp). La surface des échantillons des alliages métalliques a subi différents traitements de surface. Sur l’émail (n=15) ainsi que sur les plaquettes d’alliages Np et Sp (n=15), des cylindres de résine étaient appliqués et polymérisés. Suite au processus de collage, les échantillons ont été incubés à 37°C pendant 24 heures, puis ont subi 500 cycles de thermocyclage. Des tests de cisaillement ont été effectués, suivi par l’analyse de la surface des échantillons au microscope à balayage électronique. Une comparaison de type T-test et des comparaisons multiples post hoc, ont été effectuées pour l’analyse statistique (p 0,05). Sur l’émail, les résultats ont démontré que la résine C présentait une force d'adhésion moyenne statistiquement supérieure (33,97±17,18 MPa) à la résine R (10,48±11,23 MPa) (p 0,05). Le type d’alliage utilisé n’influençait pas la force d’adhésion, et ce, peu importe le type de résine de collage (p>0,05). Pour le groupe Sp, la résine C a démontré une adhésion statistiquement supérieure à la résine R, et ce, pour tous les traitements de surface (p 0,05). En conclusion, la résine C a démontré des résultats d’adhésion significativement supérieurs à la résine R sur l’émail ainsi que sur presque toutes les surfaces traitées des alliages de métaux. / The objective of this study was to assess and compare the shear bond strength of two types of resin cements: ClearfilTM Esthetic Cement & DC Bond Kit (C) and RelyXTM Unicem (R) when these resins cements were applied to three different surfaces: enamel, non precious metal alloy (Np) and semi-precious metal alloy (Sp). Both types of alloy surfaces were treated differently. On both enamel (n=15) and alloy plates Np and Sp (n=15) surfaces, cylinder shaped resin cements were bonded and lightpolymerized. After the adhesion process, all samples were placed into an incubator at 37°C for 24 hours and 500 thermal cycles were accomplished. Shear bond strength tests followed by electron microscopy analysis were performed. Statistical analysis was done using a T-test comparison followed by a post hoc multiple comparisons (p 0.05). The results on enamel showed that the C resin cement had a statistically significant higher bond strength (33.97±17.18 MPa) than the R resin cement (10.48±11.23 MPa) (p 0.05). The type of alloy did not influence the bond strength regardless the type of resin cement (p 0.05). For the Sp group, the bond strength was statistically higher for the C resin than for the R resin and those results are valuable for all treated surfaces (p 0.05). To conclude, the C resin cement showed a statistically significant higher bond strength than the R resin cement with enamel and most of the metal alloy treated.

La corrosion sous contrainte par l’iode (CSC-I) est l’un des mécanismes de rupture potentiels des crayons combustibles en alliage de zirconium, pouvant intervenir au cours des transitoires de puissance des réacteurs nucléaires. La fissuration par CSC-I comporte trois étapes : amorçage de la fissure, développement intergranulaire puis propagation transgranulaire. Le but du travail est d’identifier des paramètres critiques gouvernant les transitions entre ces différentes étapes. En premier lieu, des essais sur des éprouvettes en Zircaloy présentant des finitions de surface et des états métallurgiques variés permettent de discriminer l’influence de différents paramètres sur l’amorçage des fissures. Nous mettons en évidence le rôle critique du niveau des contraintes résiduelles, de leur répartition en surface ainsi que de leur profil au sein du matériau. La sensibilité des alliages à l’amorçage des fissures n’est pas directement corrélée à la rugosité de la surface. Cependant, la dispersion des paramètres de rugosité traduit l’irrégularité du profil, l’hétérogénéité du niveau des contraintes résiduelles, et donc l’existence de zones où les contraintes résiduelles sont localement moins protectrices. Dans un second temps, des éprouvettes de Zircaloy-4 possédant différents états d’écrouissage sont sollicitées sous charge constante, en présence de méthanol iodé. Les modifications microstructurales induites par l’écrouissage favorisent l’apparition de la propagation transgranulaire des fissures de CSC-I. Des observations des faciès de rupture en MET révèlent que la transition inter/transgranulaire intervient dans des zones où les grains sont fortement désorientés les uns par rapport aux autres, suite à l’augmentation des contraintes locales résultant des incompatibilités de déformation grain à grain. / Iodine-induced stress corrosion cracking (I-SCC) is one of the potential failure modes of zirconium alloy fuel claddings during power transients in nuclear reactors. I-SCC failures are usually described in three steps: initiation of cracks, intergranular development and transgranular propagation. The objective of this work is to identify critical parameters controlling transitions between crack propagation modes. First of all, experiments conducted on Zircaloy samples with various surface conditions and metallurgical states lead to discriminate the influence of several parameters responsible for cracks initiation. The critical role of residual stresses level, their distribution at the subsurface and their evolution in the bulk of the material is evidenced. Sensitivity to I-SSC is not directly correlated to surface roughness. However, dispersion in roughness parameters indicates the presence of surface irregularities, heterogeneities of residual stresses and the existence of surface areas where residual stresses are less protective. In a second step, Zircaloy-4 samples with various strain-hardening pre-treatments are submitted to constant load tests in an iodine methanol solution. Microstructural modifications induced by a strain-hardening pre-treatment enhance transgranular propagation of I-SCC cracks. TEM observations of fracture surfaces show that the intergranular to transgranular crack transition takes place preferentially where the relative crystallographic orientation is large between two adjacent grains, because of local stress concentrations resulting from strain incompatibilities between neighbouring grains.

L’objectif de cette étude était d’évaluer et de comparer la force d’adhésion de deux résines de collage: le ClearfilTM Esthetic Cement & DC Bond Kit (C) et le RelyXTM Unicem (R), sur trois adhérents différents : une surface d’émail, un alliage de métaux non précieux (Np) et un alliage de métaux semi-précieux (Sp). La surface des échantillons des alliages métalliques a subi différents traitements de surface. Sur l’émail (n=15) ainsi que sur les plaquettes d’alliages Np et Sp (n=15), des cylindres de résine étaient appliqués et polymérisés. Suite au processus de collage, les échantillons ont été incubés à 37°C pendant 24 heures, puis ont subi 500 cycles de thermocyclage. Des tests de cisaillement ont été effectués, suivi par l’analyse de la surface des échantillons au microscope à balayage électronique. Une comparaison de type T-test et des comparaisons multiples post hoc, ont été effectuées pour l’analyse statistique (p 0,05). Sur l’émail, les résultats ont démontré que la résine C présentait une force d'adhésion moyenne statistiquement supérieure (33,97±17,18 MPa) à la résine R (10,48±11,23 MPa) (p 0,05). Le type d’alliage utilisé n’influençait pas la force d’adhésion, et ce, peu importe le type de résine de collage (p>0,05). Pour le groupe Sp, la résine C a démontré une adhésion statistiquement supérieure à la résine R, et ce, pour tous les traitements de surface (p 0,05). En conclusion, la résine C a démontré des résultats d’adhésion significativement supérieurs à la résine R sur l’émail ainsi que sur presque toutes les surfaces traitées des alliages de métaux. / The objective of this study was to assess and compare the shear bond strength of two types of resin cements: ClearfilTM Esthetic Cement & DC Bond Kit (C) and RelyXTM Unicem (R) when these resins cements were applied to three different surfaces: enamel, non precious metal alloy (Np) and semi-precious metal alloy (Sp). Both types of alloy surfaces were treated differently. On both enamel (n=15) and alloy plates Np and Sp (n=15) surfaces, cylinder shaped resin cements were bonded and lightpolymerized. After the adhesion process, all samples were placed into an incubator at 37°C for 24 hours and 500 thermal cycles were accomplished. Shear bond strength tests followed by electron microscopy analysis were performed. Statistical analysis was done using a T-test comparison followed by a post hoc multiple comparisons (p 0.05). The results on enamel showed that the C resin cement had a statistically significant higher bond strength (33.97±17.18 MPa) than the R resin cement (10.48±11.23 MPa) (p 0.05). The type of alloy did not influence the bond strength regardless the type of resin cement (p 0.05). For the Sp group, the bond strength was statistically higher for the C resin than for the R resin and those results are valuable for all treated surfaces (p 0.05). To conclude, the C resin cement showed a statistically significant higher bond strength than the R resin cement with enamel and most of the metal alloy treated.

La modélisation multi-échelle multi-physique de la solidification d'alliages métalliques demande de combiner des phénomènes à l'échelle macroscopique du produit et microscopiques à l'échelle des structures de solidification. Dans cette thèse, l'empilement aléatoire des grains équiaxes avec des morphologies typiques de solidification est étudié. Nous mettons tout d'abord en évidence les paramètres hydrodynamiques adimensionnels qui régissent l'empilement de grains équiaxes : le nombre de Stokes, St, le nombre d'Archimède, Ar, et le rapport entre le temps caractéristique de la croissance et le temps caractéristique du mouvement, Γ. Un dispositif expérimental a été conçu par similitude hydrodynamique avec le phénomène réel de l'empilement de la solidification afin d'étudier l'influence de la géométrie des grains équiaxes et l'influence des conditions hydrodynamiques sur la fraction d'empilement. En outre, un outil numérique basé sur le méthode des éléments discrets a été développé pour compléter le travail expérimental de détermination de : la fraction d'empilement locale, le nombre de particules voisines en contact et l'orientation des particules. Des fractions d'empilement entre environ 0,53 et 0,67 ont été mesurées et calculées pour les grains sphériques non-cohésifs, alors que des valeurs allant jusqu'à environ 0,30 sont trouvées pour les grains dendritiques non-cohésifs. Enfin, nous étudions la dynamique de l'empilement, qui est la transition d'un régime de sédimentation à l'équilibre mécanique. L'évolution des variables comme la fraction locale de solide, le nombre de particules voisines en contact et l'orientation du grain en fonction du temps est présentée / Solidification multiphase multiscale modeling of metal alloys is based on the combination of the phenomena at the macroscopic scale of the product and at the microscopic scale of the solidification structures. In this thesis, the random packing of the typical equiaxed grain morphologies in metal alloy solidification is investigated. Firstly, we highlight the hydrodynamic dimensionless parameters governing the grain packing in the melt: the Stokes number, St, the Archimedes number, Ar, and the growth-to-motion ratio, Γ. Subsequently, an experimental setup is designed by hydrodynamic similarity with the actual solidification packing phenomenon in order to investigate the influence of the equiaxed grain geometry and the hydrodynamic conditions on the average solid packing fraction. Additionally, a numerical Discrete Element Method tool is developed to complement the experimental work by accessing to those granular variables which result difficult to be experimentally obtained such as the local packing fraction, the contacting neighbors and the particle orientation. Packing fractions between approximately 0.53 and 0.67 are measured and computed for the spherical noncohesive grains, for different hydrodynamic, frictional and polydispersity conditions, whereas values down to approximately 0.30 are found for noncohesive dendrite envelopes. Finally, we investigate the packing dynamics, which is the transition from a sedimentation regime to the mechanical equilibrium (packing). The evolution of the local solid fraction, contacting neighbors, mechanical contacts and grain orientation are given