A alta sensibilidade e a reprodutibilidade de sinal são características de dosímetros luminescentes opticamente estimulados, que instigam seu uso no controle da qualidade e dosimetria in vivo em Radioterapia. Nesse trabalho, amostras de Al2O3, Al2O3 (1%C) e Al2O3 com diferentes concentrações de terras-raras e de nanoestruturas de carbono foram estudadas para aplicação em Radioterapia. As amostras foram obtidas pelo processo manual de mistura e maceração e inseridas em cápsulas transparentes, com exceção do material Al2O3 (1%C), que foi obtido na forma de pastilhas. Os sinais OSL para todos os materiais testados apresentaram crescimento de resposta com a dose de radiação. A concentração de 0,02% apresentou maior intensidade de sinal para todos os materiais inseridos na alumina, com exceção do carbono grafite (1%). Os materiais foram caracterizados por diferentes técnicas, para análises espectroscópicas e estruturais. A sensibilidade OSL do material Al2O3 (1%C) foi investigada para feixes de elétrons de 5 a 12 MeV, para feixe de fótons de 6 MV e para uma fonte de Irídio-192. Diferentes características dosimétricas OSL dos materiais Al2O3 (0,02%Eu), Al2O3 (0,02%Tb), Al2O3 (0,02%ntC), Al2O3 (0,02%npC) foram investigadas para feixes de fótons de 50 kVp, de 6 MV e para uma fonte de Irídio-192, em um amplo intervalo de doses. Todos os materiais apresentaram reprodutibilidade de sinal OSL (desvios menores que 1%) e homogeneidade de resposta em grupo de até ±95% (conferida para o dosímetro de Al2O3 (0,02%ntC). Todos os materiais estudados apresentaram sensibilidade satisfatória para doses de interesse clínico. Amostras OSL de Al2O3 (1% C), Al2O3 (0,02%ntC) e Al2O3 (0,02%npC) foram utilizadas para um estudo piloto de dosimetria in vivo em Radioterapia. A dosimetria in vivo sugere o possível uso dos dosímetros na rotina clínica em Radioterapia, através do estabelecimento de um protocolo de medidas, calibrações para cada feixe e energia utilizada e controle do sistema de planejamento utilizado para os cálculos de dose. / High sensitivity and signal reproducibility are characteristics of optically stimulated luminescent dosimeter, instigating it use in quality control and in vivo dosimetry in Radiotherapy. In this work, samples of Al2O3, Al2O3 (1%C) and Al2O3 with different concentrations of rare-earth and carbon nanostructures, have been studied and developed for application in Radiotherapy. Samples were obtained by manual mixing and maceration and inserted into transparent capsules, except those of Al2O3 (1%C) which were produced as pellets. The OSL signals for all tested materials showed increasing response with radiation dose. The 0.02% concentration showed the highest signal intensity for all materials inserted into alumina, with exception to carbon graphite (1%). Materials were characterized by various techniques, through spectroscopic and structural analysis. The OSL sensitivity of Al2O3 (1%C) was investigated for electron beams from 5 to 12 MeV, 6 MV photons and an Iridium-192 source. Different dosimetric characteristics of some OSL materials Al2O3 (0.02%Eu), Al2O3 (0.02%Tb), Al2O3 (0.02%ntC), Al2O3 (0.02% npC) were investigated for photons beams of 50 kVp and 6 MV and a source of Iridium-192, in a wide dose range. All materials showed reproducibility of OSL signal (deviations less than 1%) and response homogeneity up to ± 95% (conferred for the dosimeter Al2O3 (0.02%ntC). All studied materials showed satisfactory sensitivity. Samples of Al2O3 (1%C), Al2O3 (0.02%ntC) and Al2O3 (0.02% npC) were used in a in vivo dosimetry pilot study in radiotherapy. The in vivo dosimetry performed with the developed OSL dosimeters suggest its possible use in clinical practice in Radiotherapy by establishing a measure protocol, calibrations for each beam and energy used and control of the planning system used for dose calculations.

Aspersão térmica é um processo de produção de revestimentos metálicos, poliméricos, cerâmicos ou compósitos sobre superfícies previamente preparadas que objetiva na maioria das vezes a prevenção contra o desgaste e/ou corrosão e também a recuperação dimensional de superfícies desgastadas. Ligas de Ni-Al são extensivamente empregadas na aspersão térmica para reconstrução dimensional e como camada de ligação como materiais que não se ligam adequadamente à superfície a ser revestida. A baixa dureza e resistência ao desgaste (principalmente em aplicações de reconstrução dimensional) desta liga poderiam ser contornadas pela adição de partículas ou compostos de altas durezas na matéria prima em pó antes da aspersão. Neste trabalho avaliou-se a influência da adição de NbC e do composto cerâmico Al2O3+TiO2 no desempenho ao desgaste de revestimentos de Ni-Al, bem como verificou-se as alterações microestruturais, químicas, e mecânicas decorrentes. Para tanto se adicionou 25%p de NbC ou 25%p do composto Al2O3+TiO2 à liga base de Ni-Al, formando-se dois materiais compósitos: Ni-Al + NbC e Ni-Al + (Al2O3+TiO2). Utilizou-se microscópio eletrônico de varredura com EDS para caracterizar as matérias primas e os revestimentos produzidos, assim como determinar o mecanismo de desgaste nos ensaios de micro-abrasão tipo \"esfera-livre\" e \"esfera-fixa\". Mediram-se as durezas superficiais e as microdurezas das fases por meio dos ensaios Rockwell Superficial e microdureza Vickers. Avaliou-se a resistência ao desgaste por meio de ensaios de micro-abrasão nas modalidades \"esfera-livre\" e \"esfera-fixa\". As adições dos materiais citados na liga a base de níquel alteraram características microestruturais importantes, como aumento do percentual de óxidos, bem como a composição química e distribuição dos elementos nas camadas formadas; ocorreram também aumentos significativos das durezas e nas resistências ao desgaste dos revestimentos. / Thermo Spray is a metallic, polymeric, ceramic and composite coating process applied over a previously prepared surface usually seeking to improve wear and/or corrosion resistance. It is also used to repair worn surfaces restoring the original dimensions. Ni-Al alloys are used as a primer coating to promote the adhesion between surface and incompatible coatings and also extensively in the reconstruction of worn surfaces. The low hardness and wear resistance (when used in reconstruction applications) of this alloy could be improved by the addition of hard particles/composites to the powdered raw material prior to the spray operation. In this work the influence of NbC and Al2O3+TiO2 additions to Ni-Al alloys were evaluated concerning wear performance and the resulting changes in microstructure, chemical and mechanical behavior. The experimental procedure included the preparation of samples of the Ni-Al base alloy with additions of 25wt% of NbC or 25wt% of Al2O3+TiO2, what resulted in two different sprayed composite materials: Ni-Al + NbC e Ni-Al + (Al2O3+TiO2). SEM with EDS microprobe was used to characterize the raw materials, the sprayed coating samples and the type of wear mechanism occurring in the wear tests of the type \"free sphere\" and \"fixed sphere\" micro abrasion that were used to evaluate the wear resistance of the samples. Surface hardness and micro hardness of the different phases in the coatings were evaluated using Rockwell and Vickers micro hardness testing machines respectively. The addition of the hard phases promoted important changes in the Ni-Al base alloy, decreasing the porosity level and increasing the percentage of oxides. Hardness were significantly increased as well as the wear resistance of the coatings.

No presente trabalho, peças com gradiente funcional de Al2O3 com reforço de NbC foram planejadas com o intuito de obter um MGF (material com gradiente funcional) com uma alta dureza e boa tenacidade à fratura a partir de diferentes técnicas de sinterização. Os MGFs apresentam-se como uma excelente alternativa quando é necessária a união de materiais com propriedades térmicas ou mecânicas muito diferentes, já que possuem uma transição suave de propriedades ao longo do corpo, como consequência de uma mudança gradual do teor das fases. No planejamento dos MGFs foram utilizadas análises dilatométricas para compatibilizar o comportamento durante a sinterização de cada camada e assim minimizar as tensões que ocorrem durante a retração, responsáveis por trincas e delaminações. Nos ensaios de dilatometria observou-se que a diferença máxima de retração entre os compósitos de teor de NbC variando de 5 a 30 %p é de 4,85%, assim, foram projetados MGFs com um passo de 5% de NbC, reduzindo esta diferença para 2,73%. Compósitos monolíticos de Al2O3 com diferentes teores de NbC foram sinterizadas a 1500ºC num forno convencional sob atmosfera de grafite. As densidades das peças sinterizadas foram inferiores a 90% da densidade teórica (DT), o que comprometeu a dureza dos compósitos (10 a 14 GPa), inferiores que as durezas dos materiais originais. Uma das maiores dificuldades no processamento destes compósitos foi sua densificação, prejudicada devido à presença de partículas de alta refratariedade na matriz de alumina, pelo que foi realizado um estudo do efeito da nióbia (Nb2O5) como auxiliar de sinterização nos compósitos Al2O3-NbC. Utilizando 0,5 %mol deste aditivo foi possível melhorar as densidades dos compósitos que, segundo os resultados da microscopia eletrônica de varredura (MEV), devido a uma densificação em presença de fase líquida. No entanto, a melhora na densidade é efetiva para temperaturas inferiores a 1450°C devido provavelmente à sobrequeima. Devido às dificuldades para obter peças densas a partir desses compósitos, foi utilizado o processo de Spark Plasma Sintering (SPS), o qual foi bem sucedido para obter peças com gradiente funcional com boa densidade (> 98 %TD) e livres de trincas. O gradiente projetado foi mantido com sucesso após a sinterização e, graças à alta densidade das peças, foi possível atingir altas durezas (até 24,3 GPa) e tenacidade à fratura ~5 MPa.m1/2, fazendo com que estes materiais apresentem potencial de aplicação como ferramentas de corte. / In the present work, Al2O3/ NbC graded composites were designed in order to obtain a FGM with a high hardness and good fracture toughness from different sintering techniques. Functionally graded materials (FGM) present enormous potential on matching materials that have different mechanical and thermal properties via a gradual transition throughout the body, as a consequence of a gradual transition of the phase content. For designing of FGMs, a dilatometric analysis was used for matching the sintering behavior of each layer in order to minimize the thermal strains occurring during shrinkage and that are responsible for cracking and delamination. It was observed that the maximum difference in shrinkage between these composites is 4.85%, which could be reduced to 2.73% if a FGM with step of 5% NbC is produced. Monolithic composites of Al2O3 with different amounts of NbC were sintered at 1500°C in a conventional oven under an atmosphere of graphite, the density of the sintered pieces were less than 90 %TD, compromising the hardness of the composites (10 to 14 GPa) that were lower than the hardness of the original materials. Due to the fact that one of the greatest difficulties in processing these composites is a densification, which is impaired due to the presence of high refractory particles in the alumina matrix, a study of the effect of the niobia (Nb2O5) as a sintering aid in the composite Al2O3-NbC was conducted, with addition of 0.5 mol% was possible to improve the density of the composites, due to the liquid state sintering according to the SEM results. However, this effect is only effective until a temperature of 1450°C probably due to the overfiring. In order to obtain dense bodies from these composites, Spark plasma sintering (SPS) was used. This process was successful for producing functional graded bodies with good density (> 98% TD) and crack free. The designed gradient was successfully maintained after sintering and due to the high density of FGMs, it was possible to attain high hardness (up to 24.3 GPa) and a fracture toughness of ~ 5 MPa.m1/2, showing that these materials have a good potential application as cutting tools.

Dosímetros Luminescentes Opticamente Estimulados (OSL) vêm sendo testados como alternativa dosimétrica no controle da qualidade e verificação de tratamentos por possuir características adequadas para esse fim, como elevada sensibilidade à radiação ionizante, alta resolução espacial e facilidade de leitura. Neste trabalho, o óxido de alumínio, dopado com diferentes concentrações de carbono (Al2O3:C), foi estudado como material dosimétrico OSL. Nanotubos de carbono de paredes simples também foi avaliado como dopante, associados ao mesmo material, Al2O3:NTC, em alguns testes preliminares de resposta em função da dose em feixes de fótons de 50 kVp. O presente trabalho apresenta o processo de fabricação do dosímetro OSL, além de testes dosimétricos envolvendo metodologia experimental e por simulação Monte Carlo com o código PENELOPE para avaliação da resposta dosimétrica do Al2O3:C em função da concentração do carbono dopante. Neste trabalho foi investigada a resposta do dosímetro OSL para doses entre 50 cGy e 1000 cGy, em um amplo intervalo de energia de feixes de fótons. Foi analisada também, a interferência do uso do dosímetro OSL de Al2O3:C nas doses superficial e profunda em tratamentos radioterápicos. O dosímetro Al2O3:C(1%) apresentou diferença percentual máxima de 12% na homogeneidade de resposta em um grupo de 100 dosímetros e linearidade de resposta entre as doses de 50 cGy e 800 cGy para feixes de fótons de alta energia de 1,25 MV, 6 MV e 15 MV. Já para feixes de fótons de baixas energias, de 50 kVp, 120 kVp e 200 kVp, o dosímetro apresentou diferença significativa entre as respostas, evidenciando dependência com a energia. Além disso, foi investigada a estabilidade do sinal OSL em função do tempo e estipulado um tempo mínimo de armazenamento do dosímetro, entre a exposição e a leitura. O dosímetro Al2O3:NTC apresentou um aumento de sensibilidade de até 30% em relação ao dosímetro Al2O3:C(1%). Os resultados encontrados neste trabalho sugerem o uso do material dosimétrico OSL estudado como ferramenta em controle da qualidade em procedimentos clínicos de rotina na Radioterapia. / Optically Stimulated Luminescent dosimeters (OSL) have been tested as a dosimetric alternative in quality control and treatment verification since they have suitable characteristics for this purpose, such as high sensitivity to ionizing radiation, high spatial resolution and readability. In this work the aluminum oxide, doped with different concentrations of carbon (Al2O3:C), was studied as OSL dosimetric material. Single-walled carbon nanotubes were also evaluated as a dopant associated with the same material, Al2O3:NTC, and preliminary tests of response to dose in photon beams of 50 kVp were performed. This work presents the fabrication process of the OSL dosimeter, and dosimetric tests involving experimental methodology and Monte Carlo simulation with PENELOPE code to evaluate the response of the dosimetric Al2O3:C as a function of the concentration of carbon dopant. In this study we investigated the response of the OSL dosimeter for doses ranging from 50 cGy to 1000 cGy in a wide range of energy of photon beams. The interference of the OSL dosimeter Al2O3:C in superficial and deep doses in Radiotherapy treatments was also analyzed. The dosimeter Al2O3:C (1%) had a maximum percentage difference of 12% in the homogeneity of a group of 100 dosimeters and presented linearity of response in a dose range of 50 cGy and 800 cGy for photon beams of high energy of 1.25 MV, 6 MV and 15 MV. As for photon beams of low energies of 50 kVp, 120 kVp and 200 kVp, the dosimeter showed a significant difference between responses, indicationg dependence on energy. In addition, we investigated the stability of the OSL signal as a function of time and set a minimum time of storage of the dosimeter, between exposure and reading. The dosimeter Al2O3:NTC showed an increased sensitivity of up to 30% over the dosimeter Al2O3:C (1%). The findings on this study suggest the use of the material studied as OSL dosimeter as a tool in quality control in routine clinical procedures in Radiotherapy.

A radiação laser tem sido amplamente utilizada em diversos dispositivos para aplicações tecnológicas. Uma área particularmente interessante que tem sido explorada para o desenvolvimento destes dispositivos é a medicina. Um campo da medicina que tem se beneficiado desse esforço é a termoterapia a laser. No entanto, algumas desvantagens do uso em larga escala desta tecnologia são devidas à falta de uniformidade da absorção da radiação pelo tecido humano. Uma maneira proposta de resolver esta problemática tem sido a utilização de um método fototérmico indireto para converter a energia da luz do laser em calor; por meio de uso de pontas de fibras ópticas revestidas. Contudo, o uso dessas pontas apresenta a desvantagem da limitada estabilidade química do revestimento. Neste trabalho, apresentamos os resultados do desenvolvimento de pontas cristalinas de Nd2O3 altamente estáveis quimicamente em fibras monocristalinas de safira (Al2O3) obtidas diretamente a partir da fase líquida (fundida), fazendo-se uso da técnica Laser-Heated Pedestal Growth (LHPG). A metodologia desenvolvida permite a produção de pontas de diâmetros variados, o que possibilita definir a dimensão da região de aquecimento dentro dos limites de interação ponta cristalina/meio. Para o crescimento dos cristais no formato de fibras, chamados de fibras monocristalinas, usando-se a técnica LHPG, preparamos pedestais de Al2O3 puros e de composição Nd2O3, utilizando-se a técnica de extrusão a frio. Fibras monocristalinas de safira de 0,67 mm de diâmetro e 200 mm de comprimento, livres de poros ou trincas, com pontas cristalinas aproximadamente cônicas foram fabricadas em atmosfera aberta. Para avaliarmos a eficiência da conversão de luz em calor, as fibras foram bombeadas com luz de um laser de comprimento de onda 810 nm. Uma correspondência linear entre a potência do laser e a temperatura da ponta cristalina foi determinada em nossos sistemas e valores de até 250 oC podem ser alcançados; o que torna a ponta cristalina da fibra promissora para aplicações em termoterapia a laser e para a área de soldagem em micro(nano) eletrônica. Neste trabalho apresentamos também um estudo sistemático sobre o processo de puxamento de fibras do compósito eutético Nd2O3-NdAl11O18, através da técnica LHPG, com velocidades de puxamento variando entre 0,08 - 0,92 mm/min. As fibras eutéticas foram fabricadas com sucesso, livres de poros ou trincas. A microestrutura analisada ao microscópio eletrônico de varredura (MEV) foi denominada como do tipo regular, presente em todas as amostras. A despeito da sua complexidade, a microestrutura desse compósito foi controlada e a relação entre o espaçamento médio entre as fases e a velocidade de puxamento &#9552v = constante = (8,2 ± 0,3) µm3/s foi mantida em todo o intervalo das velocidade de puxamento utilizadas. Devido às propriedades mecânicas e ópticas das fases eutéticas individuais, este compósito apresenta-se como candidato com enorme potencial para aplicações dentro da ciência e engenharia de materiais. Ao nosso conhecimento, este trabalho parece ser o primeiro relato sobre a microestrutura eutética do sistema binário Al2O3-Nd2O3. / The laser radiation has been extensively used as devices for technological application, for which the medicine is a hot topic. In this field, the laser-induced thermotherapy is the primary beneficiary of the main researches and applications. However, the heterogeneity associated to the light aborsorption by the human tissue is major impediment preventing the large using of the thermotherapy. To solve this situation, an indirect photothermal method has been employed in order to convert laser radiation into heat by using coated optical fiber tips. Nevertheless, the limited chemical stability of the coating is a crucial problem associated to the large scale application of these coated tips. In the present work, we prepared crystal tips of Nd2O3, chemically stable, coupled in the Al2O3 (sapphire) crystal fiber, being both obtained by the laser-heated pedestal growth technique (LHPG), providing the production of tips with different diameters. Also, the cold extrusion technique was employed to produce the Al2O3 e Nd2O3 pedestals. Besides, the Al2O3 crystal fibers with 0.67 mm in diameter and 200 mm in length, free of cracks and pores, were successfully produced in an air atmosphere. In order to account the efficiency of the light-to-heat conversion, the fibers were pumped with laser light centered at 810 nm. Finally, linear correspondence between laser power and crystal tip temperature was determined in our systems, making them appropriated to the laser-induced thermotheraphy applications and welding in micro- and nano-electronics. Furthermore, we presented a profound investigation about the pulling process of Nd2O3-NdAl11O18 eutectic fibers obtained by LHPG technique. These eutectics were successfully pulled free of cracks and pores. Using scanning electron microscopy (SEM), we were capable of identificating the regular microstructure of our eutectics. Changes in the microstructure were observed in the eutectic fibers pulled using fiber pulling rates from 0.08 to 0.92 mm/min. Despite the complexity of their microstructures, the relation &#9552v = (8,2 ± 0,3) µm3/s = constant, defined by Jackson and Hunt, applied very well for this system. Owing to the mechanical and optical properties of the eutectic phases, these compounds present huge potential for applications in the materials science and engineering related fields. To our knowledge, this work seems to be the first report on the eutectic microstructure of the Al2O3-Nd2O3 binary system.

Ces travaux de thèse ont porté sur l'étude approfondie de catalyseurs à base d'argent et d'or dans la réduction catalytique sélective des NOx par C3H6. Pour le système Ag/Al2O3, nous avons réussi à fournir une explication rationnelle de l'origine de l'existence d'un optimum d'activité pour une teneur en Ag de l'ordre de 2 %pds reporté à plusieurs reprises. La caractérisation par NOx-TPD des catalyseurs Ag/Al2O3 a permis d'attribuer l'origine de cet optimum à la teneur maximale en Ag pour laquelle la dispersion quasi-atomique de l'argent est préservée. Nous avons aussi démontré pour la première fois que l'activité des catalyseurs Ag/Al2O3 dans la réduction des NOx par C3H6 en présence de H2 augmentait lorsque la densité surfacique en Ag diminuait. Ceci a été expliqué par l'augmentation du nombre de sites du support pouvant adsorber les NOx lorsque la teneur en Ag diminue. Le système catalytique Au/Al2O3 a été également étudié. En diminuant le nombre de sites d'or dans le réacteur, un effet promoteur de H2 a été mis en évidence pour la première fois pour ce système dans la réduction des NOx par C3H6. Cet effet promoteur était plus important lorsque la teneur en Au diminue. L'activité catalytique du système Au/Al2O3 a été optimisée par la cérine, le catalyseur présentant 1%pds en CeO2 et 0,5%pds en Au a montré la meilleure conversion des NOx. L'activité catalytique d'un système Au-Ag/Al2O3 a également été examinée mais trouvée moins intéressante que celles des systèmes monométalliques. La conversion des NOx en N2 en présence de H2 sur un catalyseur Ag/Al2O3 a pu être améliorée de prés de 30 % en déposant l'argent sur un support prétraité hydrothermalement. / This work provides further insights into C3H6-SCR on alumina supported silver and gold catalysts. The origin of the optimum loading of 2 wt% of Ag on Al2O3 in the C3H6-SCR of NOx was elucidated with the help of an original characterization method (NOx-TPD). The optimum loading was attributed to the maximum loading of silver on Al2O3 for which highly dispersed Ag species are preserved. Our study highlights for the first time that the H2-C3H6-SCR catalytic performance of Ag/Al2O3 samples improved in the 150-550 °C temperature domain as the Ag loading decreased well below 2 wt%. A detailed kinetic study of H2-C3H6-SCR was performed and led us to conclude that the unexpected higher catalytic performance of the Ag samples with the lower Ag surface densities was attributed to the higher concentration of active sites on the Al2O3 supporting oxide able to chemisorb NOx species. Regarding Au/Al2O3 catalysts, our work provides the first experimental evidence of an H2 effect in C3H6-SCR over Au/Al2O3 catalysts. This effect could only be observed when the number of Au catalytic sites in the reactor was decreased. The influence of the Au loading on the H2-C3H6-SCR was investigated. Au/CeO2-Al2O3 system was optimized with addition of ceria. Among the Au/CeO2-Al2O3 catalysts evaluated, the sample containing 0.5 wt% Au and 1 wt% CeO2 exhibited the best NOx conversion in C3H6-SCR at low temperature (from 150 °C). The catalytic activity of bimetallic Au-Ag /Al2O3 catalysts was investigated in C3H6-SCR and H2-C3H6-SCR. Finally, NOx conversion to N2 on Ag/Al2O3 in H2-C3H6-SCR could be improved substantially by nearly 30 % when silver is added on hydrothermally pretreated Al2O3 support.

La valorisation de la biomasse lignocellulosique en molécules plateforme pour l'industrie chimique rend nécessaire l'adaptation des méthodes de raffinage à la transformation de composés organiques oxygénés. La déshydratation des alcools connaît dans ce contexte un fort regain d'intérêt. Les travaux de cette thèse s'attachent à comprendre à l'échelle moléculaire la réactivité d'un alcool modèle (isopropanol) sur catalyseurs aluminiques, au travers d'une étude mettant en jeu expériences et modélisation aux échelles moléculaire (DFT) et du réacteur (modélisation cinétique). En combinant expériences de spectroscopie infrarouge, mesures cinétiques et modélisation moléculaire appliquée à l'adsorption et aux chemins réactionnels de l'isopropanol sur l'alumine gamma, il est montré que la réactivité de cet alcool est principalement gouvernée par la facette (100) de l'alumine. Les formations compétitives de propène, majoritaire, et de diisopropyléther, minoritaire, impliquent un même intermédiaire alcoolate, adsorbé sur un atome d'aluminium acide de Lewis, qui évolue soit par élimination directe d'une molécule d'eau (mécanisme E2), soit par condensation avec une seconde molécule d'alcool adsorbée à proximité (mécanisme SN2). Un modèle microcinétique fondé sur ce site unique de réaction, incluant de surcroît la décomposition de l'éther en isopropanol et en propène, permet de reproduire les résultats expérimentaux à condition de prendre en compte l'effet de molécules d'eau et d'alcool co-adsorbées dans l'environnement du site actif, la formation de dimères eau - intermédiaire et la stabilisation de la seconde molécule d'alcool contribuant à l'ajustement du rapport éther/propène. / The upgrading of lignocellulosic biomass into strategic molecules for the chemical industry requires the adaptation of refining procedures to the transformation of oxygenated species. In this context, the dehydration of alcohols has seen renewed interest over the last decade. The work presented here aims at unravelling the reactivity of a model alcohol (isopropanol) over aluminic catalysts at the molecular scale. To this purpose, a study combining experiments and modelling at the molecular scale (DFT) and at the reactor scale (kinetic modelling) has been set up. By combining infrared spectroscopic experiments, kinetic measurements and molecular modelling of the adsorption and reaction pathways of isopropanol on gamma alumina, it is shown that this reactivity is mainly governed by the (100) facets of alumina. The competing formation of propene (major product) and diisopropylether (minor product) involves a common alcoolate intermediate adsorbed on a Lewis acidic aluminium atom, either by direct elimination of a water molecule (E2 mechanism) or by condensation with a second alcohol molecule adsorbed in vicinity (SN2 mechanism).A micro-kinetic model involving this single reaction site and including the transformation of the ether into isopropanol and propene allows reproducing the experimental results, provided that the effect of co-adsorbed water and alcohol molecules in the environment of the active site is taken into account, as the formation of water – intermediate dimers and the stabilization of the second alcohol molecule both contribute to an adjustment of the ether/propene ratio.

This work deals with electrolytic conductivity of gel polymer electrolytes. In the theoretical part of the work the methacrylates, the polymerization and the basic outlines of gel polymer electrolytes conductivity are described. The preparation and electrical conductivity of gels based on PMMA are described in the experimental part.

De nos jours, l'effet du réchauffement planétaire devient une question primordiale pour l'humanité. La plupart des sources d'énergie traditionnelles comme l’énergie thermique, le nucléaire, l'hydroélectricité, etc. sont dangereux et/ou potentiellement dangereux pour la nature et l'être humain. Par conséquent, une «énergie verte» est fortement souhaitée. L'énergie verte a deux caractéristiques : d'une part l’utilisation de sources d'énergie renouvelables comme l'énergie solaire ou géothermique, etc au lieu des sources d'énergie traditionnelles, ainsi qu’un meilleur rendement. Un rapport récent a souligné que la perte d'énergie aux États-Unis est plus importante que la somme de toutes les énergies renouvelables générées. Il est donc essentiel d'utiliser efficacement l'électricité et de limiter les pertes. Malheureusement, les pertes sont l'endémie des composants semi-conducteurs, le dispositif central de tout système de conversion de puissance. Le silicium (Si), le matériau le plus utilisé dans les composants semi-conducteurs a atteint sa limite physique. Des semi-conducteurs à large bande interdite tels que SiC, GaN, Ga2O3 et le diamant sont des matériaux prometteurs pour fabriquer des dispositifs à faibles pertes en état ON et avec une tension de claquage à l’état OFF élevée. Parmi eux, le diamant est un semi-conducteur idéal pour les appareils de haute puissance en raison de ses propriétés physiques supérieures aux autres matériaux. Les progrès récents sur ce sujet permettent de considérer le développement de dispositifs de puissance en diamant, par exemple les MOSFETs. Afin de réaliser un MOSFET en diamant semi-conducteur, le nombre de problèmes à surmonter est important, particulièrement maîtriser l'interface diamant/oxyde. Dans ce contexte, G. Chicot et A. Marechal (anciens doctorants de notre groupe) ont introduit les dispositifs de test MOSCAP O-diamant/Al2O3 et montré que l'alignement des bandes est de type I à l'interface O-diamant/Al2O3, ce qui est favorable pour réaliser à la fois un MOSFET à inversion et un MOSFET à déplétion. Ce doctorat s’inscrit dans la suite de ces deux thèses. Il a eu deux objectifs principaux: 1. Les recherches fondamentales, qui se consacrent à la compréhension de la caractéristique électrique d'un dispositif de test de diamant MOSCAP; 2. Partant de la compréhension du MOSCAP, un MOSFET en diamant est réalisé par le contrôle de la conduction de courant volumique. La thèse comprend ainsi trois chapitres : Le chapitre 1 traite du contexte des dispositifs de puissance ainsi que des propriétés physiques du diamant et de l'état de l'art des dispositifs en diamant. Nous introduisons également le principe de fonctionnement d'un dispositif de test MOSCAP idéal et de l'état de l'art des O-diamant MOSCAP. Le chapitre 2 est consacré à la compréhension fondamentale des O-diamant MOS capacités et comprennent trois parties principales: la partie 1 traite des questions de méthodologie liées à la croissance du diamant, le procédé de fabrication et de caractérisation électrique. Nous allons construire un modèle électrostatique empirique pour les MOSCAP O-diamant. La partie 2 discute de l'origine du courant de fuite et de la dispersion de la caractéristique capacitance-fréquence lorsque la MOSCAP est polarisée en négatif. La partie 3 traite de l'origine du courant de fuite et de la dispersion de la caractéristique capacitance-fréquence lorsque la MOSCAP est polarisée en positif. Le chapitre 3 présente notre approche pour réaliser un MOSFET en diamant dopé au Bore. Les performances du transistor et ses paramètres importants seront quantifiées. Le benchmark du dispositif et la projection vers son amélioration seront mentionnés. / Nowadays, global warming effect is one of most challenging issue for human being. Most of “traditional energy” sources like thermal power; nuclear power, hydroelectricity power, etc. are dangerous and/or potentially dangerous for nature and human being. Therefore, the "greener energy" is highly desired. The "greener energy" has two folds meaning: on one hand, using renewable energy sources like solar power, wind power or geothermal energy, etc. instead of the traditional energy sources. One another hand, use the electricity more effectively and more efficiency. A recent report has pointed out that the energy loss in US is in fact more than sum of all renewable energy generate in US. Therefore, effectively utilizing electricity and limiting the waste is critical.Unfortunately, losses are the endemic of semiconductor components, the central device of all power conversion system. Silicon (Si), the main material for semiconductor components has reached its physical limit. Wide band-gap semiconductors such as SiC, GaN, Ga2O3 and diamond are promising materials to fabricate the devices low ON-state loss and high OFF-state breakdown voltage. Among them, diamond is an ideal semiconductor for power devices due to its superior physical properties. Recent progresses on diamond technology permits one consider the diamond power devices, e.g. MOSFET.In order to realize a diamond MOSFET by controlled diamond semiconductor, the numbers of issues needed to be overcome is important, especially mastering the diamond/oxide interface. In this context, G. Chicot and A. Marechal (former PhD students in our group) has introduced the O-diamond/Al2O3 MOSCAP test devices and measured the type I band alignment at O-diamond/Al2O3 interface, which is favorable to realize both inversion MOSFET and depletion MOSFET in his PhD these. This PhD project is a continuation of two-mentioned thesis and including two main objects: 1. Fundamental investigations dedicate to understand the electrical characteristic of an O-diamond MOSCAP test device; 2. Realize a unipolar diamond MOSFET by controlling the diamond semiconductor epilayer. The thesis will include three chapters:Chapter 1 discusses the context of power devices as well as the physical properties of diamond and state-of-the-art of diamond devices. We also introduce the working principle of an ideal MOSCAP test device and States-of-the-art of O-diamond MOSCAP test devices.Chapter 2 dedicates for the fundamental understanding O-diamond MOSCAP and include three main parts: Part 1 addresses the methodology issues related to diamond growth, fabrication processing and electrical characterizations. We will construct an empirical electrostatics model for O-diamond MOSCAP. Part 2 discusses the origin of leakage current and capacitance-frequency dependent when O-diamond MOSCAP is biasing in negative direction. We quantify the interface states density at O-diamond/Al2O3 interface by conductance method and the complete electrostatics model for O-diamond/Al2O3 MOSCAP will be constructed. Part 3 discusses the origin of leakage current and the capacitance-frequency dependent when the O-diamond MOS capacitor is biasing in positive direction.Chapter 3 introduces our approach to realize a depletion mode diamond MOSFET. Transistor performance and the important parameters of the transistor will be quantified. The benchmark of the device and the projection towards its improvement will be mentioned.

Les transistors à effet de champ sensibles aux ions (ISFET) sont des composants électroniques conçus pour fonctionner en phase liquide. Pour résumer, ce sont des MOSFET dont la grille métallique est remplacée par une membrane isolante ionosensible. Au début des années 2000, ces composants ont évolué avec l'introduction des premiers dispositifs à base de nanofils de silicium. Grâce à leurs faibles dimensions, ces capteurs ont ouvert de nouvelles perspectives, comme par exemple, l'étude des métabolismes intracellulaires. L'objectif de cette thèse a été de développer et d'étudier un capteur de type ISFET, à base de nanofils de silicium, ayant comme couche sensible l'alumine Al2O3. Les premiers travaux ont porté sur l'intégration de films minces d'alumine Al2O3 dans un procédé de type MOSFET. Ce matériau devant être déposé sur des nanofils de silicium, la technique de dépôt successif de couches moléculaires (Atomic Layer Deposition ALD) a été retenue. Cette méthode offre la possibilité de déposer des films d'épaisseur homogène tout autour des nanofils. Après l'étude de l'ALD-Al2O3, la deuxième grande partie de ce projet a consisté à développer, en utilisant les techniques de la microélectronique, des structures innovantes à base de nanofils de silicium. Des transistors constitués d'un seul nanofil, et d'autres constitués de réseaux parallèles de nanofils ont été réalisés. Ces capteurs ont été intégrés dans des canaux microfluidiques, permettant ainsi de localiser précisément le liquide sur les nanofils, mais aussi de pouvoir travailler en micro/nanovolumes. La dernière partie de ce projet a consisté à caractériser ces capteurs en phase liquide. Les différentes configurations ont montré leurs avantages et inconvénients en termes de transconductance, courants de fuite, pentes sous le seuil, sensibilités au pH et aux ions interférents (Na+ et K+). Les caractérisations se sont avérées excellentes et laissent entrevoir des perspectives intéressantes pour des applications biologiques. Les principales innovations de ces capteurs concernent : l'utilisation de nanofils suspendus, la réalisation d'une gaine isolante ionosensible bicouche SiO2/Al2O3 tout autour des nanofils, la variation du dopage le long des nanofils ce qui a conduit à la réalisation de jonctions N+/P/N+, et l'intégration des capteurs dans des canaux microfluidiques couverts. / Ion-sensitive field effect transistors (ISFET) are electronic components designed to operate in liquid phase. To summarize, they are MOSFET-based devices whose metal gate is replaced by an ionosensitive insulating layer. In the early 2000s, these components evolved with the introduction of the first device based on silicon nanowires. Thanks to their small dimensions, these sensors opened up new perspectives, such as the study of intracellular metabolisms. The aim of this thesis was to develop and study a type of ISFET sensor, based on silicon nanowires, with Al2O3 alumina as sensitive layer. The first part of this work was focused on the integration of thin alumina Al2O3 films in a MOSFET process. This material had to be deposited on silicon nanowires, that is why Atomic Layer Deposition (ALD) was used. This method allows to deposit films with uniform thickness all around nanowires. After the study of ALD-Al2O3, the second major part of this project was to develop innovative structures, based on silicon nanowires, using microelectronics methods. Transistors consisting of a single nanowire, and others consisting of parallel networks of nanowires were fabricated. These sensors were integrated in microfluidic channels, allowing to precisely locate the liquid on nanowires and also to work in micro/nanovolumes. The last part of this project consisted in characterizing these sensors in liquid phase. The different configurations showed their advantages and disadvantages in terms of transconductance, leakage currents, slopes below the threshold, sensitivities to pH and interfering ions (Na+ and K+). The characterizations proved to be excellent and suggest interesting prospects for biological applications. The main innovations of these sensors are: the use of suspended nanowires, the realisation of a bilayer SiO2/Al2O3 ion-sensitive sheath all around the nanowires, the doping variation along the nanowires which led to the realization of N+/P/N+ junctions, and the integration of sensors into covered microfluidic channels.