Conselho Nacional de Desenvolvimento Científico e Tecnológico / Nesse trabalho foram realizadas reações de substituição nucleofílica (SN2), utilizando aquecimento térmico convencional e por irradiação de micro-ondas (MO), de alguns átomos cloro em amostras comerciais de poli(cloreto de vinila) (PVC), por grupos nitrila e também por grupos azida. Os grupos nitrila e azida foram substituidos na matriz em diferentes teores (10% e 20%). As reações do PVC com azida foram eficazes, apresentado percentuais de derivatização muito próximos dos valores desejados. Já no estudo com a nitrila não foi obtido o resultado esperado. Os copolímeros PVC azido substituídos foram modificados com propargilato de etila, sob catálise de iodeto de cuproso (CuI), para a obtenção de heterocíclicos do tipo triazólicos. Todos os copolímeros obtidos foram caracterizados por espectroscopia na região do infravermelho (FTIR) e os teores de nitrogênio incorporado foram determinados por análise elementar (AE). Através da análise dos dados obtidos, foi comprovado que a utilização da irradiação micro-ondas, quando comparada ao aquecimento convencional, é um processo mais seletivo e diminui, significativamente, os tempos de reação / In this work we had performed nucleophilic substitution reactions (Sn2) of some chlorine atoms in commercial samples of poly (vinyl chloride) (PVC), nitrile groups and also by azide groups, using both conventional thermal heating and microwave irradiation (MW).Nitrile and azide groups were replaced in the matrix at diverse levels (10% and 20%). The reactions of PVC with azide were effective, reaching a percentage derivatization very near to the desired values. In the study with the nitrile although we have not obtained the expected results. The substituted azido copolymers were modified with propargilato acetate, under catalysis of copper iodide (CuI) to obtain triazole heterocyclic type. All copolymers were labeled by infrared spectroscopy (FTIR) and nitrogen contents were determined by corporate elemental analysis (EA). Through analysis of the data obtained, it was verified that the use of microwave irradiation in comparison to conventional heating is a more selective process and reduces significantly reaction times

Cette étude porte sur l'amélioration de la qualité de la tomate séchée par microondes assistés par air chaud (MOAC). Le principal but recherché est la préservation de la qualité de la tomate séchée en évitant notamment l'apparition de tâches noires qui souvent surviennent lors d'un chauffage microondes suite à une surchauffe locale du produit quand il devient sec. Pour ce faire, un système de séchage microondes assistés par air chaud avec la capacité de contrôler automatiquement la puissance spécifique a été développé sous labView®. Après une première étude où la puissance microondes appliquée est maintenue constante, une seconde stratégie de séchage MOAC, avec deux modes différents de régulation de la puissance spécifique, a été mise en oeuvre. Ces modes consistent à ajuster la puissance microondes appliquée à la masse du produit, représentative de la quantité d'eau restante. Dans le premier mode, l'adaptation est faite toutes les secondes (ajustement "continu") alors que dans le second mode, la puissance a été ajustée seulement chaque cinq minute (ajustement intermittent). L'ajustement permet de travailler avec un rapport puissance appliquée sur masse résiduelle du produit (puissance spécifique) constant. Tous les paramètres du procédé incluant la puissance appliquée on été enregistrés chaque seconde. De même, la température et la masse du produit sont mesurées chaque seconde. Le produit final a été caractérisé en réalisant des mesures de couleur, de texture, de structure ainsi que de taux résiduel de lycopène. La première étude sur le séchage MOAC réalisée à puissance constante (puissance spécifique variable), a produit des tomates avec des points chauds par endroit et plus de la moitié de la teneur en lycopène de la tomate est dégradée. En revanche, les tomates séchées par MOAC utilisant les deux modes de régulation du séchage, présentent une meilleure qualité en termes de couleur et de structures comparées à deux tomates séchées commerciales de référence (d'origine italienne et ivoirienne). Par ailleurs, l'observation de la structure des tomates par Microscopie Electronique à Balayage (MEB), a permis d'expliquer les changements observés au niveau de la texture de la tomate séchée. D'un point de vue chimique, le taux résiduel de lycopène de la tomate séchée par les modes de régulation (1 et 2) est situé respectivement entre 64,78 et 55,63% pour les puissances et températures d'air basses (3W/g-30°C) et entre 30,91 et 28,75% pour les puissances et températures d'air élevées (7W/g-50°C), contre 30,56 et 22,30% pour les tomates commerciales d'origine italienne et ivoirienne. / The aim of this study was to improve the quality of dried tomato by the use of microwaves combined to hot air (MOAC). The main point was to preserve the quality of dried tomato avoiding the appearance of black spots which often occur during microwaves heating which result from local overheating of the product when it becomes dry. Therefore, an MOAC drying system with ability of automatic control of the power density was developed under LabView®. After an initial study where the applied microwave power remained constant during the drying, a second MOAC drying strategy, with two different control modes, was implemented. This modes consisted to adjust the microwave power density to the remaining amount of water (actually the weight of the product). In the fist one, it is adjusted every second, while in the second, the power was adjusted only every 5 min. Therefore the ratio between the power applied and the weight of the product (i.e. the specific power) remained constant. All the process parameters, including the power applied and the product temperature and weight were recorded every second. The final product was characterized by performing measurements on color, texture, structure and residual lycopene content. In our initial study on MOAC drying performed at constant power (i.e. variable specific power), we have obtained dried tomatoes with hot spots and with a residual lycopene content lower than 50%. The tomatoes dried at constant specific power showed a better physical aspect and a higher nutritional quality, even compared to two commercial products from Italy and Ivory Coast. In addition, the structure of dried tomatoes observed by Scanning Electron Microscopy (SEM) allowed to explain changes in dried tomatoes texture. Chemically, the residual rate of lycopene in tomatoes dried at constant specific power ranged respectively between 64.78 and 55.63% for low power and air temperatures (3W/g-30 °C) and between 31.91 and 28.75% for high power and air temperatures (7W/g-50° C), while only 30.56 and 22.30% for commercial tomatoes from Italy and Ivory Coast.

Orientador: Celia Marisa Rizzatti Barbosa / Tese (doutorado) - Universidade Estadual de Campinas. Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-07-28T03:15:46Z (GMT). No. of bitstreams: 1 Zanetti_GlaucoRangel_D.pdf: 4522575 bytes, checksum: 4717fe0797e79a21a39c9cbeebb8ac1d (MD5) Previous issue date: 2000 / Resumo: Este estudo avaliou a influência do material de inclusão (gesso tipo 11 Herodent@ "G", silicone por condensação laboratorial Zetalabor@ "Z"), e da configuração da porção distal da grade metálica (com apoio "C" e sem apoio "s" sobre o modelo), nas alterações horizontais (esquerda "HE" e direita "HD") e verticais (esquerda "VE" e direita "VD") , entre as porções distais de estruturas metálicas de prõteses parciais removíveis (PPR's) e seus respectivos modelos durante o processamento das bases em resina acrílica. Foram utilizados modelos simulando uma arcada inferior parcialmente desdentada classe I de Kennedy. Quarenta amostras padronizadas foram divididas em quatro grupos. As bases foram processadas com uma resina polimerizada por energia de microondas (Onda-Cryl@). Os dados foram submetidos à análise de variância e as médias, ao teste de Tukey (p<O,O5). Os resultados das médias das alterações em milímetros, nos grupos GC (HE=0,2043; HD=0,1610; VE=0,0599; VD=0,0599), GS (HE=O,1888; HD=0,1156; VE=0,2063; VD=O,2420), ZC (HE=0,1796; HD=0,2025; VE=O,0717; VD=0,1396), ZS (HE=0,2043; HD=0,O746; VE=O,2143; VD=0,2880) indicaram que: na VE e VD, G não diferiu de Z, mas C apresentou alterações significativamente menores que S; na HE os grupos não diferiram estatisticamente entre si; na HD não houve diferença significativa entre (ZC e GC), (GC e GS), (GS e ZS) e as alterações foram progressivamente maiores em ZS, GS, GC e ZC / Abstract: This study evaluated the effect of two types of investment material ("G", type 11 dental stone, Herodent@; "Z", condensation silicone, Zetalabor@) and two types of design of the distal portion of the metallic framework ("S", with support in the model; "N", without support in the model) in the horizontal ("H L", left; "HR", right) and vertical ('VL", left; 'VR", right) distance changes between the distal portion of the metallic framework and their respective models during processing of the acrylic bases. A lower Kennedy Class I model was used. Forty standardized RPD's were prepared and equally divided into 4 groups. The RPD's bases were processed using a microwave-cured acrylic resin (OndaCryl@). Data was submitted to a "Tukey's Studentized" test (p<O.O5). The results of the means alterations in millimeters, in the groups GS (HL=O.2043; HR=O.1610; VL=O.O599; VR=O.O599), GN (HL=O.1888; HR=O.1156; VL=O.2063; VR=O.2420), ZS (HL=O.1796; HR=O.2025; VL=O.O717; VR=O.1396), ZN (HL=O.2043; HR=O.O746; VL=O.2143; VR=O.2880) showed that for VL and VR measurements, G and Z were not different, and S showed statistical lower changes than N. There was not difference of HL among groups. Considering HR, there was no statistical difference between groups for each following pair: ZS-GS, GS-GN and GN-ZN. Changes were crescent in the order ZN, GN, GS and ZS / Doutorado / Protese Dental / Doutor em Clínica Odontológica

Orientadores: Sandra Cristina dos Santos Rocha, Antonio Marsaioli Junior / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-13T10:14:46Z (GMT). No. of bitstreams: 1 Lescano_CesarAugustoAgurto_D.pdf: 2604640 bytes, checksum: f057c35fa84a33f1e932ab0c420a5210 (MD5) Previous issue date: 2009 / Resumo: O aproveitamento de resíduos industriais tem se tornado muito importante para evitar contaminação do meio e reaproveitar recursos até então considerados desperdícios ou perdas nas indústrias químicas e de alimentos. Na atualidade não se tem um valor aproximado da produção de leite de soja no mundo, mas sabe-se que grandes quantidades de resíduo são geradas pela produção do leite de soja, resíduo este que na literatura se denomina "Okara". Uma forma de aproveitar este resíduo é através de uma operação de secagem. A secagem é uma tecnologia amplamente utilizada pelas indústrias para manter a qualidade e prolongar a vida de prateleira dos produtos devido à diminuição das reações degradativas. Outro resultado da secagem é a diminuição do tamanho e peso do produto, facilitando assim seu transporte e armazenamento. No entanto, ainda hoje, apesar dos avanços tecnológicos nas indústrias químicas e de alimentos, persistem problemas quanto aos métodos específicos adequados para a secagem dos diferentes materiais biológicos, especialmente aqueles usados para alimentação humana. O resíduo de leite de soja é rico em proteínas, fibras e vitaminas, o que o torna de grande importância para diminuir o grande déficit de proteína que tem a população mundial, além de ser possível elaborar novos produtos utilizando o Okara seco como ingrediente e desta forma dar valor agregado aos novos produtos. O Okara apresenta-se como um material particulado muito úmido 80% (b.u.), e com alto teor de umidade superficial. A realização de uma operação mecânica de prensagem anterior à operação de secagem é necessária, para reduzir o teor de umidade até cerca de 60% (b.u.), otimizando dessa maneira a secagem, sem gastos não necessários de energia. O Okara é um material termo-sensível e, enquanto úmido, altamente deteriorável. Após o processo de prensagem, este material é particulado, altamente coesivo, de difícil escoamento, poroso e com alto teor de umidade interna (não podendo ser caracterizado como uma pasta). O objetivo desta pesquisa é estudar a secagem do resíduo do leite de soja, Okara, utilizando três tipos de secadores: secador de leito de jorro, secador de cilindro rotativo com aplicação de microondas e secador de forno de microondas. A secagem no leito de jorro foi realizada em batelada, enquanto, no secador de cilindro rotativo com aplicação de microondas, foi realizada em forma contínua. Foi necessária a utilização de material inerte nestes dois secadores: no secador de leito de jorro o inerte que apresentou melhor fluidodinâmica junto com o Okara úmido foi o polipropileno; diferente do secador rotativo, onde o inerte que apresentou melhor acompanhamento no transporte do Okara. dentro do cilindro foi o poliestireno. O processo de elaboração do Okara foi o mesmo para os dois equipamentos. As variáveis de processo analisadas no secador de leito de jorro foram: temperatura do ar de secagem, razão entre a vazão do ar e a vazão de jorro mínimo e tempo de trituração do material; no secador rotativo com aplicação de microondas as variáveis independentes analisadas foram: temperatura e vazão do ar de secagem e potência das microondas. Para os dois secadores foi elaborado um planejamento fatorial 2³, tendo como respostas avaliadas: teor de umidade para um determinado tempo de secagem e constantes do modelo de Page para a cinética de secagem (esta última apenas para o secador de leito de jorro). Foi ainda avaliado o desempenho operacional de ambos secadores, através da produtividade e eficiência térmica do processo. Foram também determinadas as propriedades físicas para o material antes e à saída nos secadores. O secador de forno de microondas foi utilizado para determinar as curvas de secagem, controlando-se as mesmas variáveis independentes analisadas no secador de cilindro rotativo. / Abstract: The use of industrial residues has become more and more important to avoid the environment contamination and to make use of resources considered wastes in the chemical and food industries. Actually, the approximated soy milk production in the world is unknown; however, it is known that large amounts of its residue, named "Okara", are generated by its production. Drying is an operation that could make this residue viable. The drying is a technology widely used by the industries to improve the quality and extend the shelf-life of the products due the decrease of the degraded reactions. Another result of a drying process is the decrease of the product's weigh and size, facilitating its transport and storage. However, until now, despite the technologic overhauls in the chemical and food industries, problems persist on defining the specific appropriate methods to dry different biological materials, mainly those used as human food. The soy milk residue is rich in proteins, fibers and vitamins, what makes it important in decreasing the enormous protein deficit of the world population, beyond the possibility of elaborating new products using Okara as ingredient, thus giving aggregate value to these new products. Okara is a very moist particulate material, 80% (b.u.), with high content of superficial moisture. A mechanic pressing operation before drying is indicated to decrease the Okara initial moisture content to around 60% (b.u.) and in this way optimize the drying process, without non-necessaries energy losses. The Okara is a thermo-sensible material and, while wet, highly deteriorative. After pressing, this material is particulate, highly cohesive, hard flowing, porous and with highly internal moist content (being not possible to be characterized as a paste). The objective of this research is the analysis of the soy milk residue drying using three types of dryers: conventional spouted bed dryer, rotary cylindrical dryer assisted by microwaves and microwave oven drier. The drying in the spouted bed was made in batch process while, in the rotary cylindrical dryer with application of microwaves it was conducted continuously. The use of inert material inside the dryer was necessary in both cases: in the spouted bed dryer, the inert that showed better fluid-dynamic with the Okara was the polypropylene, while in the rotary dryer the inert that showed better transport monitoring of Okara particles was the polystyrene. The same procedure was followed to prepare the Okara for both equipments. The variables analyzed in the spouted bed dryer were: drying air temperature, ratio between the air flow rate and minimum spout flow rate and time of material shredding; in the rotary cylindrical dryer assisted by microwaves, the independent variables were: drying air temperature and flow rate and microwave power. For both dryers, an experimental factorial design, 2³, was applied and the responses analyzed were: Okara moisture content for a fixed drying time and parameters of Page model for the drying kinetics (the last for the spouted bed dryer only). Operational performance was also determined for both dryers by productivity and process thermal efficiency. Physical properties were determined for Okara before drying and after the dryer exit. The microwave oven dryer was used to determine the drying kinetics, controlling the same variables as in the rotary cylindrical dryer. / Doutorado / Engenharia de Processos / Doutor em Engenharia Química

Orientador: Edison Bittencourt / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-09T15:54:46Z (GMT). No. of bitstreams: 1 Vieira_AdalenaKennedy_D.pdf: 3876527 bytes, checksum: 24d0e24d715ff4f8fefc97ffd5a4e1b9 (MD5) Previous issue date: 2007 / Resumo: Em todo o mundo inicia-se uma nova era. A qualidade de vida e segurança dependem cada vez mais da capacidade de toda humanidade em resolver problemas cada dia mais complexos e demorados. Com o advento da comunicação e a globalização o tempo cada vez mais torna-se um bem escasso e precioso. Os materiais semicondutores usados para desempenhar as funções lógicas e de memória de alta velocidade utilizados no processamento de informação e hardware de armazenagem são os materiais mais difíceis de serem produzidos. Com relação a estes materiais nesta indústria, a capacidade de transformação é enorme, pois o que era o equipamento mais moderno num piscar de olhos passa a ser obsoleto. Assim, avanços nas áreas de tecnologias de informação estão relacionados a avanços em semicondutores e conseqüentemente em materiais. Conforme aumenta a funcionalidade dos chips, aumentam também substancialmente as alternativas para melhorá-los, porque a demanda por este produto não para de crescer e aumenta exponencialmente com relação à população que os consome. Para satisfazer à demanda por densidades mais elevadas nos chips, serão necessárias novas tecnologias de empacotamento e interconexão e a integração destas com toda a tecnologia microeletrônica. É, pois, neste contexto que se insere o presente trabalho. Um dos objetivos principais foi a obtenção de uma cobertura que pode ser um início de uma nova tecnologia para o desenvolvimento de um ¿microchip¿ sobre materiais poliméricos. É o nascer de uma nova era na área de materiais e dispositivos eletro-eletrônicos. Para a indústria nacional e para o Pólo Industrial de Manaus, talvez seja uma tecnologia de ponta com um material mais barato e acessível a todos. Para a execução deste trabalho foram feitos planejamentos experimentais visando melhorar as condições ¿ótimas¿ para o recobrimento por spin coating. Através da deposição de filmes de óxido de silício sobre lentes oftálmicas produziu-se os filmes de óxido de sílicio que foram depositados através de um reator de Microwave Electron Cyclotron Resonance, com o auxílio de um campo magnético em um plasma constituído por uma mistura de argônio, oxigênio e silana. Esse método de deposição é conhecido como ¿ECR¿. A estrutura dos filmes de óxidos de silício depositados foi estudada através de transmitância na região do visível. A morfologia das superfícies recobertas com os filmes foi analisada por Microscopia Óptica e também através de Microscopia de Varredura Eletrônica (MEV). Os resultados de transmitância para os filmes mostram que na medida em que a camada é depositada são formadas estruturas que melhoram a proteção oferecida pela cobertura. As micrografias ópticas revelaram que as lentes sofrem um ¿stress¿ em razão da diferença do coeficiente de expansão entre os dois materiais. As micrografias de MEV mostraram, também, que as superfícies melhores protegidas pelo óxido de silício são as obtidas através de fabricação e moldagem feita com resina acrílica, como comprovam os testes anti-risco. A análise de ângulo de contato do filme mostrou que a cobertura serve como camada aderente ao polímero, mas não como camada hidrofóbica, pois o polímero ainda assim absorve água. As medidas de parâmetros S encontradas foram tiradas com base nas características dos protótipos ensaiados e de acordo com as limitações da resposta em frequência do equipamento utilizado para o ensaio. O resultado dos ensaios também não pode ser melhor detalhado, pois o material foi depositado sem a expectativa dessa finalidade inicialmente. Podemos, entretanto, comprovar que a metodologia é viável e a partir do mesmo principio poderão ser desenvolvidas diversas utilidades para essa técnica inovadora / Abstract: A new era has begun all around the world. The quality of life and health depends more and more on the human capacity of resolving problems that are becoming longer and more complex day by day. As communication and globalization advance, time becomes scarcer and more precious. The semiconductor materials which are used to activate the logical functions, the high velocity memory used in processing information and the storage ¿hardware¿ are the most difficult materials produced in this area. The ability to change is enormous, due to the fact that what was considered the most modern equipment has become obsolete in the blink of an eye. Consequently, the advances in the areas of technological information are related to the advances in those in semiconductors and as result in materials. As the use of the ¿chip¿ increases, the alternatives also become varied, with the objective of improving the chip¿s functions, this is because the demand for the product is getting stronger, increasing, when referring to the population, the search for these products. This study has achieved a covering which can be perceived as a beginning to New Technology, in order to create a ¿microchip¿ with polymeric materials. It¿s the start of a new era when dealing with the area of electro-electronic materials and models. For the National Industry and for Manaus¿ Industry Pole, it might be viewed as cheaper and more accessible technology for all. An adaptation of a reactor has become full filled that produces electronic components for a deposition on a polymer substratum (ophtalmic lenses) for the attainment of a treatment of alternative anti-reflexive. This methodology is used in the industry of electronic components, more known as "chip". In this work they had been experiment design facts to optimize the excellent conditions for the covering for spin coating. Through the deposition of silicon oxide films on ophtalmic lenses one produced the silicon oxide films that had been deposited through a reactor of Microwave Electron Cyclotron Resonance, with aid of a magnetic field, a plasma constituted by a mixture of argon, oxygen and silane.This method of deposition is known as "ECR". The structure of deposited the silicon oxide films was studied through transmittance in the region of the visible light. The morphology of the surfaces re-covered with the films was analyzed by Optic Microscopy and also through Scanning Electron Microscopy Analysis (MEV). The results of transmittance for the films show that the measure where the layer is deposited form structures that improve the protection offered for the covering. The MEV micrographs had shown, also, that the surfaces best protection for silicon oxide are the gotten ones through acrylic resin, as they prove the anti-risk tests. The analysis of angle of contact of the film showed that the covering does not serve as hydrophobic layer. The measurements of parameter S which were found, were based on characteristics of the resulted prototypes and the answer limitations regarding the frequency of the equipment used for these readings. Moreover, the overall results can¿t be better detailed due to the fact that the material wasn¿t deposited with this objective. The methodology is viable, and based on the same principles it can develop diverse utilities to this innovate technique / Doutorado / Ciencia e Tecnologia de Materiais / Doutor em Engenharia Química

In recent years a new class of materials, the metamaterials, has emerged in the scientific community. The use of these materials makes possible to achieve unique electromagnetic properties, such as the negative refractive index. Today there exist several applications that take advantage of these special properties, such as sensors, antennas and invisibility cloaks, aiming at improving their intrinsic characteristics. Based on these considerations, this project aims at developing metamaterials structures to control the radiation properties of antennas in the microwave range, such as gain and directivity. More specifically, it was also chosen chiral metamaterials, mainly due to the phenomenon of electromagnetic field rotation which opens the possibility to control efficiently the radiation properties of antennas. In addition, chiral metamaterials, which have proved to be a more attractive alternative to obtain negative or zero refractive index, enable a greater degree of freedom in the design of different structures. This work encompasses all different phases of the structure design, namely: project, computational modeling, fabrication, and characterization of the proposed structures. We show improvements for the gain that in some cases reaches more than the double of the conventional monopole antenna gain and for the return loss parameter, which reaches minimum values. We also could maintain good efficiency and improve the input impedance matching. Finally, it is worth mentioning that this new technology also has the great potential to be applied in the telecommunication devices, particularly to improve communications based on antennas. / Nos últimos anos uma nova classe de materiais, os metamateriais, emergiu na comunidade científica. O uso desses materiais torna possível alcançar propriedades eletromagnéticas singulares, como o índice de refração negativo. Hoje existem vastas aplicações que usufruem destas propriedades especiais, como os sensores, mantas de invisibilidade e antenas, onde se procura o aperfeiçoamento de suas características intrínsecas. Com base nestas considerações, este projeto buscou desenvolver estruturas metamateriais para controle das propriedades de radiação de antenas na faixa de micro-ondas, tais como diretividade e ganho. Mais especificamente, foram utilizados os metamateriais quirais, principalmente devido ao fenômeno de rotação do campo eletromagnético que abre a possibilidade de controle mais eficiente das propriedades de radiação de antenas. Além disso, os metamateriais quirais, por se mostrarem uma alternativa mais atraente para se obter meios com índice de refração zero ou negativo, possibilitam um maior grau de liberdade no projeto de diferentes estruturas. Este trabalho contempla, ainda, todas as etapas de projeto de tais estruturas, quais sejam: projeto, modelagem computacional, fabricação, e caracterização das estruturas. Mostramos melhorias para o ganho que, em alguns casos, chega a mais do que o dobro do ganho da antena monopolo convencional e para o parâmetro de perda de retorno, que atinge valores mínimos. Nós também mantivemos uma boa eficiência e melhoramos o casamento de impedância de entrada. Finalmente, vale salientar que essa nova tecnologia também apresenta grande potencial de ser aplicada em dispositivos de telecomunicações, com o intuito de aprimorar a comunicação baseada em antenas.

Dans le contexte de la bioraffinerie végétale, notamment pour la production du bioéthanol, le prétraitement est une étape incontournable pour réduire la récalcitrance et accroitre la réactivité de la biomasse lignocellulosique vis-à-vis des procédés de conversion enzymatique/biologique. La récalcitrance est principalement due à la présence de la lignine et à la forme cristalline de la cellulose. Le but de tout prétraitement de la biomasse est d’altérer la structure du matériau lignocellulosique pour accroitre l’accessibilité de la cellulose et les hémicelluloses aux enzymes. Les prétraitements conventionnels, comportent généralement des étapes agressives, utilisant des réactifs nocifs, en exposant la matière à des températures et pressions élevées et ce pour de longues durées. Dans ce travail, nous avons développé un procédé original de délignification des résidus de colza, en combinant des prétraitements physiques (ultrasons (US), microondes (MO) et électrotechnologies (CEP, DEHT)) aux prétraitements chimiques conventionnels (organosolv, alcalin). Ce couplage a permis d’améliorer les performances du procédé en terme de rendement d’extraction des phytomélanines (jusqu’à 40 % de gain) dans le cas des pellicules de colza et de rendement de délignification (plus que 2 fois la performance d’un procédé chimique seul) dans le cas des menues pailles de colza tout en réduisant pour la plupart des technologies étudiées la sévérité du procédé global. En termes qualitatifs, la caractérisation des pâtes cellulosiques par microscopie électronique a révélé des modifications au niveau du tissu végétal représentées par l’apparition de pores au niveau des pellicules de colza et une déstructuration des fibres des menues pailles de colza traitées induisant de meilleurs rendements d’hydrolyse enzymatique.Cependant, une perte des sucres de la cellulose et des hémicelluloses a été observée avec les prétraitements physiques. L’analyse structurale des lignines récupérées a confirmé la contamination par ces sucres et a permis d’identifier certains mécanismes d’action tels que la recondensation de la lignine sous l’effet des ultrasons et le clivage des ponts férulates sous l’action des décharges électriques à haute tension. Une étude préliminaire concernant la conception d’adhésifs «verts » éco-sourcés a été menée à partir des fractions de phytomélanines isolées par les procédés étudiés. Enfin, une étude de l'incidence des technologies innovantes en terme de performances technico-économiques a été réalisée pour permettre d'envisager une éventuelle suite à plus grande échelle et il a été conclu que l’étape physique permettait de réduire l’écart entre les coûts et les revenus de l’implantation d’une telle bioraffinerie. / In the context of plant biorefinery, especially for bioethanol production, pretreatment step is important to reduce the recalcitrance of lignocellulosic biomass and to increase the reactivity towards enzymatic / biological conversion processes. Recalcitrance is mainly due to the presence of lignin and crystalline cellulose. The goal of any pretreatment of biomass is to alter the structure of the lignocellulosic material in order to increase the accessibility of cellulose and hemicellulose to the enzymes. Conventional pretreatments include aggressive steps, using harmful reagents and exposing the material to high temperatures and pressures for long periods. In this work, we developed a new process for delignification of rapeseed residues, combining physical pretreatments (ultrasounds (US), microwaves (MW)) and electrotechnologies (PEF, HVED)) to conventional chemical pretreatments (Organosolv, alkaline). This coupling has improved the process in terms of phytomelanin extraction yield (up to 40 % gain) in the case of rapeseed hulls and delignification efficiency (more than 2 times more efficient than the chemical process performed alone) in the case of rapeseed straw while reducing for most studied technologies the severity of the overall process. Characterization through electron microscopy revealed changes in plant tissue represented by the appearance of pores in the treated rapeseed hulls and fiber breakdown of treated rapeseed straw inducing better enzymatic hydrolysis performance. However, loss of sugars from cellulose and hemicellulose was observed with physical pretreatments. Analysis of the recovered lignins allowed us to observe lignin modifications during physical treatments such as recondension reactions in presence of ultrasounds and cleavage of ferulates bridges with high-voltage electrical discharges. Then the formulation of « eco-sourced » adhesives from phytomélanins extracted by the previous studied processes was attempted. Finally, a study of the impact of innovative technologies in terms of technical and economic performances was carried out to consider a scale-up of these technologies. It was concluded that physical step enhanced the profitability of this biorefinery.

Ces dernières années, la recherche de solutions au problème de l'élimination de déchets polymères, notamment les déchets issus de pneumatiques qui posent de graves problèmes environnementaux, connait un développement croissant. Dans ce contexte, ce projet de recherche a pour objectif de contribuer au développement et à la promotion de solutions innovantes qui font appel aux connaissances développées dans les domaines des nanotechnologies, de la science et l’ingénierie des matériaux nouveaux et du génie des procédés et des produits. Il s’agit plus particulièrement de d’étudier la possibilité de valoriser les déchets issus de pneumatiques en les utilisant comme matière première (en tant que agents de renfort ou agents de modification de la résistance aux chocs) pour l'élaboration de matériaux nanostructurés. Ce travail met l'accent sur l'étude des mélanges de polyéthylène haute densité (PEHD) contenant des particules d’argile (dispersées à l'échelle du nanomètre) et des déchets de caoutchouc issus de pneumatiques usagés (ou Ground Rubber Tire ou GRT). Il est attendu que ce matériau présente des propriétés typiques des mélanges de polymères appelés Vulcanisats Thermoplastiques (TPVs), résultant de la vulcanisation dynamique de la phase de caoutchouc pendant le traitement à l'état de fondu (extrusion). Dans le système étudié, la matrice est le PEHD et la phase dispersée de la poudrette de pneu, préalablement dévulcanisée par micro-ondes. L'argile dispersée dans la phase de la matrice, agit comme un agent compatibilisant entre les phases du mélange et comme agent de renforcement, apportant une amélioration des propriétés mécaniques des matériaux préparés. La caractérisation des mélanges met l'accent sur leur morphologie et leur structure ainsi que sur leurs propriétés rhéologiques, thermiques et mécaniques. Une étude approfondie de l'évolution de la morphologie du mélange au cours de l’extrusion a été effectuée car ce paramètre est la clé pour optimiser le procédé et obtenir les meilleures propriétés pour le matériau final. Ceci représente la contribution plus importante de ces travaux de recherche. / The main objective of this work was the production of dynamically revulcanized blends containing HDPE and GTR devulcanized by microwaves. It comes against a big global problem which is the waste disposal of vulcanized elastomers, especially tires, which bring with them serious environmental and public health problems, since these materials require long periods of time to degrade naturally due to their structure of cross-linkings, and the presence of stabilizers and other additives in its formulation. A way of using the GTR that has been widely studied by researchers is as polymer blends in which one of the phases is a thermoplastic polymer. In this context, the role of elastomers devulcanization is to increase the interaction between raw and recycled material, reducing the degradation of properties of the finished product with its incorporation and making it possible the increase of the recycled rubber amount in the compound recycled rubber/thermoplastic. The devulcanization transformes devulcanized elastomer into a fluid material, allowing a better control of the particle size during the mixing process of the blend by breaking processes in the application of high shear rates. In addition, by becoming a fluid material, it is possible the incorporation of a higher amount of elastomer to the thermoplastic without great damage to its processability. However, the literature does not have works in which the study of the processing parameters of dynamically revulcanized blends containing devulcanized elastomer, as well as the influence of addition of clays from different shapes (lamellar and tubular) on their final properties, especially on rheological properties, which sets out the present work. Summarizing, this work aims to propose a possible solution to the problem of solid waste disposing by producing a dynamically revulcanized blend containing HDPE and GTR devulcanized by microwaves, in addition to decrease some gaps observed currently in the literature from the obtained results.

Les matériaux III-N sont présents dans la vie quotidienne pour des applications optoélectroniques (diodes électroluminescentes, lasers). Les propriétés remarquables du GaN (grand gap, grand champ de claquage, champ de polarisation élevé, vitesse de saturation des électrons importante…) en font un candidat de choix pour des applications en électronique de puissance à basse fréquence, mais aussi à haute fréquence, par exemple en gamme d'ondes millimétriques. L’enjeu de ce travail de thèse consiste à augmenter la fréquence de travail des transistors tout en maintenant une puissance élevée. Pour cela, des hétérostructures HEMTs (High Electron Mobility Transistors) sont développées et les épaisseurs de cap et de barrière doivent être réduites, bien que ceci soit au détriment de la puissance délivrée. Une étude sera donc menée sur l’influence des épaisseurs de cap et de barrière ainsi que le type de barrière (AlGaN, AlN et InAlN) de manière à isoler les hétérostructures offrant le meilleur compromis en termes de fréquence et de puissance. De plus, les moyens mis en œuvre pour augmenter la fréquence de travail entrainent une dégradation du confinement des électrons du canal. De manière à limiter cet effet, une back-barrière est insérée sous le canal. Ceci fera l’objet d’une deuxième étude. Enfin, une étude de la passivation de surface des transistors sera menée. La combinaison des ces trois études permettra d’identifier la structure optimale pour délivrer le plus de puissance à haute fréquence (ici à 40 GHz). / Nitride based materials are present in everyday life for optoelectronic applications (light emitting diodes, lasers). GaN remarkable properties (like large energy band gap, high breakdown electric field, high polarization field, high electronic saturation velocity…) make it a promising candidate for low frequency power electronic applications, but also for high frequency like microwaves range for example. The aim of this work is to increase the transistors working frequency by keeping a high power. To do this, high electron mobility transistor heterostructures are developed, and cap and barrier thicknesses have to be reduced, although it is detrimental for a high power. A first study deals with the influence of cap and barrier thicknesses as well as the type of barrier (AlGaN, AlN and InAlN), in order to isolate heterostructures offering the best compromise in terms of power and frequency. Moreover, the means implemented to increase the working frequency lead to electron channel confinement degradation. In order limit this effect, a back-barrier is added underneath the channel. It will be the subject of the second study. Finally, a transistor surface passivation study will be led. The combination of those three parts will allow identifying the optimum structure to deliver the highest power at high frequency (here at 40 GHz).

Avec plus de 170 millions de personnes infectées, l'infection par le virus de l'hépatite C (VHC) représente une des premières infections virales dans le monde. La recherche et la mise au point de nouvelles molécules, capables de traiter de cette maladie sont donc d'une grande importance. Dans ce contexte et sur la base de résultats préliminaires obtenus avec des dinucléotides phosphoramidates GpC inhibant l'initiation de la réplication par la polymerase NS5B, nous avons conçu des inhibiteurs de seconde génération de type dimère de PNA (Peptide nucleic Acid). Nous présentons dans ce manuscrit la mise au point d'une méthode de synthèse originale de monomères et dimères de PNA, basée sur l'utilisation d'une réaction de Ugi à quatre composants (U-4CR). Cette méthode par U-4CR offre une grande variabilité de structures et séquences (G, A, C, T, U) en un nombre limité d'étapes, de plus la combinaison avec une activation micro-ondes permet d'augmenter l'efficacité et de réduire considérablement les temps de réaction. Cette stratégie a été appliquée en série dimère de PNA et en série chimère PNA-ARN. / With more than 170 millions people chronically infected, hepatitis C virus represents one of the major viral infections in the world. The research and development of novel antiviral is hence of great importance. In this context and on the basis of preliminary results obtained with dinucleotide phosphoramidates GpC inhibiting the initiation of replication of the NS5B polymerase, we designed a second generation of inhibitors type PNA dimers (Peptides Nucleic Acid). We describe in this manuscript the development of an original strategy to synthesize PNA monomers and dimers based on the use of the well-known Ugi four component reactions (U-4CR). This method allows a great structural variability in a limited number of steps. More, combining this efficient tool with microwaves irradiations allows an increase of the efficiency and a dramatic acceleration of the reaction time. This strategy was applied in PNA dimers series and PNA-RNA chimera series.