Os resíduos sólidos urbanos (RSU) são particularmente difíceis de gerenciar por se tratar de um resíduo muito heterogêneo em sua composição (resíduos domésticos, de construção civil, de poda de árvore, entre outros). Com isso torna-se necessário o conhecimento das atuais tecnologias de tratamento de resíduos, para que busquem soluções ambientalmente adequadas, economicamente viáveis, socialmente justas e politicamente aceitáveis. Com base nessa premissa e com a necessidade de se estudar novas fontes renováveis de energia na busca por combustíveis alternativos aos combustíveis fósseis, a utilização de resíduos de poda de árvore como fonte energética apresenta aspectos benéficos ao país, desde que viável econômica e tecnicamente. Assim este trabalho analisa a atual situação da destinação dos resíduos de poda de árvore, e apresenta algumas alternativas para seu aproveitamento energético e não energético. Sendo o objetivo principal desta dissertação avaliar o potencial de utilização dos resíduos de poda de árvore para o seu aproveitamento energético por meio dos processos de adensamento de biomassa (peletização e briquetagem), utilizando como base o caso do campus da Universidade de São Paulo na capital. Nos ensaios de peletização foi possível obter pellets com densidade energética elevada, entre 6 GJ/m3 e 8 GJ/m3, o que corresponde a uma densidade energética de 6 a 9 vezes maior que a da poda de árvore in natura. Os briquetes apresentaram uma densidade energética entre 5 GJ/m3 a 6 GJ/m3, ou seja, uma densidade energética de 5 a 6 vezes maior que da poda de árvore in natura. Entretanto os valores obtidos de durabilidade mecânica dos briquetes foram considerados insatisfatórios nas condições estudadas, ao contrário dos pellets, que apresentaram elevados valores. Neste estudo o processo de peletização se mostrou mais viável tecnicamente do que o de briquetagem, visto que os pellets de resíduo de poda de árvore garantiram uma densidade energética elevada e boa resistência mecânica. / Municipal solid wastes (MSW) are particularly difficult to manage because it is a very heterogeneous waste in its composition (household waste, construction, tree pruning, etc). It becomes more than necessary knowledge of current waste treatment technologies, to seek environmentally adequate solutions, economically viable, socially fair and politically acceptable. Based on these assumptions and the need to study new renewable energy sources in the search for alternative fuels to replace fossil fuels, the use of tree pruning waste as an energy source have beneficial aspects to the country, since economic viable and technically. So this paper analyzes the current situation of final disposal of tree pruning waste, and presents some alternatives for its energy and non-energy use. Since the main objective of this work is to evaluate the potential use of tree pruning waste for their energy application through biomass densification processes (pelletizing and briquetting), based on the case of the campus of the University of São Paulo in capital. In the pelleting tests it was possible to obtain pellets with high energy density between 6 GJ/m3 and 8 GJ/m3, which corresponds to an energy density of 6 to 9 times greater than that of tree pruning in nature. The briquettes had an energy density of between 5 GJ/m3 6 GJ/m3, in other words a power density of 5 to 6 times that of tree pruning in nature. However the values obtained from mechanical durability of briquettes were found to be unsatisfactory under the conditions studied, unlike pellets, they showed high values. In this study, the pelleting process is technically more feasible than briquetting. Since the tree pruning waste pellets ensured a high energy density and good mechanical strength.

Os resíduos sólidos urbanos (RSU) são particularmente difíceis de gerenciar por se tratar de um resíduo muito heterogêneo em sua composição (resíduos domésticos, de construção civil, de poda de árvore, entre outros). Com isso torna-se necessário o conhecimento das atuais tecnologias de tratamento de resíduos, para que busquem soluções ambientalmente adequadas, economicamente viáveis, socialmente justas e politicamente aceitáveis. Com base nessa premissa e com a necessidade de se estudar novas fontes renováveis de energia na busca por combustíveis alternativos aos combustíveis fósseis, a utilização de resíduos de poda de árvore como fonte energética apresenta aspectos benéficos ao país, desde que viável econômica e tecnicamente. Assim este trabalho analisa a atual situação da destinação dos resíduos de poda de árvore, e apresenta algumas alternativas para seu aproveitamento energético e não energético. Sendo o objetivo principal desta dissertação avaliar o potencial de utilização dos resíduos de poda de árvore para o seu aproveitamento energético por meio dos processos de adensamento de biomassa (peletização e briquetagem), utilizando como base o caso do campus da Universidade de São Paulo na capital. Nos ensaios de peletização foi possível obter pellets com densidade energética elevada, entre 6 GJ/m3 e 8 GJ/m3, o que corresponde a uma densidade energética de 6 a 9 vezes maior que a da poda de árvore in natura. Os briquetes apresentaram uma densidade energética entre 5 GJ/m3 a 6 GJ/m3, ou seja, uma densidade energética de 5 a 6 vezes maior que da poda de árvore in natura. Entretanto os valores obtidos de durabilidade mecânica dos briquetes foram considerados insatisfatórios nas condições estudadas, ao contrário dos pellets, que apresentaram elevados valores. Neste estudo o processo de peletização se mostrou mais viável tecnicamente do que o de briquetagem, visto que os pellets de resíduo de poda de árvore garantiram uma densidade energética elevada e boa resistência mecânica. / Municipal solid wastes (MSW) are particularly difficult to manage because it is a very heterogeneous waste in its composition (household waste, construction, tree pruning, etc). It becomes more than necessary knowledge of current waste treatment technologies, to seek environmentally adequate solutions, economically viable, socially fair and politically acceptable. Based on these assumptions and the need to study new renewable energy sources in the search for alternative fuels to replace fossil fuels, the use of tree pruning waste as an energy source have beneficial aspects to the country, since economic viable and technically. So this paper analyzes the current situation of final disposal of tree pruning waste, and presents some alternatives for its energy and non-energy use. Since the main objective of this work is to evaluate the potential use of tree pruning waste for their energy application through biomass densification processes (pelletizing and briquetting), based on the case of the campus of the University of São Paulo in capital. In the pelleting tests it was possible to obtain pellets with high energy density between 6 GJ/m3 and 8 GJ/m3, which corresponds to an energy density of 6 to 9 times greater than that of tree pruning in nature. The briquettes had an energy density of between 5 GJ/m3 6 GJ/m3, in other words a power density of 5 to 6 times that of tree pruning in nature. However the values obtained from mechanical durability of briquettes were found to be unsatisfactory under the conditions studied, unlike pellets, they showed high values. In this study, the pelleting process is technically more feasible than briquetting. Since the tree pruning waste pellets ensured a high energy density and good mechanical strength.

O presente estudo teve como objetivo geral avaliar o efeito da aplicação do tratamento térmico torrefação - com diferentes intensidades em resíduos florestais de Eucalyptus grandis e bagaço de cana-de-açúcar como proposta para a melhoria de suas características visando o uso como combustível. As biomassas foram submetidas a torrefação laboratorial compreendendo temperaturas de 250 e 280°C, além dos tempos de residência na temperatura de tratamento de 0,5 e 2,0 horas. Em seguida, para a avaliação do efeito do tratamento térmico nos materiais, as biomassas originais e as torradas foram submetidas às seguintes avaliações laboratoriais: composição química (teor de lignina e extrativos), composição imediata através da determinação dos teores de materiais voláteis, carbono fixo e cinzas, poder calorífico, termogravimetria, granulometria e friabilidade. Os resultados mostraram que existe influência da temperatura no rendimento das biomassas analisadas. De modo geral, quanto maior a temperatura do tratamento térmico, menor o rendimento obtido e, consequentemente, maior a perda de massa para ambas as biomassas. Houve incremento no teor de carbono fixo, redução do teor de materiais voláteis e aumento no teor de cinzas para ambas as biomassas. Os dois materiais apresentaram, de modo geral, comportamentos muito semelhantes em relação a composição química. Foi observado que o aumento da intensidade do tratamento térmico ocasionou tendência de aumento no teor de lignina dos materiais. Observou-se também que a torrefação exerceu influência na redução da granulometria e aumento da friabilidade tanto dos resíduos florestais de Eucalyptus grandis quanto no bagaço de cana-de-açúcar. / The objective of this study was to analyze the effect of the heat treatment application, with different intensities in forest residues of Eucalyptus grandis and sugar cane bagasse in order to improve its features to use as fuel. The biomasses were subjected to laboratory heat treatments comprising temperatures of 250 and 280°C during 0,5 and 2,0 hours. After that, the original and treated biomasses were subjected to laboratory tests including: chemical composition (lignin and extractives), immediate composition by determining the levels of volatiles, fixed carbon and ash, calorific value, thermogravimetry, grain size and friability. The results show that there is an influence of temperature on the yields of biomass analyzed. In general, the treatments with higher temperatures present lower yield. There was an increase in fixed carbon content, reducing the volatile components and ash content increased for both biomasses. The two materials showed very similar behavior on chemical composition. The increase of the intensity of heat treatment caused an increase in lignin content of the materials. It was possible to observe that the heat treatment presented an influence on particle size reduction and increases friability in both the forest residues of Eucalyptus grandis and sugar cane bagasse.

O presente estudo teve como objetivo geral avaliar o efeito da aplicação do tratamento térmico torrefação - com diferentes intensidades em resíduos florestais de Eucalyptus grandis e bagaço de cana-de-açúcar como proposta para a melhoria de suas características visando o uso como combustível. As biomassas foram submetidas a torrefação laboratorial compreendendo temperaturas de 250 e 280°C, além dos tempos de residência na temperatura de tratamento de 0,5 e 2,0 horas. Em seguida, para a avaliação do efeito do tratamento térmico nos materiais, as biomassas originais e as torradas foram submetidas às seguintes avaliações laboratoriais: composição química (teor de lignina e extrativos), composição imediata através da determinação dos teores de materiais voláteis, carbono fixo e cinzas, poder calorífico, termogravimetria, granulometria e friabilidade. Os resultados mostraram que existe influência da temperatura no rendimento das biomassas analisadas. De modo geral, quanto maior a temperatura do tratamento térmico, menor o rendimento obtido e, consequentemente, maior a perda de massa para ambas as biomassas. Houve incremento no teor de carbono fixo, redução do teor de materiais voláteis e aumento no teor de cinzas para ambas as biomassas. Os dois materiais apresentaram, de modo geral, comportamentos muito semelhantes em relação a composição química. Foi observado que o aumento da intensidade do tratamento térmico ocasionou tendência de aumento no teor de lignina dos materiais. Observou-se também que a torrefação exerceu influência na redução da granulometria e aumento da friabilidade tanto dos resíduos florestais de Eucalyptus grandis quanto no bagaço de cana-de-açúcar. / The objective of this study was to analyze the effect of the heat treatment application, with different intensities in forest residues of Eucalyptus grandis and sugar cane bagasse in order to improve its features to use as fuel. The biomasses were subjected to laboratory heat treatments comprising temperatures of 250 and 280°C during 0,5 and 2,0 hours. After that, the original and treated biomasses were subjected to laboratory tests including: chemical composition (lignin and extractives), immediate composition by determining the levels of volatiles, fixed carbon and ash, calorific value, thermogravimetry, grain size and friability. The results show that there is an influence of temperature on the yields of biomass analyzed. In general, the treatments with higher temperatures present lower yield. There was an increase in fixed carbon content, reducing the volatile components and ash content increased for both biomasses. The two materials showed very similar behavior on chemical composition. The increase of the intensity of heat treatment caused an increase in lignin content of the materials. It was possible to observe that the heat treatment presented an influence on particle size reduction and increases friability in both the forest residues of Eucalyptus grandis and sugar cane bagasse.

Bien que proposant des avantages importants par rapport à d'autres matériaux, les céramiques présentent un défaut récurrent, qui est leur plus ou moins grande fragilité due à des défauts de structure ou à des impuretés dans les réseaux structuraux. On s’affranchit de ces contraintes en améliorant la pureté des matériaux de base, en maîtrisant mieux les processus de fabrication, en les renforçant et en nanostructurant le matériau. C’est ce qui a donné naissance aux méthodes chimiques d’élaboration dites de « Bottom-up » qui reprennent le schéma de principe de la conception de la céramique naturelle en s’adaptant à la démarche des chimistes : des briques élémentaires représentant une architecture moléculaire sont assemblées pour former un composé macromoléculaire dont la composition est contrôlée à l’échelle atomique. Ce composé est mis en forme, durcit pour être transformé par cuisson en une céramique dont la composition est directement liée à la structure moléculaire des briques. Cette démarche est à l’origine de la voie dite des « polymères précéramiques ». Cette voie chimique s’adapte aux exigences des domaines de l’énergie. Notamment et afin d’exploiter et de saisir les opportunités que constituent l’apparition de nouveaux besoins en matériaux et/ou l’établissement de cahiers des charges stricts au regard des propriétés des matériaux dans ce domaine, la présente étude a pour objet d’élaborer des matériaux à base de BN comme les composites à renforts fibreux, les nanocomposites et les mousses.Après une introduction générale, le chapitre 1 décrit l’état de l’art de BN. Il s’intéresse à la littérature sur les propriétés des différentes formes du BN. La voie PDCs est détaillée et son application à l’élaboration du h-BN. Les différents types de précurseurs et de polymères sont décrits et l’accent est mis sur le borazine et le polyborazylène. La dernière partie concerne l’élaboration des composites à renforts fibreux, les nanocomposites et les mousses à base de BN qui sont considérés.Le chapitre 2 s’intéresse à l’élaboration de C/BN composites à partir de polyborazylènes qui est un projet de recherche sur ITER. Après un rappel sur le contexte de CEA, les différentes étapes liées au procédé d’élaboration des composites sont décrites et étudiées à l’aide d’outils de caractérisation comme la RMN solide,TGA, XRD et SEM. Le chapitre 3 s’intéresse à des nanocomposites qui se caractérisent par des phases nanocristallines de nitrure métallique parmi le nitrure de titane, de zirconium et d’hafnium dispersés dans une matrice de BN faiblement cristallisée. L’accent est mis sur la chimie moléculaire et sur la synthèse de polymétalloborazines qui permettent de conduire par pyrolyse à la formation directe de ces nanocomposites par croissance in-situ de la phase nanocristalline dans la matrice BN. Une étude préliminaire sur la possibilité de mettre en forme les polyméres en vue d’élaborer des structures massives nanocomposites est abordée.Le chapitre 4 se consacre à deux procédés de préparation de mousses. Le premier procédé qui combine la voie PDCs à la chimie intégrative vise à élaborer des mousses BN à porosité hiérarchisée. Le second procédé consiste à mélanger PMMA avec polyborazylènes pour subir des étapes de compactage et de pyrolyse générant des mousses. Pour ces deux types de matériaux, des mesures texturales comme BET et la porosimétrie mercure sont entreprises.Une conclusion générale termine le manuscrit. Elle fait un rappel des travaux entrepris dans chacun des trois chapitres et donne des perspectives liées aux trois types de matériau étudiés pendant la thèse. / Energy developments have brought hexagonal boron nitride-based materials increasing interest for future materials and technologies. The objective of this thesis concerns the preparation of BN shapes for energy applications including fiber-reinforced BN composites, BN-based nanocomposites and BN foams. Fiber-reinforced BN composite and BN nanocomposites display potential as tiles for protection limiters for the Ion Cyclotron Range Frequency antennas in fusion nuclear reactors. Porous BN materials have interests as host material for hydrogen storage and as catalyst supports. The Polymer-Derived Ceramics route which offers new preparation opportunities in chemistry and ceramic sciences is applied to manufacture shaped BN-based materials.Firstly, in the context of C/BN composite, polyborazylene vacuum-assisted infiltration and pyrolysis process was successfully introduced. We focused on the design, elaboration and properties of the C/BN composite through the study of the (1) synthesis and polymerization of borazine, (2) the polyborazylene-to-boron nitride conversion, (3) the morphological texture and mechanical properties of derived C/BN composites. We firstly demonstrated that it is possible to obtain dense-derived C/BN composites (density: 1.773 g cm-3, open porosity: 5.09%) by tuning the viscosity of polyborazylene in the infiltration process. SEM observation presented a very strong bonding between fibers and matrix. TGA under air analysis confirmed the improved oxidation resistance property of C/BN composite compared with C fiber.Secondly, we investigated the design, processing, and properties of transition metal-containing boron nitride nanocomposites from polymetalloborazine. With proper choice of boron nitride precursor, and by controlling the B/M ratio (M = Ti, Zr, Hf), a set of representative polymetalloborazines has been prepared as precursors of nanocomposites. In the reaction of BN source with metal precursor leading to polymetalloborazines, two main mechanisms are mainly concerned: N-H and B-H units of BN percursor react with N-alkyl groups presented in metal precursors. After its pyrolysis under ammonia up to 1000 oC then nitrogen from 1000 to 1500oC, the derived nanocomposites reveal the presence of metal nitride nanocrystales with an average diameter of 6.5 nm homogeneously embedded in a poorly crystallized boron nitride matrix. A preliminary study is presented on the preparation of monolith-type nanocomposites from selected polytitanoborazines. Finally, we applied two PDCs route-based strategies to prepare hierarchically porous and micro cellular BN foams. In the first strategy, monolith-type BN foams with a hierarchical porosity were synthesized from polyborazylene using an integrative chemistry combined-based sequence set-up that consists of the impregnation of silica and carbonaceous templates followed by pyrolysis process and elimination of the template. These novel porous BN architectures display hierarchical and high porosity (76 %) with an open-cell interconnected macroporosity and a surface area up to 300 m2g-1. In the second strategy, a sacrificial processing route has been proposed to fabricate micro cellular BN foams with a porosity of 79 % from a mixture of polyborazylene and poly(methylmethacrylate) (PMMA) microbeads by warm-pressing followed by pyrolysis consisting of the burn-out of PMMA while polyborazylene is converted into BN. These novel BN foams display potential as catalyst supports and host material for hydrogen storage.

Depuis plus d’un siècle, la radiographie sur film est utilisée pour le contrôle non destructif (CND) de pièces industrielles. Avec l’introduction de méthodes numériques dans le domaine médical, la communauté du CND industriel a commencé à considérer également les techniques numériques alternatives au film. La radiographie numérique (en anglais Computed radiography -CR) utilisant les écrans photostimulables (en anglais imaging plate -IP) est une voie intéressante à la fois du point de vue coût et facilité d’implémentation. Le détecteur (IP) utilisé se rapproche du film car il est flexible et réutilisable. L’exposition de l’IP aux rayons X génère une image latente qui est ensuite lue et numérisée grâce à un système de balayage optique par laser. A basse énergie, les performances du système CR sont bonnes ce qui explique son utilisation importante dans le domaine médical. A haute énergie par contre, les performances du système CR se dégradent à la fois à cause de la mauvaise absorption de l’IP mais également de la présence de rayonnement diffusé par la pièce qui, étant d’énergie plus faible, est préférentiellement absorbée par l’IP. Les normes internationales préconisent l’utilisation d’écrans métalliques pour améliorer la réponse des systèmes CR à haute énergie. Néanmoins, la nature et l’épaisseur de ces écrans n’est pas clairement définie et la gamme des configurations possibles est large. La simulation est un outil utile pour prévoir les performances d’une expérience et déterminer les meilleures conditions opératoires. Les méthodes Monte Carlo sont communément admises comme étant les plus précises pour simuler les phénomènes de transport de rayonnement, et ainsi comprendre les phénomènes physiques en jeu. Cependant, le caractère probabiliste de ces méthodes implique des temps de calcul importants, voire prohibitifs pour des géométries complexes. Les méthodes déterministes au contraire, peuvent prendre en compte des géométries complexes avec des temps de calcul raisonnables, mais l’estimation du rayonnement diffusé est plus difficile. Dans ce travail de thèse, nous avons tout d’abord mené une étude de simulation Monte Carlo afin de comprendre le fonctionnement des IP avec écrans métalliques à haute énergie pour le contrôle de pièces de forte épaisseur. Nous avons notamment suivi le trajet des photons X mais également des électrons. Quelques comparaisons expérimentales ont pu être menées à l’ESRF (European Synchrotron Radiation Facility). Puis nous avons proposé une approche de simulation hybride, qui combine l'utilisation de codes déterministe et Monte Carlo pour simuler l'imagerie d'objets de forme complexe. Cette approche prend en compte la dégradation introduite par la diffusion des rayons X et la fluorescence dans l'IP ainsi que la diffusion des photons optiques dans l'IP. Les résultats de différentes configurations de simulation ont été comparés. / For over a century, film-based radiography has been used as a nondestructive testing technique for industrial inspections. With the advent of digital techniques in the medical domain, the NDT community is also considering alternative digital techniques. Computed Radiography (CR) is a cost-efficient and easy-to-implement replacement technique because it uses equipment very similar to film radiography. This technology uses flexible and reusable imaging plates (IP) as a detector to generate a latent image during x-ray exposure. With an optical scanning system, the latent image can be readout and digitized resulting in a direct digital image. CR is widely used in the medical field since it provides good performance at low energies. For industrial inspection, CR application is limited by its poor response to high energy radiation and the presence of scattering phenomena. To completely replace film radiography by such a system, its performance still needs to be improved by either finding more appropriate IPs or by optimizing operating conditions. Guidelines have been addressed in international standards to ensure a good image quality supplied by CR system, where metallic screens are recommended for the case of using high energy sources. However, the type and thickness of such a screen are not clearly defined and a large panel of possible configurations does exist. Simulation is a very useful tool to predict experimental outcomes and determine the optimal operating conditions. The Monte Carlo (MC) methods are widely accepted as the most accurate method to simulate radiation transport problems. It can give insight about physical phenomena, but due to its random nature, a large amount of computational time is required, especially for simulations involving complex geometries. Deterministic methods, on the other hand, can handle easily complex geometry, and are quite efficient. However, the estimation of scattering effects is more difficult with deterministic methods. In this thesis work, we have started with a Monte Carlo simulation study in order to investigate the physical phenomena involved in IP and in metallic screens at high energies. In particular we have studied separately the behavior of X-ray photons and electrons. Some experimental comparisons have been carried out at the European Synchrotron Radiation Facility. Then, we have proposed a hybrid simulation approach, combining the use of deterministic and Monte Carlo code, for simulating the imaging of complex shapes objects. This approach takes into account degradation introduced by X-ray scattering and fluorescence inside IP, as well as optical photons scattering during readout process. Different simulation configurations have been compared.