Made available in DSpace on 2016-12-08T17:19:24Z (GMT). No. of bitstreams: 1 Claudinei Franco.pdf: 6129117 bytes, checksum: 6059aaddb2af97db39be8b6299acf549 (MD5) Previous issue date: 2014-10-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The interest for improvements in tribological properties of materials, more specifically in steels with low and medium carbon content are of great importance for mechanical components life time. In this work, thermochemical treatments were carried out on ABNT 1020 and ABNT 1045 steels, in order to compare and evaluate the tribological behavior and also the phases and layers formed, to the different types of treatments which are: boronizing, nitriding and multi component boronizing (also known as duplex treatment). The specific objectives were to plan the different ways of treatment; evaluate and compare the effect of the substrate according to the microstructure, support and interface of the layers formed through the treatments; characterize the wear mechanisms for the different treatments and compare the results of both materials. The thermochemical treatments were carried out, using as basis previous works performed by the powder metallurgy research group. Boronizing and nitriding treatments were carried out by solid means, multi component boronizing treatment was performed in two ways: in the first one, boronizing was followed by nitriding (BN) and the in the second one, nitriding was followed by boronizing (NB). These duplex treatments were performed with the same conditions of time and temperature used for nitriding and boronizing treatments. Pin-on-disk sliding wear tests were performed using WC-Co (hard metal) balls as counter body. Through the test it was possible to evaluate the tribological behaviour. Friction coefficient, volume of removed material and wear mechanisms were determined. The microhardness of the formed layers was measured at the surface and on the cross section of the specimens. X-ray diffraction was used to confirm the formed compounds on nitriding, boronizing and boron-nitriding (duplex) treatments. The results showed an increase in the hardness of the surface layer and a reduction in the amount of removed material (volume) in all thermochemical treatments comparing with the condition of non-treated samples. Regarding the tribological behavior, by evaluating the thermochemically treated samples, the nitrided samples of ABNT 1020 presented the highest amount of removed material (0,078 mm3) and its hardness was 436 HV0.05. The boronized ABNT 1020 steel presented the lower amount of removed material (0,013 mm3). The boronized ABNT 1045 steel reached the highest mean hardness on the surface (1750 HV0.05) and the NB duplex treatment in this material provided the highest hardness of the formed layer, about 2270 HV0.05. / O interesse por melhorias nas propriedades tribológicas de materiais, mais específico em aços com baixo e médio teor de carbono são de grande importância para a vida útil de componentes mecânicos. Neste trabalho foram realizados diversos tratamentos termoquímicos em aços ABNT 1020 e ABNT 1045, com o objetivo de comparar e avaliar o comportamento tribológico e também as fases e camadas formadas, para as diferentes formas de tratamentos que são: boretação, nitretação e boretação multicomponente (também conhecido como tratamento duplex). Os objetivos específicos foram: planejar as formas de tratamentos; avaliar e comparar o efeito do substrato relacionado à microestrutura, ao suporte e interface das camadas formadas nos tratamentos realizados; caracterizar os mecanismos e formas de desgastes para os diversos tratamentos e comparar entre os dois materiais. Os tratamentos termoquímicos foram realizados, utilizando como base trabalhos anteriores que foram realizados no grupo de pesquisa de metalurgia do pó. Os tratamentos de boretação e nitretação foram realizados por via sólida, o tratamento de boretação multicomponente foi realizado de duas formas: na primeira foi realizada a boretação seguido de nitretação (BN) e a segunda foi a nitretação seguido de boretação (NB), nos tratamentos duplex utilizaram-se os mesmos parâmetros de boretação e nitretação. Foram realizados ensaios de desgaste por deslizamento do tipo pino sobre disco, com esferas de WC-Co (metal duro) como contra corpo. Foram avaliados: o coeficiente de atrito, o volume de material removido e os mecanismos de desgaste. A dureza da camada formada foi avaliada por microdureza na superfície e na seção transversal. Difratometria de raios-X foi utilizada para a comprovação da formação das camadas de nitretos, boretos e boro-nitretos (duplex). Os resultados mostraram melhoras principalmente na dureza da camada superficial e redução no volume de material removido, em todos os tratamentos termoquímicos, quando comparado com amostras sem tratamento. Em relação ao comportamento tribológico, avaliando as amostras tratadas termoquimicamente, as amostras nitretadas do aço ABNT 1020 foram as que apresentaram os piores resultados com volume de material removido de 0,078 mm3 e dureza de 436 HV0,05. Já a boretação no aço ABNT 1020 foi o tratamento que apresentou o melhor desempenho em volume de material removido com 0,013 mm3. O aço ABNT 1045 com tratamento de boretação apresentou a maior dureza média na superfície, com 1750 HV0,05 e o tratamento duplex NB neste mesmo material proporcionou a maior dureza na seção transversal, resultante da camada formada de nitretos-boro com 2270 HV0,05.

Made available in DSpace on 2014-12-17T14:08:46Z (GMT). No. of bitstreams: 1 AnelieseLF_DISSERT.pdf: 3198107 bytes, checksum: 808e93eb6952cb8e374d91afa53cabe1 (MD5) Previous issue date: 2011-07-01 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / This master thesis aims at developing a new methodology for thermochemical degradation of dry coconut fiber (dp = 0.25mm) using laboratory rotating cylinder reactor with the goal of producing bio-oil. The biomass was characterized by infrared spectroscopy with Fourier transform FTIR, thermogravimetric analysis TG, with evaluation of activation energy the in non-isothermal regime with heating rates of 5 and 10 ?C/min, differential themogravimetric analysis DTG, sweeping electron microscopy SEM, higher heating value - HHV, immediate analysis such as evaluated all the amounts of its main constituents, i.e., lignin, cellulose and hemicelluloses. In the process, it was evaluated: reaction temperature (450, 500 and 550oC), carrier gas flow rate (50 and 100 cm?/min) and spin speed (20 and 25 Hz) to condensate the bio-oil. The feed rate of biomass (540 g/h), the rotation of the rotating cylinder (33.7 rpm) and reaction time (30 33 min) were constant. The phases obtained from the process of pyrolysis of dry coconut fiber were bio-oil, char and the gas phase non-condensed. A macroscopic mass balance was applied based on the weight of each phase to evaluate their yield. The highest yield of 20% was obtained from the following conditions: temperature of 500oC, inert gas flow of 100 cm?/min and spin speed of 20 Hz. In that condition, the yield in char was 24.3%, non-condensable gas phase was 37.6% and losses of approximately 22.6%. The following physicochemical properties: density, viscosity, pH, higher heating value, char content, FTIR and CHN analysis were evaluated. The sample obtained in the best operational condition was subjected to a qualitative chromatographic analysis aiming to know the constituents of the produced bio-oil, which were: phenol followed by sirigol, acetovanilona and vinyl guaiacol. The solid phase (char) was characterized through an immediate analysis (evaluation of moisture, volatiles, ashes and fixed carbon), higher heating value and FTIR. The non-condensing gas phase presented as main constituents CO2, CO and H2. The results were compared to the ones mentioned by the literature. / O presente trabalho tem como objetivo o desenvolvimento de uma metodologia de degrada??o termoqu?mica da fibra do coco seco (dp = 0,25 mm) utilizando reator de cilindro rotativo em escala de laborat?rio, visando a produ??o de bio-?leo. A biomassa foi caracterizada por an?lise elementar (C, H, N), espectroscopia no infravermelho com transformada de Fourier - IVTF, an?lise termogravim?trica ATG, com avalia??o da energia de ativa??o no regime n?o isot?rmico com taxas de aquecimento de 5 e 10 oC/min, an?lise diferencial termogravim?trica - DTG, microscopia eletr?nica de varredura - MEV, poder calor?fico superior - PCS, an?lise imediata (avalia??o da umidade, materiais vol?teis, cinzas e carbono fixo) bem como avalia??o dos teores dos principais constituintes, ou seja, lignina, celulose e hemicelulose. No processo de pir?lise os seguintes par?metros foram estudados: temperatura da rea??o (450, 500 e 550 ?C), vaz?o do g?s de arraste (50 e 100 cm?/min) e velocidade de centrifuga??o para condensa??o do bio-?leo (20 e 25 Hz). O fluxo de alimenta??o da biomassa (540 g/h), a rota??o do cilindro rotativo (33,7 rpm) e o tempo de rea??o (30 33 min) foram mantidos constantes. Os produtos obtidos no processo da pir?lise da fibra do coco seco foram o bio-?leo, os finos de carv?o e a fase gasosa n?o condensada. Um balan?o de massa macrosc?pico aplicado tendo como base o peso de cada produto permitiu obter o rendimento dessas fases. O melhor rendimento de 18,1 % em bio-?leo foi obtido nas seguintes condi??es: temperatura de 500 ?C, vaz?o de g?s inerte 100 cm?/min e velocidade de centrifuga??o de 20 Hz. Nessas condi??es, o rendimento em finos de carv?o foi de 21,7 %, fase gasosa n?o condens?vel 37,6 % e perdas da ordem de 22,6 %. Algumas propriedades f?sicas do bio-?leo foram avaliadas, a saber, a densidade, viscosidade, pH, poder calor?fico superior, teor de finos de carv?o, an?lise por IVTF e CHN. A an?lise cromatogr?fica do bio-?leo mostrou que os principais constituintes de sua composi??o foram o fenol seguido do sirigol, aceto vanilona e vinil guaiacol. A fase s?lida (finos de carv?o) obtida foi caracterizada por an?lise imediata, poder calor?fico superior e IVTF. A fase gasosa n?o condensada apresentou como principais constituintes o CO2, CO e H2. Os resultados foram comparados com dados da literatura.

Maitriser la logistique de la chaine du froid à des températures de -20°C/-30°C reste un enjeu majeur de sécurité sanitaire. Des solutions auto-réfrigérées basées sur des systèmes thermochimiques sont très adaptées à la mise en température rapide de caissons isothermes et de leur maintien pendant plusieurs heures. Différents concepts et configurations de procédés répondant à cette problématique sont proposés. Leur modélisation dynamique de type nodale, impliquant une gestion thermodynamique d'un ou plusieurs réacteurs, a permis d'analyser leur comportement et d'évaluer leur pertinence. Les configurations les plus performantes sont sélectionnées et analysées afin d'établir un pré-dimensionnement industriel du procédé. D'autre part, la fiabilité de ces systèmes thermochimiques repose sur la qualité des transferts de masse et de chaleur au sein des réacteurs. A cette fin, une approche de diagnostic de dysfonctionnements possibles de réacteurs est développée. La méthodologie proposée s'appuie sur la comparaison de la réponse expérimentale du réacteur testé à celle modélisée d'un réacteur opérant dans les mêmes conditions opératoires présentant ou non des défauts. Une base de données de comportements de réacteurs défaillants, établie par simulation de défauts de typologie et d'intensité connues, permet ainsi la détection et l'identification rapide de possibles dysfonctionnements de réacteurs issus de la chaine de fabrication. / A better cold chain logistics understanding and control is a major safety issue in deep freezing processes within -20°C/-30°C. Self-cooling solutions based on thermochemical systems appear very suitable for rapid cooling of isothermal containers and its temperature regulation for several hours. Different process concepts and configurations are presented to tackle this problem. Through their dynamic nodal modeling, involving thermodynamic management of one or various reactors, an analysis of their behaviors is performed to evaluate their relevance. A selection of the best performing configurations leads us to an industrial pre-design.To undertake quality measures, a diagnosis approach for possible reactors malfunctions is developed. The methodology is based on a comparison of experimental responses between tested reactor and reference one under the same operating conditions. A database of simulated faulty behaviors will allow the detection and identification of possible malfunctions of reactors coming from the production line.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O objetivo deste trabalho é a aplicação de um Planejamento Fatorial Completo, ferramenta estatística que auxiliará a obter dados empíricos para otimizar um tratamento termoquímico, a cementação. Partindo-se de um levantamento da profundidade de camada cementada e da dureza de uma corrente de aço de baixo teor de carbono, usada para amarração, e para resistir à abrasão reproduziu-se uma nova cementação, variando-se seus parâmetros de influência, para se alcançar o ponto ótimo, definindo o melhor aço e o melhor processo. Foram realizados dois planejamentos, um fatorial 2 e dois 2, comparando o comportamento do processo na prática em relação aos resultados teóricos de uma simulação computacional, que permite a obtenção das curvas de enriquecimento de carbono, baseado na segunda Lei de Fick, para várias condições de contorno. Os perfis teóricos de cementação apresentaram valores de profundidade efetiva próximos aos valores obtidos experimentalmente, evidenciando o planejamento realizado.

De nombreux corps du système solaire possèdent des enveloppes liquides internes, comme par exemple les noyaux métalliques des planètes telluriques et les océans profonds des satellites de glace de Jupiter et Saturne, dans lesquelles se produisent des courants de convection. La modélisation de la dynamique de ces enveloppes est cruciale pour comprendre la génération des champs magnétiques planétaires (pour les noyaux) et pour mieux déterminer l’habitabilité potentielle des satellites joviens. La convection dans ces enveloppes est généralement produite par la combinaison d’au moins deux sources de flottabilité : une source thermique et une source solutale. Une telle situation est plus complexe qu’un régime de convection purement thermique ou purement solutale, d’une part en raison de l’existence d’un couplage thermochimique lorsqu’un processus de fusion ou de cristallisation se produit à l’une des frontières de l’enveloppe, et d’autre part à cause de la forte différence de diffusivité moléculaire entre les champs thermique et compositionnel qui permet potentiellement le développement d’instabilités double-diffusives. Classiquement, ces complexités ont été ignorées dans les simulations numériques de la dynamo terrestre ; les champs thermique et compositionnel ayant été combinés en une seule variable nommée « codensité ». Cette approche est sans doute simpliste mais permet d’esquiver une difficulté technique liée à la description du champ compositionnel dont la très faible diffusivité nécessite de recourir à des méthodes numériques adaptées. Cette thèse présente d’abord l’implémentation d’une méthode semi-Lagrangienne du type « particle-in-cell » dans un code de dynamo pré-existant, permettant ainsi de traiter de manière plus réaliste le champ de composition dans les enveloppes liquides internes des planètes. Les optimisations réalisées sont détaillées ainsi que les résultats de tests sur des cas de benchmark qui valident cet outil. Une comparaison avec des méthodes Eulériennes est également présentée. Une première exploration de la physique de la convection compositionnelle et thermochimique en rotation dans la limite d’un nombre de Prandtl compositionnel infini est ensuite conduite dans le contexte du noyau liquide terrestre. Il est montré que la dynamique convective est très différente de celle de la convection thermique pure. Notamment, les matériaux légers injectés à la frontière graine/noyau liquide sont capables d’atteindre la frontière noyau/manteau et de s’y accumuler pour former une couche chimiquement stratifiée, dont l’existence a été évoquée théoriquement mais qui n’a jamais pu être produite dans de précédentes simulations. Enfin, la dynamique double-diffusive des couches stratifiées est également discutée, et de premières simulations de « salt fingers » sont présentées. / Numerous planetary bodies contain internal liquid layers in which convective currents are generated by the combination of buoyancy sources of thermal and compositional origin. The strong difference between the thermal and chemical molecular diffusivities and the possibility of thermo-chemical coupling at melting or freezing boundaries create a convective regime that is much more complex than pure thermal convection, partly due to the potential occurrence of double-diffusive instabilities. Traditionally, numerical simulations have modeled the dynamics of the liquid part of planetary cores in a more simplistic way by neglecting the diffusivity difference and combining both fields into one single variable, an approximation that is convenient but maybe not relevant. However, distinguishing both fields and dealing with a large or infinite diffusivity ratio makes it compulsory to use numerical methods that minimize numerical diffusion as much as possible. In this thesis, I adapted a semi-Lagrangian particle-in-cell method into a pre-existing dynamo code to describe the weakly diffusive compositional field. I optimized the code for massively parallel computing and validated it on two different benchmarks. I compared the particle-in-cell method to Eulerian schemes and showed that its advantages extend beyond its lower numerical dissipation. Using this new tool, I performed first numerical simulations of rotating pure compositional and thermochemical convection in the limit of null chemical diffusivity. I explored the physics of pure compositional convection and addressed questions related to the existence and the dynamics of a stratified layer below the Earth’s core mantle boundary. In particular, I showed that the stratification could potentially be of chemical origin and proposed some mechanisms to explain its formation. In the case of a thermally stratified layer, I performed a scaling analysis of fingering instabilities, wrote the first steps of a linear stability analysis and ran a few simulations of fingering instabilities in the rotating case. The potential effects of the magnetic field and the coupling of thermochemical boundary conditions in planetary cores are finally discussed in this thesis.

Le défi énergétique imposé par l’épuisement des énergies fossiles d’une part et par leur consommation croissante d’autre part, a favorisé l’apparition d’une gestion optimale de l’énergie basée sur l’utilisation de ressources propres et renouvelables telles que l’énergie solaire. Le secteur du bâtiment est le principal consommateur d’énergie. Une grande partie de cette énergie est consommée par les systèmes de chauffage. Par conséquent, une bonne gestion peut être réalisée grâce à l’utilisation des technologies de stockage thermochimique d’énergie. L’avantage principal d’utiliser ce type de système est la possibilité de stocker de la chaleur pendant la période de disponibilité maximale du rayonnement solaire, en été (étape de déshydratation) et la libérer pour chauffer une maison pendant la période hivernale (étape d’hydratation). L’amélioration des propriétés d’adsorption des matériaux pour le stockage thermochimique de la chaleur est l’objectif principal de ce travail. L’utilisation d’adsorbants poreux tels que les zéolithes dans le domaine du stockage saisonnier de la chaleur s’avère être une solution intéressante pour la réduction de la consommation d’énergie. Par ailleurs, le développement de nouveaux matériaux composites à base d’hydrate de sel a été étudié pour améliorer les capacités de stockage à la fois des matrices mésoporeuses et des hydrates salins. Une comparaison entre les différentes séries de matériaux de stockage thermochimiques sélectionnés et synthétisés a été réalisée, concernant l’impact de la nature et de la quantité de sel ajouté et des propriétés physicochimiques des matériaux poreux sur leurs densités de stockage de chaleur et leurs capacités de sorption d’eau. Afin de mieux comprendre le comportement d’adsorption-désorption, les différents types de matériaux de stockage sélectionnés ont été caractérisés d’un point de vue structural et textural en utilisant des techniques appropriées et par adsorption de la vapeur d’eau en utilisant un analyseur thermique TG-DSC 111 de Setaram. Des cycles successifs d’hydratation (à 20°C) / déshydratation (à 150°C) ont été effectués / The energy challenge imposed by exhaustion of fossil fuels and their increasing consumption has favored the emergence of optimal energy management based on the use of alternative resources such as solar energy. The household sector is the main consumer of energy. A large part of this energy is consumed by heating systems. Therefore, good management can be achieved through the use of thermochemical energy storage technology. The main advantage to use this type of system is the possibility to store heat during the maximum availability of solar radiation in summer (dehydration step) and release the energy on demand for heating houses in winter (hydration step). The improvement of the adsorption properties of materials for thermochemical heat storage is the main objective of this work. The use of porous adsorbents such as zeolites in the field of seasonal heat storage is an attractive solution for the reducing of energy consumption. On the other hand, the development of new composite materials based on hydrate salt is made to improve the heat storage capacities of both pure mesoporous host matrix and hydrate salt. A comparison among different series of thermochemical storage materials selected and synthesized was done by analyzing the impact of salt addition and physico-chemical properties of porous materials on the heat storage and water sorption performances. In order to understand the adsorption-desorption behavior, different kinds of materials were characterized in their structural, textural and surface properties by using appropriate techniques and by adsorption of water vapor using a Setaram TG-DSC 111 apparatus. Successive cycles of hydration (at 20°C) / dehydration (at 150 °C) were performed

Les actions conjointes en faveur d’une meilleure isolation du bâti et de l’expansion des énergies renouvelables dans l’habitat jouent un rôle de premier plan dans la politique de réduction des gaz à effet de serre et la recherche d’une plus grande efficacité énergétique. La présente thèse vise à développer un système de stockage de chaleur par voie thermochimique dédié au chauffage solaire d’une maison individuelle. A cet effet, un matériau de stockage spécifique à été mis au point, à base de zéolithe et de sulfate de magnésium. Le principe, reposant sur un phénomène mixte d’adsorption physique de vapeur d’eau et de réaction chimique d’hydratation, est à caractère inter-saisonnier : en été, la chaleur issue de capteurs solaires thermiques à air est stockée par le matériau, qui se déshydrate selon une réaction endothermique ; en hiver, l’exothermicité de la réaction inverse est exploitée afin de chauffer l’habitat. Après un état de l’art des technologies de stockage thermique, un protocole de préparation de ce matériau composite innovant est établi. Des travaux de caractérisation sont alors entrepris à l’échelle micro et macroscopique. A partir de ces données expérimentales macroscopiques, le système de stockage est dimensionné en fonction des besoins en chaleur pour le chauffage d’une maison individuelle de type Bâtiment Basse Consommation. A l’issue de cette étude, un modèle de réacteur de stockage thermique est élaboré, afin d’interpréter les transferts couplés de matière et de chaleur intervenant dans le lit de matériau et d’optimiser le réacteur de stockage en conséquence. La validité du modèle est ensuite testée et discutée à la lumière des résultats expérimentaux. / The combined efforts promoting an improved insulation and a growth of renewable energies use in buildings play a key role in the road towards greenhouse gas reduction and better energy efficiency. This thesis purpose is to develop a chemicalbased thermal energy storage system devoted to solar space heating of single-family houses. A specific heat storage material has thus been created, made of zeolite and magnesium sulphate. The storage principle, based on a hybrid phenomenon between water vapour physical adsorption and chemical hydration reaction, is seasonal : during the summer, the material stores heat obtained from evacuated tube solar collectors using an endothermic dehydration reaction ; the stored heat is released by rehydration of the material during the winter to produce hot air dedicated to space heating. After a state of the art regarding thermal energy storage technologies, a preparation method is set up. Then, characterization studies of this innovative composite material have been performed, at both micro- and macroscopic scales. Thanks to the macroscopic experimental data, the system size is estimated to meet the space heating energy demand of a low energy single-family house. Afterwards, a thermochemical storage model is developed to understand the coupled heat and mass transfer occurring in the composite sorbent bed, and consequently optimize the reactor design. The model relevancy is finally discussed with respect to experimental results.

Orientadora: Profa. Dra. Ana Maria Pereira Neto / Coorientador: Profª. Drª. Juliana Tófano de Campos Leite Toneli / Dissertação (mestrado) - Universidade Federal do ABC. Programa de Pós-Graduação em Energia, Santo André, 2016. / No ano 2010, o Congresso Nacional do Brasil aprovou a Política Nacional de Resíduos Sólidos (PNRS) com o objetivo de buscar soluções aos problemas causados pela geração de resíduos, que vêm afetando a qualidade de vida da população. Além disso, a PNRS propõe uma gestão eficaz que inclui desde a redução da geração dos resíduos até sua disposição final adequada, aprovando a possibilidade de recuperação de energia a partir dos mesmos. Alguns países incluíram a Conversão de Resíduos em Energia do inglês Waste to Energy-WTE, nos seus planos nacionais de gestão de resíduos como tratamento mediante o processo de combustão in natura. O objetivo deste trabalho foi caracterizar as frações combustíveis (matéria orgânica, resíduos sanitários, plásticos, papel/papelão/tetra pak e têxteis) dos Resíduos Sólidos Urbanos (RSU) úmidos gerados no município de Santo André localizado no estado de São Paulo com vistas ao seu aproveitamento energético. As frações combustíveis foram caracterizadas tendo em conta sua composição gravimétrica, analisando suas propriedades densidade a granel, umidade, análise imediata e poder calorífico avaliadas na estação de primavera-verão de 2015, visando sua conversão em energia mediante o processo de combustão in natura. Com o objetivo de obter amostras representativas foi utilizada a norma MODECOMTM para o cálculo do número de amostras para a caracterização dos RSU. Para a determinação de suas propriedades foram usadas as normas ASTM para combustível derivado de resíduos (CDR). De acordo com os resultados obtidos os RSU úmidos gerados no município têm umidade de 51,5%, poder calorífico inferior (PCI) de 7,53 MJ/kg e capacidade de geração de energia elétrica de 565 kWh por tonelada de resíduo incinerado com eficiência de conversão de 27%, características favoráveis para sua conversão em energia mediante sua combustão in natura, oferecendo assim uma opção de tratamento, ao invés da sua disposição no aterro sanitário. / In 2010, Brazil approved the National Politic of Municipal Solid Waste (NPSW) in order to seek for solutions to the problems caused by the generation of waste, that has been affecting the population's quality of life. The NPSW also proposes an efficient management including the reduction of waste generation and the correct final disposition, by evaluating its energy recovery. Currently some countries include in their national management plans, the conversion of Waste to Energy (WTE) using the combustion process. The objective of this work was to evaluate the energy potential of fraction combustible (organic matter, sanitary waste, plastics, paper/cardboard/tetra pak and textiles) of the Municipal Solid Waste (MSW) generated by Santo André, a town located in the state of Sao Paulo. The fraction combustible was characterized taking into account their composition and analyzing their physical (bulk density), chemical (proximate analysis) and thermal (calorific value) properties, evaluated in the spring and summer season, aiming its conversion to energy using combustion process. With the purpose of having representative samples, MODECOMTM methodology has used to calculate the samples number in the MSW characterization. To determinate the physical, chemical and thermal properties in the laboratory, were used the ASTM standards for Refuse Derived Fuel (RDF). According to the results obtained, the MSW generated in the municipality the humidity is 51,5%, lower heating value (LHV) 7,53 MJ/kg and generation capacity in electricity 565 kWh tonne of waste incinerated a conversion efficiency of 27% , showed favorable characteristics to their conversion to energy using mass burning, providing a treatment option, instead of its disposal at the landfill.

Thermochemical nonequilibrium widely exists in supersonic combustion, cold plasma and hypersonic flight. The effect can influence heat transfer, surface ablation and aerodynamic loads. One distinct feature of it is the coupling between internal energy excitation and chemical reactions, particularly the vibration-dissociation coupling. The widely used models are empirical and calibrated based on limited experimental data. Advances in theories and computational power have made the first-principle calculation of thermal nonequilibrium reaction rates by methods like quasi-classical trajectory (QCT) almost a routine today. However, the approach is limited by the uncertainties and availability of potential energy surfaces. To the best of our knowledge, there is no study of thermal nonequilibrium transport properties with this approach. Most importantly, non-trivial effort is required to process the QCT data and implement it in flow simulation methods. In this context, the first part of this work establishes the approach to compute transport properties by the QCT method and studies the influence of thermal nonequilibrium on transport properties for N₂-O molecules. The preponderance of the work is the second part, a comprehensive study of the development of a new thermal nonequilibrium reaction model based on reasonable assumptions and approximations. The new model is as convenient as empirical models. By validating against recent QCT data and experimental results, we found the new model can predict nonequilibrium characteristics of dissociation reactions with nearly the same accuracy as QCT calculations do. In general, the results show the potential of the new model to be used as the standard dissociation model for the simulation of thermochemical nonequilibrium flows.

Zeolithgranulate sind etablierte Materialien für die Speicherung von Wärme mittels Wassersorption. Eine Erhöhung der Wärmespeicherdichte des Granulats ist durch Kombination mit hygroskopischen Salzen wie Calciumchlorid, Magnesiumchlorid oder Magnesiumsulfat möglich. In der vorliegenden Dissertation wird gezeigt, dass die Wär-mespeichereigenschaften derartiger Komposite von der Deliqueszenzluftfeuchte des Salzes, von der Salzbeladung und von der Luftfeuchte bei der Wassersorption abhängen. Liegt die Luftfeuchte unterhalb der Deliqueszenzluftfeuchte des Salzes, so nehmen Was-serbeladungshub, Wärmespeicherdichte und thermische Leistung mit steigender Salz-beladung um bis zu 71 % ab. Dies wird darauf zurückgeführt, dass Salzionen in die Mik-roporen des Zeoliths inkludiert werden und das für die Wassersorption zur Verfügung stehende Volumen verringern. Unterhalb der Deliqueszenzluftfeuchte ist das einge-brachte Salz daher thermochemisch inaktiv. Oberhalb der Deliqueszenzluftfeuchte und oberhalb einer salz- und luftfeuchteabhängigen Mindestsalzbeladung kommt es zur Ausbildung einer Salzlösung im Sekundärporensystem des Granulats. Die Absorption von Wasserdampf in der Salzlösung führt gegenüber dem salzfreien Granulat zu einer Steigerung von Wasserbeladungshub und Wärmespeicherdichte um bis zu 53 %. Dies geht jedoch einher mit einer Verringerung der thermischen Leistung um bis zu 50 %. Die Hydratation von kristallinem Salz im Granulat spielt gegenüber Salzinklusion und Ausbildung der Salzlösung nur eine untergeordnete Rolle. Die aus den experimentellen Befunden abgeleiteten Erkenntnisse konnten in ein semiempirisches mathematisches Modell überführt werden, welches den Wasserbeladungshub der Komposite quantitativ beschreibt. / Zeolite beads are established materials for the storage of heat by water sorption. An increase of the heat storage density of the beads is possible via the combination with hygroscopic salts. In this thesis it is shown, that the heat storage properties of compo-sites of this kind depend in a complex manner on the deliquescence humidity of the salt, on the salt loading, and on the humidity during water sorption. When the humidity is below the deliquescence humidity of the salt, water loading lift, heat storage density, and thermal power are reduced by up to 71 % with increasing salt content. This is at-tributed to the inclusion of salt into the micropores of the zeolite and the reduction of the volume available for the sorption of water. Thus, below the deliquescence humidity, the salt is thermochemically inactive. Above the deliquescence humidity and above a salt- and humidity-dependend minimum salt loading, a salt solution is formed in the secondary pore system of the beads. The absorption of water vapor in the salt solution gives rise to an increase of the water loading lift and of the heat storage density by up to 53 %, compared to the salt-free zeolite beads. However, this is accompanied by a reduc-tion of the thermal power output by up to 50 %. The hydration of crystalline salt in the beads is only of minor importance for the composites. The findings from the experi-mental work were transferred into a semi-empirical mathematical model, which de-scribes the water loading lift of the composites.