The past few years have seen an upsurge in the use of renewable biomass as a source of energy due to growing concerns over greenhouse gas emissions caused by the combustion of fossil fuels and the need for energy independence due to depleting fossil fuel resources. Although coal will continue to be a major source of energy for many years, there is still great interest in replacing part of the coal used in energy generation with renewable biomass. Combustion converts inherent chemical energy of carbonaceous feedstock to only thermal energy. On the other hand, partial oxidation processes like gasification convert chemical energy into thermal energy as well as synthesis gas which can be easily stored or transported using existing infrastructure for downstream chemical conversion to higher value specialty chemicals as well as production of heat, hydrogen, and power. Devolatilization or pyrolysis plays an important role during gasification and is considered to be the starting point for all heterogeneous gasification reactions. Pyrolysis kinetic modeling is, therefore, an important step in analyzing interactions between blended feedstocks. The thermal evolution profiles of different coal-biomass blends were investigated at various heating rates using thermogravimetric analysis. Using MATLAB, complex models for devolatilization of the blends were solved for obtaining and predicting the global kinetic parameters. Parallel first order reactions model, distributed activation energy model and matrix inversion algorithm were utilized and compared for this purpose. Using these global kinetic parameters, devolatilization rates of unknown fuel blends gasified at unknown heating rates can be accurately predicted using the matrix inversion method. A unique laboratory scale auto-thermal moving bed gasifier was also designed and constructed for studying the thermochemical conversion of coal-biomass blends. The effect of varying operating parameters was analyzed for optimizing syngas production. In addition, stable carbon isotope analysis using Gas Chromatography-Combustion-Isotope Ratio Mass Spectrometry (GC-C-IRMS) was used for qualitatively and quantitatively measuring individual contributions of coal and biomass feedstocks for generation of carbonaceous gases during gasification. The predictive models utilized and experimental data obtained via these methods can provide valuable information for analyzing synergistic interactions between feedstocks and also for process modeling and optimization.

Biodegradable, edible wheat gluten films offer a renewable alternative to plastic food packaging or can be incorporated directly in the food product. Wheat gluten is a good option because it forms a fibrous network, lending strength and elasticity to films. The goal of this research project was to produce, with a water-based film formulation and methodology, smooth, homogeneous wheat gluten films with low water vapour permeability (WVP). The water-based film formulation also served to compare the FT Wonder wheat cultivar, grown in Ontario, to commercially produced wheat gluten and determine the effect of wheat source on the film properties, surface morphology, surface hydrophobicity, WVP, and film swelling in water for different pH, temperature and casting surface conditions. Fluorescence, SPR, and casting formulation viscosity provided preliminary information on the mechanism of film formation and on gluten protein structure induced by modifying the film formulation. This research provides an alternate use for some Ontario wheat cultivars based on their properties in films compared to commercial sources of gluten. As a result, using Ontario cultivars to prepare gluten film packaging material has potential as an alternate source of income for Ontario farmers. This research also defines the film properties for gluten films produced from aqueous solutions, helping to identify processing parameters that could bring gluten films on par with plastic packaging and make gluten films a viable alternative food packaging material. Finally, it was determined that the water vapour permeability of wheat gluten films was not correlated to film surface contact angle.

Submitted by Morgana Andrade (morgana.andrade@ufes.br) on 2016-04-08T19:43:32Z No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) tese_8940_Lorena Coelho Benevides verso final.pdf: 1351644 bytes, checksum: 36811571a6fc31c4766e3cc2e0db0ce7 (MD5) / Approved for entry into archive by Patricia Barros (patricia.barros@ufes.br) on 2016-05-13T13:34:04Z (GMT) No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) tese_8940_Lorena Coelho Benevides verso final.pdf: 1351644 bytes, checksum: 36811571a6fc31c4766e3cc2e0db0ce7 (MD5) / Made available in DSpace on 2016-05-13T13:34:04Z (GMT). No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) tese_8940_Lorena Coelho Benevides verso final.pdf: 1351644 bytes, checksum: 36811571a6fc31c4766e3cc2e0db0ce7 (MD5) / CAPES / O Brasil produz 1,4 milhões de toneladas de suco de laranja, sendo responsável por 50% da produção mundial. Estima-se que 40-60% do volume processado seja considerado rejeito. Uma alternativa de aproveitamento da biomassa residual é a sua utilização para a obtenção de energia a partir do processo de pirólise. A compreensão desse processo envolve o estudo da cinética de degradação da biomassa residual, dos fenômenos de transporte, bem como do tipo, configuração e condições ótimas de operação do reator. O objetivo principal deste trabalho é o estudo cinético da pirólise de bagaço de laranja. Com relação à análise termogravimétrica, esta foi avaliada em dois estágios: o primeiro referente à perda de água livre até 373 K (secagem) e o segundo referente às reações de pirólise (devolatilização). Para a fase de secagem, modelos semi-empíricos de secagem foram usados em suas formas não isotérmicas. Já para a fase de devolatilização, utilizaram-se os modelos isoconversionais e o das reações paralelas independentes (RPI) reparametrizado. Para o primeiro estágio, o modelo que melhor descreveu a etapa de secagem dinâmica foi o de Overhutz, obtendo-se energia de ativação média de 11,24 kJ/mol. Já para o segundo estágio, os modelos isoconversionais apresentaram energia de ativação entre 104,94 e 417,27 kJ/mol. O modelo de Reações Paralelas Independentes Reparametrizado apresentou energia de ativação entre 130,32 e 153,62 kJ/mol, 144,00 e 194,65 kJ/mol, 59,23 e 85,41 kJ/mol, 74,16 e 148,89 kJ/mol, e 163,95 e 184,23 k/mol para hemicelulose, celulose, lignina, pectina e componente não conhecido, respectivamente. As frações dos subcomponentes do bagaço de laranja também foram estimados e obtiveram-se valores aproximados de 21, 31, 17, 25 e 6% de hemicelulose, celulose, lignina, pectina e componente x, respectivamente. Além disso, avaliou-se a cinética de secagem convectiva do bagaço, visto que o mesmo possui uma alta umidade inicial, empregando-se as equações semi-empíricas de cinética de secagem. A energia de ativação para a cinética convectiva do bagaço de laranja foi de 20,99 kJ/mol e o modelo de Overhultz foi o que melhor se adequou aos dados experimentais. / Brazil produces 1.4 million tons of orange juice, accounting for 50% of world production. It is estimated that 40-60% of the volume processed is considered tailings. An alternative use of residual biomass is their use for obtaining energy from the pyrolysis process. Understanding this process involves the study of the residual biomass degradation kinetics, transport phenomena, and the type, configuration, and optimal conditions of reactor operation. The aim of this work is the kinetic study of orange bagasse pyrolysis. With respect to thermogravimetric analysis, this was assessed in two stages: the first refers to the free water loss to 373 K (drying) and the second referring to the pyrolysis reactions (devolatilization). For the drying step, the semi-empirical models of drying were used in their non-isothermal forms. As for the devolatilization phase, they used the isoconversionais models and independent parallel reactions (RPI) reparametrized. For the first stage, the model that best describes the dynamic drying step was to Overhutz, obtaining average activation energy of 11,24 kJ/mol. As for the second stage, isoconversionais models showed activation energy between 104,94 and 417,27 kJ/mol. The reparametrized Independent Parallel Reactions model presented activation energy between 130,32 and 153,62 kJ/mol, 144,00 and 194,65 kJ/mol, 59,23 and 85,41 kJ/mol, 74,16 and 148,89 kJ/mol, and 163,95 and 184,23 kJ/mol for hemicellulose, cellulose, lignin, pectin, and component not known respectively. Fractions of subcomponents of orange bagasse were also estimated and is obtained approximate values of 21, 31, 17, 25 and 6% hemicellulose, cellulose, lignin, pectin and component x, respectively. In addition, it evaluated the convective drying kinetics bagasse, since it has a high initial moisture content, using the semi-empirical equations drying kinetics. The activation energy for convective kinetics of orange bagasse was 20,99 kJ/mol and the Overhultz model was the one best suited to the experimental data.

L’épuisement des combustibles fossiles et l’augmentation de la demande d’énergie, entrainent l’intérêt croissant du développement des énergies renouvelables et des systèmes efficaces énergétiquement. Néanmoins, le décalage entre le besoin en énergie et la fourniture de celle-ci par les énergies renouvelables rend nécessaire l’utilisation d’un système de stockage. Parmi les différentes technologies de stockage d’énergie thermique, les composites formés d’une matrice poreuse et d’un sel hygroscopique, permettent de profiter à la fois des capacités d’adsorption/désorption de la matrice et des réactions chimiques du sel. La difficulté principale du développement d’un tel système est la compréhension incomplète des phénomènes physico-chimiques mis en jeu.Le premier objectif de cette thèse est d’étudier les réactions d’hydratation et de déshydratation du sel MgSO4. La caractérisation physico-chimique des solides ainsi que des expériences de thermogravimétrie isotherme et isobare ont été réalisées. Il a été montré que le système est divariant et que les hydrates obtenus sont non-stœchiométriques. Un modèle thermodynamique a été développé et appliqué aux données expérimentales. Les études cinétiques des réactions de déshydratation et d’hydratation ont été réalisées ce qui a permis de définir les étapes limitantes ainsi que d’écrire deux modèles et d’appliquer aux résultats expérimentaux. Enfin différents matériaux composites zéolite/ MgSO4 ont été synthétisés. Ces matériaux ont été caractérisés et leur capacité de sorption a été mesurée. Les résultats mettent en évidence une augmentation de la capacité de sorption, mais uniquement pour des pressions de vapeur d’eau importantes. / Exhaustion of fossil fuels and increase of energy demand, lead to growing interest in the development of renewable energies and energy efficient systems. Nevertheless, the gap between the supply and the demand of energy by renewable energies makes necessary the using a storage system. Among various thermals energy storage technologies, the composites formed by a porous matrix and a hygroscopic salt, allow to benefit advantage of both the adsorption/desorption capacities of the matrix and the chemical reactions of salt. The main difficulty to develop of such a system is the incomplete understanding of the involved physicochemical phenomena.The first objective of this thesis is to study the hydration and dehydration reactions of MgSO4 salt in presence of water vapor. Firstly, the physicochemical characterization of solids and isothermal and isobaric thermogravimetry experiments were carried out. It has been shown that the system is divariant and that the hydrates obtained are non-stoichiometric with localized water molecules. A thermodynamic model was developed and applied to the experimental data. In a second step, the kinetic studies of both the dehydration and hydration reactions were carried out. The rate limiting steps were defined, two kinetic models have been written and applied to the experimental results. Finally, various zeolite/MgSO4 composite materials have been synthesized. These materials have been characterized and their sorption capacity has been measured. The results show an increased sorption capacity, but only for water vapor pressures different from those used for thermal energy storage.

Submitted by ANA KARLA PEREIRA RODRIGUES (anakarla_@hotmail.com) on 2017-08-08T13:12:39Z No. of bitstreams: 1 arquivototal.pdf: 2266227 bytes, checksum: d3171f9e7352fd7ad3ac2fd448b412dc (MD5) / Made available in DSpace on 2017-08-08T13:12:39Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2266227 bytes, checksum: d3171f9e7352fd7ad3ac2fd448b412dc (MD5) Previous issue date: 2016-08-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In this investigation we studied the polymer films formed of poly (vinyl alcohol) (PVA) and carboxymethylcellulose (CMC), both polymers readily available, and the synthetic first and second semi-synthetic. The films were prepared by evaporation of the solvent method and crosslinked with citric acid (CA) in order to improve their hydrophobicity characteristics. The crosslinked films and uncrosslinked were characterized via swelling measurements, the solubility and permeability to water vapors for testing the barrier properties of the films. In addition to these, antimicrobial activity assays were performed, scanning electron microscopy (SEM), thermal gravimetric analysis and spectroscopy in the infrared region. Infrared spectra suggested the formation of the blend by displacement of bands and showed that the crosslinking process occurred. Crosslinked films showed better results in relation to the water barrier properties (solubility, swelling and permeability) compared to films not lattices, results as they were, in fact, expected some time crosslinking rearranges the polymer chains in order to hinder the passage of water molecules and control the passage of smaller molecules. Thermal degradation analysis showed that the stability of the films was affected by the presence of citric acid crosslinking agent so that crosslinked films with higher concentrations of BC had greater stability of the thermal point of view. The SEM of the films showed a smooth and homogeneous surface without phase separation of blends and no porosities. The antimicrobial activity performed with strains of S. aureus, S. epidermidis, Pseudomonas aeruginosa, Candida albicans and C. topicalis showed that no film inhibition activity on the growth of microorganisms. Besides characterization was carried out applying the transdermal films for controlled drug release, which we evaluated the release kinetics of acetaminophen and drugs fluconazole crosslinked films 20 and 30% citric acid. The results of controlled drug release showed that the film exhibited different behaviors across the control release so that the blends presented model release of zero order, carboxymethylcellulose films to uncontrolled release and PVA films were able to maintain a concentration drug constant in the receiving environment after 12 hours of testing. / Nesse trabalho foram estudados os filmes poliméricos formados por poli (álcool vinílico) (PVA) e carboximetilcelulose (CMC), dois polímeros de fácil obtenção, sendo o primeiro sintético e o segundo semissintético. Os filmes foram preparados pelo método da evaporação do solvente e reticulados com ácido cítrico (AC), a fim de melhorar suas características de hidrofobicidade. Os filmes reticulados e não reticulados foram caracterizados via ensaios de intumescimento, solubilidade e permeabilidade aos vapores de água para testar as propriedades de barreira dos filmes. Além desses, foram realizados ensaios de atividade antimicrobiana, microscopia eletrônica de varredura (MEV), análise termogravimétrica e espectroscopia na região do infravermelho. Os espectros de infravermelho sugeriram formaçãoda blenda através de deslocamento de bandas e mostrou que o processo de reticulação ocorreu. Os filmes reticulados apresentaram melhores resultados em relação às propriedades de barreira à água (solubilidade, intumescimento e permeabilidade) quando comparados aos filmes não reticulados, resultados como eram, de fato, esperados, umas vez que a reticulação reorganiza as cadeias poliméricas de forma a dificultar a passagem de moléculas de água e controlar a passagem de moléculas menores. A análise de degradação térmica mostrou que a estabilidade dos filmes foi afetada pela presença do agente reticulante ácido cítrico, de forma que os filmes reticulados com maior concentração de AC apresentaram a maior estabilidade do ponto de vista térmico. O MEV dos filmes mostrou uma superfície lisa e homogênea, sem separação de fases das blendas e ausência de porosidades. A atividade antimicrobiana realizada com cepas de S. aureus, S. epidermides, Pseudomonas aeruginosa, Candida albicans e C. topicalis, mostrou que nenhum filme apresentou atividade de inibição sobre o crescimento dos microorganismos. Além da caracterização, foi realizada a aplicação dos filmes para sistemas transdérmicos de liberação controlada de fármacos, onde foi avaliada a cinética de liberação dos fármacos paracetamol e fluconazol em filmes reticulados com 20 e 30% de ácido cítrico. Os resultados da liberação controlada de fármacos mostraram que os filmes apresentaram diferentes comportamentos frente ao controle da liberação, de forma que as blendas apresentaram modelo de liberação de ordem zero, os filmes de carboximetilcelulose não controlaram a liberação e os filmes de PVA conseguiram manter uma concentração constante de fármaco no meio receptor após as 12 horas de ensaio.

Nos últimos anos o principal desafio da humanidade foi a substituição total ou parcial dos combustíveis fósseis que são responsáveis pelas mudanças climáticas e contribuem para a formação dos gases do efeito estufa. Como alternativa, os combustíveis renováveis - denominados biocombustíveis - têm se tornado uma alternativa viável. Este trabalho investigou o comportamento térmico e a energia de ativação de dois biocombustíveis (farnesano e biodiesel de soja) e suas misturas com diesel fóssil. Além disso, foram feitos estudos comparativos de comportamento térmico e energia de ativação entre todos os combustíveis. Os estudos foram feitos empregando-se análise termogravimétrica (TGA) sob atmosfera de ar sintético. As condições experimentais para os testes termogravimétricos foram: massa das amostras de 4,0 ± 0,5 mg, razões de aquecimento de 5, 10, 15, 20 e 25ºC min-1 e faixa de temperatura entre 30ºC e 400ºC. Outras técnicas, tais como calorimetria, Calorimetria Exploratória Diferencial (DSC - \"Differential Scanning Calorimetry\") e testes em motor diesel OM 926 LA CONAMA P7/EURO 5 também foram aplicadas para se avaliar o comportamento térmico destes combustíveis. Os valores de poder calorífico superior (PCS) para o farnesano, diesel fóssil e biodiesel são 46,9 MJ/kg, 45,3 MJ/kg e 39,7 MJ/kg, respectivamente. Os experimentos no motor diesel mostraram uma economia de 3% para o farnesano e um consumo de 14,25 % para o biodiesel em relação ao diesel fóssil. Em média, os valores de energia de ativação para os combustíveis puros encontrados neste estudo foram de 82,20 ± 3,38 kJ mol-1, 86,61 ± 8,48 kJ mol-1 e 96,61 ± 3,74 kJ mol-1 para farnesano, diesel fóssil e biodiesel de soja, respectivamente. Como a energia de ativação está diretamente relacionada com o atraso de ignição e, consequentemente, ao processo de combustão, o farnesano apresentou uma melhor qualidade de combustão em relação ao biodiesel de soja. Por meio das emissões obtidas nos testes European Stationary Cycle test (ESC) com a utilização do motor diesel foi possível obter correlações lineares entre energia de ativação e as emissões de óxidos de nitrogênio (NOx) e hidrocarbonetos (HC) e correlações polinomiais entre energia de ativação e as emissões de monóxido de carbono (CO), dióxido de carbono (CO2) e material particulado (MP). A adição de biodiesel de soja ao diesel provocou um aumento das emissões tanto para o NOx quanto para o HC em até 21,29% e 19,31%, respectivamente, e queda nas emissões de CO, CO2 e MP em até 33,44%, 2,44% e 47,37%, respectivamente. Por outro lado, a adição de farnesano ao diesel proporcionou uma diminuição de todas as emissões, ou seja, 11,22 %, 15,67%, 15,09%, 4,66% e 6,14% para NOx, HC, CO, CO2 e MP, respectivamente. A partir dos resultados obtidos neste estudo é possível entender o comportamento dos combustíveis durante suas respectivas queimas tendo como base as suas energias de ativação. / In recent years, the main challenge of the humanity was the total or partial replacement of fossil fuels, which are responsible for both the climate changes and the production of greenhouse gases. As an alternative, renewable fuels - named biofuels - have become viable. This study investigated the thermal behavior and the activation energy of two biofuels (farnesane and soybean biodiesel) and their mixture with fossil fuel. In addition, the thermal behavior of the biofuels and their mixtures with fossil fuel were compared with pure fossil diesel. Experiments were performed applying thermogravimetric analysis (TGA) under synthetic air atmosphere and other conditions such as, sample mass of 4,0 ± 0,5 mg, heating ratios of 5, 10, 15, 20 and 25 °C min-1 and temperature range between 30ºC and 400°C. In addition, calorimetry, differential scanning calorimetry (DSC) and experiments in a diesel engine OM 926 LA CONAMA P7 / EURO 5 were applied. Calorific value (CV) of the farnesane, biodiesel and fossil diesel are 46.9 MJ kg-1, 45.3 MJ kg-1 and 39.7 MJ kg-1, respectively. Experiments in the engine showed a fuel saving of 3% for farnesane and an increase consumption of 14.24 % for biodiesel, compared to fossil diesel. On average, the values of activation energy for pure fuels determined in this study were 82.20 ± 3.38 kJ mol-1, 86.61 ± 8.48 kJ mol-1 and 96.61 ± 3.74 kJ mol-1 for farnesane, fossil diesel and soybean biodiesel, respectively. As the activation energy is directly related to the ignition delay and hence the combustion process, it was observed that farnesane presented a better quality of combustion in comparison to the biodiesel. By means of the emissions obtained by the European Stationary Cycle test (ESC) in the diesel engine, it was possible to observe linear correlations between activation energy for both nitrogen oxide (NOx) and hydrocarbon (HC) emissions, and polynomial correlations between activation energy and carbon monoxide (CO), carbon dioxide (CO2) and particulate matter (PM) emissions. The addition of soybean biodiesel to the diesel promoted an increase of both NOx and HC emissions in 1.29% and 19.31%, respectively and a decrease of 33.44%, 2.44% and 47.37% for CO, CO2 and PM emissions, respectively. On the other hand, the addition of farnesane to the fossil diesel, a reduction in all emissions were observed, i.e, 11.22%, 16.67%, 15.09%, 4.66%, 6.14%. of NOx, HC, CO, CO2 and PM, respectively. From the results obtained in this study, it is possible to understand the behavior and the emissions of the fuels produced during their burning based on their activation energies.

A interação da água com a celulose e com o amido é de grande importância para a compreensão das propriedades de ambos polissacarídeos e fundamental para o desenvolvimento de novas aplicações tecnológicas. Entre as novas aplicações estão em destaque a nanocelulose, como os nanocristais e microfibrilas. A preparação desses materiais é fortemente influenciada pela interação das ligações de hidrogênio presente nas fibras de celulose, tanto de caráter intra como intermolecular. Essas interações são responsáveis pelas propriedades mecânicas desses materiais uma vez que as moléculas estão ligadas umas às outras por meio de ligações de hidrogênio onde a água pode participar como elemento de ligação. Para o amido, dependendo da concentração da água, pode modifica-lo em termos da solubilidade e em propriedades pelo processo de gelatinização ou atuar como plastificantes como parcial despolimerização em amido termoplástico. Neste trabalho é descrito o estudo da interação do sistema água com a celulose e com o sistema água com amido por meio da análise termogravimétrica para a identificação de diferentes espécies de água: i) água livre, ii) água ligada congelável iii) água ligada não congelável. Para a realização deste estudo foi utilizado o método auto stepwise, método que permite uma maior resolução dos diversos fenômenos separadamente que ocorrem durante a dessorção da água. A dessorção da água no amido se demostrou mais complexa que a celulose devido à alternância da parte amorfa e cristalina em sua estrutura. Para o cálculo da energia de ativação da dessorção da água ligada e da degradação do polissacarídeo foi utilizado o método cinético de Osawa-Flynn-Wall, sendo possível estimar a energia de ativação dos fenômenos. Variando de 35-65 kJ/mol para dessorção da água ligada e 144,6-184 kJ/mol para degradação dos materiais. / The interaction of water with cellulose and starch are of great importance for understanding the properties of both polysaccharides and fundamental to the development of new technological applications. Among the new applications are highlighted to nanocellulose such as nanocrystals and microfibrils. The preparation of these materials is strongly influenced by the interaction of hydrogen bonds present in the cellulose fibers, both intra as intermolecular. These interactions are responsible for the mechanical properties of these materials since the molecules are linked to each other through hydrogen bonds where water can participate as a connecting element. For starch, depending on the concentration of the water, can modify it in terms of solubility and properties by gelatinization process or act as plasticizers as partial depolymerization of thermoplastic starch. This paper describes the study of the interaction of the water/cellulose system and the starch/water system by means of thermogravimetric analysis for the identification of different species of water: i) the free water or freezing water, ii) the freezing bound water and iii) the non-freezing bound water. For this study we used the auto stepwise method, that allows greater resolution of the various phenomena separately that occur during the water desorption. The water desorption in the starch is more complex that cellulose, due to alternating crystalline and amorphous parts of the structure. To calculate the bound water desorption activation energy and polysaccharide degradation energy was used kinetic method of Osawa-Flynn-Wall, that possible to estimate the phenomena of the activation energy, ranging from 35-65 kJ / mol for bound water desorption and from 144.6 to 184 kJ / mol for material degradation.

Les incendies sont complexes et mettent en jeu une multitude de phénomènes. Afin de les étudier, l’approche multiéchelle permet de séparer les processus.Parmi ceux-ci, la décomposition thermique des solides joue un rôle très important. Terme source, elle traduit la quantité, le débit et la nature des composés volatils émis. Sa description numérique est donc capitale. Les modèles utilisés aujourd’hui sont formés d’une loi de variation de la vitesse de forme « Arrhenius », couplée à une fonction de conversion de la masse pour chaque espèce étudiée et d’un mécanisme réactionnel organisant les réactions entre elles. Toutefois, ce modèle s’appuie sur les théories utilisées dans la phase gazeuse et de sérieux doutes peuvent être émis sur sa représentativité pour une application dans la phase condensée.Les travaux de thèse exposés dans ce rapport se focalisent sur le développement d’un modèle en partant des réactions et des processus les plus fondamentaux dans la phase condensée afin de permettre la simulation de la cinétique de décomposition des matériaux solides. Le second aspect concerne l’étude de ce modèle pour déterminer la méthode de résolution et d’optimisation la plus adéquate, le rôle de chacun des paramètres, les éventuels mécanismes de compensation et l’unicité de la solution.Finalement, l’ensemble de la démarche est appliquée à un matériau complexe, le bois. Les résultats obtenus, à partir d’une nouvelle démarche développée lors de ces travaux de thèse, montrent une amélioration significative du modèle aux aspects physiques et chimiques de la dégradation thermique des matériaux solides. / Fires are complex and a variety of phenomena are involved. In order to study them, the up-scaling approach separates all the processes.Among them, the solid thermal decomposition has an important role to play. Source term, it reflects the amount, rate and nature of volatile compounds emitted and its numerical description is essential. The models used currently are formed by a law of variable speed (the Arrhenius law) coupled with a conversion function of mass for each species and a kinetic mechanism organizing all reactions between them. However, this model is based on the theories used in the gas phase and serious doubts might be raised with regard to the representativeness for application in the condensed phase.The thesis works exposed in this report are focused on the model development departing from the reactions and the processes the more fundamental in the condensed phase in order to permit the simulation of the solid kinetic decomposition. The second aspect concerns the study of this model to determine the resolution and the optimization method the most appropriate, the role of each parameter, the possible compensation mechanisms and the uniqueness of the solution.Finally, the entire process is applied to a complex material, the wood. The results obtained from a new approach developed in this work, show a significant improvement of the model to the physical and chemical aspects of the thermal degradation of solid materials.

Diploma thesis studies the effect of temperature (75 and 105 °C) and the effect of 3 kinds of liquids (silicone and hydraulic oil and coolant) at room temperature and at 105 °C on change of the structure of 3 species butadiene-acrylonitrile (NBR) seals (o-ring and two types of bolts). The seals are inspected by the thermogravimetric analysis, differential scanning calorimetry and infrared spectroscopy, the influence of 105 °C on the o-rings is also evaluated in terms of changes in tensile properties. The greatest changes in the composition and structure are observed on o-rings particularly due to temperature of 105 °C, there was a significant reduction in dilatability and an increase in stiffness and glass transition temperature. The root cause is the surface and centre additive decomposition and oxidation. The bolts have suffered from decomposition of the protective surface layer and the additives in the centre, structural change was minor. Exposure to 75 °C has resulted in a gradual loss of low molecular weight substances. Liquids at room temperature didn‘t affect the structure of the seals, at 105 °C it caused a loss of weight due to decomposition of the protective surface layer and release of additives and the products of their decomposition. Results showed that the common use of the NBR seals at 105 °C is unsuitable, at 75 °C it leads to gradual changes, loss in mechanical and sealing properties.

The present study investigates the thermochemical conversion of spruce wood and its extracted components by thermogravimetric analysis. The extracted components are two pulps, three xylan-lignin samples and one lignin sample; they were produced by the kraft cooking method with different cooking times. The study involves characterization of the biomass through proximate analysis and pyrolysis. A qualitative comparison between the thermal behaviours of the extracted components and wood is also performed. The study showed that the thermal behaviour of the biomass was highly influenced by the content of cellulose and lignin in the samples. Compounds rich in cellulose produced large quantities of volatiles and had a higher rate of pyrolysis compared to compounds rich in lignin, which produced more char and had a slower rate of pyrolysis. It was also shown that, the amount of char is not solely depending on the amount of the lignin; the structure of the compound also plays a role. On the other hand, the original wood sample showed some deviations regarding the trends in volatile and char production and these deviations were attributed to component interactions. Both cellulose and lignin rich compounds had an increase in thermal stability with increasing cooking time. For the pulps the increase in thermal stability is believed to be caused by increase in crystallinity, while for the lignin rich samples is believed to be caused by the increase in lignin content and structural changes in the compounds. The results also show that although changes are introduced in the cooking process, the extracted component still retain properties exhibited by the source biomass.