Pour relever le défi énergétique du 21 ième siècle, une solution consiste à mettre au point des procédés solaires de production de vecteurs énergétiques par photosynthèse artificielle permettant la synthèse photo-catalytique de carburants solaires. L’obtention de performances cinétiques et énergétiques élevées pour ces procédés nécessite le développement d’outils de conception optimale tels des modèles de connaissance robustes et prédictifs considérant le transfert de rayonnement comme processus physique contrôlant le procédé à plusieurs échelles. Une chaine prédictive de modélisation, avec ses différents maillons, a donc été développée, mise en œuvre et validée sur une réaction modèle de photo-production d’hydrogène à partir d’une suspension de particules de CdS. Ainsi, à partir de leurs caractéristiques (taille, forme...) et de leurs propriétés optiques, les propriétés radiatives des particules, à savoir sections efficaces d’absorption, de diffusion et fonction de phase ont été calculées au moyen de la théorie de Lorenz-Mie et validées par des mesures de transmission sur un banc optique de précision. Ces paramètres ont ensuite été utilisés comme données d’entrée pour la résolution de l’équation de transfert radiatif, effectuée au moyen de la méthode de Monte Carlo. L’accord entre transmissions prédite et expérimentale, tenant compte éventuellement de la diffusion du rayonnement par les bulles d’hydrogène, est bon dans la bande spectrale absorbée. En parallèle, l’utilisation d’un équipement complet et d’une chaine d’acquisition de mesures autour d’un petit photoréacteur d’étude, pour lequel les densités de flux incidentes ont été validées par actinométrie, a permis d’obtenir des résultats expérimentaux de haute précision en photo-production d’hydrogène. Un premier modèle de couplage thermocinétique original a alors été formulé, validé après identification d’un seul paramètre agrégé, dont la réification sera abordée ultérieurement, et utilisé de façon prédictive avec succès. Ce travail ouvre de très nombreuses perspectives de recherche, il a ainsi permis de vérifier la possible transposition à la photosynthèse artificielle de la chaine prédictive de modélisation multi-échelles et donne des pistes quant à l’optimisation cinétique et énergétique des photo-procédés produisant des carburants solaires. / To address the energy challenge of the 21 st century, a solution is the development of solar processes for the production of energy vectors by artificial photosynthesis, in particular photocatalytic synthesis of solar fuels. However high kinetic and thermodynamic performances for these processes must be reached, this requires the development of tools for optimal design, including predictive knowledge models addressing radiative transfer that is the controlling physical process at different scales. A predictive multi-scale model has therefore been developed, implemented and validated on a simple reaction for hydrogen photo-production from CdS particle slurry. On the basis of their characteristics (size, shape, etc.) and their optical properties, the radiative properties of the particles, namely absorption and scattering cross sections and phase function, were calculated using the Lorenz-Mie theory and validated by measurements of transmittances on a high accuracy optical bench. These parameters were then used as input parameters to solve rigorously the radiative transfer equation with the Monte Carlo method. The agreement between predicted and experimental transmittance, taking into account light scattering by hydrogen bubbles, is good in the absorbed spectral band. In parallel, the use of complete experimental bench centered on a small photoreactor, where incident flux densities have been validated by actinometry, yielded high accuracy hydrogen photo-production results. A first and original model of thermokinetic coupling was then formulated and validated after identification of a single lumped parameter whose reification will be approached later and used predictively with success. This work opens up a large number of research prospects because it makes possible to transpose the predictive chain to artificial photosynthesis. This work provides also guidance on the kinetic and thermodynamic optimization of photo-processes producing solar fuels.

Submitted by HUMBERTO FABRIZZI DE FIGUEIREDO PUPO null (betopupo@gmail.com) on 2017-08-31T20:25:11Z No. of bitstreams: 1 Tese_Humberto_Pupo.pdf: 4727522 bytes, checksum: bc9418ef91885cfe96ab6372394b80b6 (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-09-01T14:51:09Z (GMT) No. of bitstreams: 1 pupo_hff_dr_bot.pdf: 4727522 bytes, checksum: bc9418ef91885cfe96ab6372394b80b6 (MD5) / Made available in DSpace on 2017-09-01T14:51:09Z (GMT). No. of bitstreams: 1 pupo_hff_dr_bot.pdf: 4727522 bytes, checksum: bc9418ef91885cfe96ab6372394b80b6 (MD5) Previous issue date: 2017-03-03 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A utilização dos resíduos sólidos como matéria-prima pode diminuir consideravelmente a extração de recursos naturais, diminuindo assim o impacto sobre o meio ambiente. Dentre os resíduos, os plásticos estão entre os que mais apresentam problemas, pois, mesmo quando descartados corretamente nos aterros sanitários, causam danos ao formarem uma camada impermeável que dificulta a compactação do lixo, afetando as trocas de líquidos e gases gerados e reduzindo a eficiência do processo de biodegradação da matéria orgânica. Diante dos problemas, este trabalho teve por objetivos avaliar a viabilidade técnica de utilização de dois tipos de processos: a extrusora dupla rosca e o misturador termocinético (Drais), na produção de compósitos de BOPP (Polipropileno Biorientado metalizado), reforçados com resíduos de cascas, de eucalipto (CE) e de arroz (CA). Das misturas entre esses resíduos, foram confeccionados 10 tratamentos, de onde se extraíram os corpos de provas, moldados por injeção. Foram avaliadas as propriedades mecânicas (flexão – módulo de ruptura-MOR e módulo de elasticidade-MOE, resistência à tração, resistência ao impacto e dureza Shore D), térmicas (avaliação da condutividade térmica e isolamento térmico), termomecânica (temperatura de deflexão sob aquecimento-HDT) e morfológica, com microscópio estéreo e aumento de 50 vezes para analisar a estrutura interna do corpo de prova, depois de fraturado pelo ensaio de impacto. Para análise das propriedades mecânicas dos corpos de provas, foram utilizadas como referência as normas ASTM D638-14, ASTM D790-10, ASTM D256-10 e a ASTM D-2240-15, para os ensaios de tração, flexão, impacto e dureza Shore D, respectivamente. Para as análises térmicas foi utilizada a norma ASTM E1530-11. Para o HDT, foi utilizada a norma ASTM D648-16. Os resultados mostraram influência de todos os parâmetros analisados nas propriedades dos compósitos. O uso de reforço (CE e CA) nos dois tipos de processos melhorou as propriedades de flexão e de resistência à tração em relação à matriz sem reforço e piorou as propriedades de resistência ao impacto e de dureza Shore D. Com relação à matriz sem reforço, a extrusora mostrou influência no ensaio de resistência à tração. Para adição de casca de eucalipto, o misturador termocinético (Drais) mostrou influência no ensaio de MOE. Já para adição de casca de arroz, a drais mostrou influência nos ensaios de flexão – MOR e MOE e na resistência à tração. Houve melhor adesão entre fibra e matriz nos compósitos confeccionados por extrusão em relação aos confeccionados na drais. As CE apresentaram melhor adesão com a matriz, em relação às CA. Os vazios – bolhas de ar foram observados em todos os tratamentos, com exceção dos tratamentos com ausência de reforço (BOPP 100). Esses vazios foram observados em maior proporção nos compósitos com CE em relação aos compósitos com CA, e também nos compósitos processados na extrusora em relação à drais. Os melhores resultados foram obtidos utilizando o misturador termocinético (Drais) e para as maiores proporções de cascas usadas ou na ausência delas. Porém, pelo fato de o processo utilizado na Drais ser por batelada, a extrusora se torna mais eficiente, levando em consideração o rendimento da produção. Os melhores resultados foram com a utilização de casca de eucalipto. Para os ensaios de flexão MOR, MOE e de resistência à tração, apresentaram interação entre os processos e os resíduos testados. Confirmou-se a viabilidade técnica de utilização de resíduos sólidos industriais (BOPP e CE) e agroindustrial (CA) na produção de compósitos fibra-polímero, sendo que o controle dos processos utilizados é fundamental para a qualidade do produto final. / The use of solid waste as raw material can considerably reduce the extraction of natural resources, thus reducing the impact on the environment. Among residues, plastics are among the most problematic ones because, even when they are properly disposed in landfills, they cause damage by forming a barrier layer which makes it difficult to compact the garbage, affecting the exchange of generated liquids and gases, reducing the efficiency of the biodegradation process of the organic matter. Before such problems, the objective of this work was to evaluate the technical feasibility of two types of processes, the double screw extruder and the thermokinetic mixer - dryser, in the production of BOPP (Bioriented metallized Polypropylene) composites, strengthened by residues of barks eucalyptus (CE) and rice (CA). From the mixtures among these residues 10 treatments have been prepared, from where the test bodies were extracted, molded by injection. Mechanical properties (flexurerupture modulus-MOR and elasticity modulus-MOE, tensile strength and impact strength towards Shore D hardness), as well as thermal (thermal conductivity and thermal insulation evaluation), thermo-mechanical (heat deflexion temperature-HDT) and morphological characteristics have been evaluated by using a stereo microscope and 50x magnification to analyze the internal structure of the test body, after being fractured by the impact test. For analyzing the mechanical properties of the proof bodies the standards ASTM D638-14, ASTM D790-10, ASTM D256-10 and ASTM D-2240-15 have been used as a reference for tensile, bending, impact and Shore D hardness tests, respectively. For the thermal analyzes, the ASTM E1530-11. For the HDT the ASTM D648-16 standard was used. The results showed the influence from all the analyzed parameters on the composites properties. The use of reinforcement (CE and CA) in both types of processes have improved the flexure and tensile strength properties in relation to the non-reinforced matrix and has worsened the impact strength properties as well as the Shore D hardness. Concerning the non-reinforced matrix, the extruder showed influence on the tensile strength test. For the addition of CE, the thermokinetic mixer - dryser has showed influence in the flexure modulus test. As for rice husk addition, dryser has showed influence in flexure (stress tests on maximum strengthMOR and elasticity modulus-MOE and tensile strength). There was a better adhesion between fiber and matrix, in the composites made by extrusion, compared to those made in the dryser. The CE has shown better adhesion with the matrix, compared to CA. The voids - air bubbles have been observed in all treatments with no reinforcement (BOPP 100). These voids have been more often observed in composites with CE, compared to the composites with CA and also in composites processed in the extruder, in relation to the dryser. The best results were obtained by using the thermokinetic mixer - dryser and for the largest proportions of the barks or in their absence. However, because the process used in Drais is by batch, the extruder becomes more efficient, taking into account the yield of the production. The best results have been from the use of CE. For flexure - MOR and MOE and tensile strength, there was an interaction among the processes and the tested residues. The technical feasibility of the use of industrial solid wastes (BOPP and CE) and agroindustrial (CA) in the production of fiberpolymer composites has been confirmed, and the control of the processes used is fundamental for the quality of the final product.