Une Pile à Combustible Microbienne (PCM) convertit l’énergie chimique issue de l’oxydation de la matière organique directement en énergie électrique. L’oxydation du combustible est assurée par un biofilm dit « électroactif » se développant à la surface de l’anode et jouant le rôle de catalyseur microbien. L’anode microbienne formée à partir d’un consortium bactérien, issu dans cette étude de terreau de jardin, est associée à une cathode à air abiotique à la surface de laquelle se produit la réduction de l’oxygène. L’assemblage d’une anode microbienne et d’une cathode à air abiotique pour construire une PCM est un réel challenge tant les conditions optimales de chacune sont différentes. Ces travaux de thèse ont donc pour objectif d'anticiper le fonctionnement global de la PCM pour concevoir une anode microbienne et une cathode abiotique capables de fonctionner ensemble de façon optimale. Une partie expérimentale conséquente vise à concevoir une PCM optimale en menant des essais sur différents designs de réacteur. Un modèle numérique, basé sur l’expérimentation et calculant les distributions secondaires de courant et de potentiel au sein de la PCM, vient compléter l’étude expérimentale afin d’optimiser l’architecture de la PCM et maximiser les performances délivrées. La configuration « Assemblage Séparateur-Electrodes » consiste à intercaler le séparateur entre la bioanode et la cathode à air dans le but de diminuer la résistance interne du système. Ce design a permis de concevoir des PCMs délivrant d’excellentes performances jusqu’à 6.42 W.m-2. In fine, le prototype « Bioelec », utilisé comme modèle de démonstration, est réalisé à l’échelle du laboratoire avec un assemblage en série et en parallèle de plusieurs PCMs élaborées avec cette configuration « ASE ». / A Microbial Fuel Cell (MFC) can convert the chemical energy contained in low-cost organic matter directly into electrical energy. The oxidation of organic matter is performed by a biofilm known as “electroactive” that develops on the anode surface and acts as a microbial catalyst. The microbial anode, formed from indigenous bacteria of compost leachate, is combined with an abiotic air-cathode catalyzing the reduction of oxygen. The association of a bioanode and an abiotic air-cathode in an MFC is a major challenge as their optimal conditions are so divergent. The purpose of this PhD work is to anticipate the global mechanisms of an MFC in order to develop a microbial anode and an abiotic air-cathode able to operate together in an optimal way. A consequent experimental part aims to develop an optimal MFC by carrying out tests on several reactor designs. A numerical model, based on the experimental results, calculates the secondary distributions of current and potential in the cell. The model supports the experimental study and is used to optimize the MFC architecture and maximize the delivered performances. The configuration “Separator-Electrodes Assembly” consists of sandwiching the separator between the bioanode and the air-cathode in order to decrease the internal resistance of the system. This design provided excellent results as MFCs delivered great power densities up to 6.42 W.m-2. Finally, a prototype “Bioelec”, used as a demonstrative model, was built with several MFCs connected in series or in parallel, each of them designed with the “ASE” configuration.

A literatura corrente possui informações limitadas sobre o projeto da área de troca térmica de tanques com jaqueta, serpentina helicoidal, serpentina espiral e chicana tubular vertical, em operação com fluidos não-Newtonianos. A presente tese teve por objetivo principal analisar a transferência de calor, potência consumida e ampliação de escala em tanques com impulsores mecânicos na agitação de fluidos não-Newtonianos com duas superfícies de transmissão de calor, chicana tubular vertical e serpentina em espiral. O trabalho também visou fornecer métodos de ampliação de escala de tanques com agitação para fluidos não-Newtonianos que sigam o modelo reológico da lei das potências. A unidade experimental contemplou dois tanques de acrílico, com volume de 10 litros e 50 litros, respectivamente, chicanas tubulares verticais e serpentina em espiral. Os impulsores mecânicos utilizados foram o axial com 4 pás inclinadas a 45° e o radial turbina com 6 pás planas. Como fluidos utilizaram-se soluções aquosas de carboximetilcelulose (0,5%, 1,0% e 1,5%), solução aquosa de carbopol 940 (1,5%), solução aquosa de sacarose (50%) e água. Todos os experimentos foram conduzidos em batelada. Com os dados obtidos, empregou-se o uso de regressões para a obtenção da Equação de Nusselt, as quais forneceram valores de coeficiente de determinação ajustados entre 0,83 e 0,89 com Reynolds no intervalo de 20 a 405000, Prandtl na faixa de 4 a 6400 e índice reológico do modelo da lei das potências entre 0,45 e 1,00. Observou-se que no aquecimento realizado com a chicana tubular vertical, o impulsor radial forneceu coeficientes de convecção 20% acima quando comparado com o impulsor axial, entretanto o consumo de potência foi cerca de 66% maior em relação ao impulsor axial. No caso da serpentina espiral, o impulsor axial promoveu coeficientes de convecção por volta de 15% superiores em relação ao impulsor radial com um consumo de potência 65% menor. Desse modo, em processos em que não é necessária uma elevada turbulência, recomenda-se o uso do impulsor axial com a serpentina espiral, porém, se o processo demandar uma turbulência significativa, deve-se usar o impulsor radial com a chicana tubular vertical. Em uma última análise, os modelos não-lineares obtidos para ampliação de escala forneceram erros entre 11% e 20% na predição da rotação no tanque industrial, os quais são válidos para Reynolds modificados de Metzner e Otto (1957) na faixa de 20 a 4000 e para fluidos não-Newtonianos pseudoplásticos com índices reológicos entre 0,45 e 1,00. / Current literature has limited information on the design of the thermal exchange area of tanks with jacket, helical coil, spiral coil and vertical tuber baffle, in operation with non-Newtonian fluids. The main purpose of this thesis was to analyze heat transfer, power consumption and scale-up in tanks with mechanical impellers in the agitation of non-Newtonian fluids with two heat transfer surfaces, vertical tube baffle and spiral coil. The work also aimed to provide methods of scale-up tank scale with agitation for non-Newtonian fluids that follow the rheology model of the law of powers. The experimental unit included two acrylic tanks, with a volume of 10 liters and 50 liters, respectively, vertical tube baffles and spiral coil. The mechanical impellers used were the 45° pitched blade turbine (PBT) and the Rushton turbine (RT). Aqueous solutions of carboxymethylcellulose (0.5%, 1.0% and 1.5%), aqueous solution of carbopol 940 (1.5%), aqueous solution of sucrose (50%) and water were used as fluids. All the experiments were conducted in batch. With the obtained data, we used the regressions to obtain the Nusselt Equation, which provided coefficient of determination values adjusted between 0.83 and 0.89 with Reynolds in the range of 20 to 405000, Prandtl in the range of 4 to 6400 and rheological index of the power law model between 0.45 and 1.00. It was observed that in the heating performed with the vertical tube baffle, the RT provided convection coefficients 20% higher when compared to the axial impeller, however the power consumption was about 66% higher in relation to the PBT. In the case of the spiral coil, the PBT promoted convection coefficients around 15% higher than the RT with 65% lower power consumption. Thus, in processes where high turbulence is not required, it is recommended to use the PBT with the spiral coil, but if the process requires significant turbulence, the RT must be used with the vertical tubular chassis. In a final analysis, the nonlinear models obtained for scaling provided errors between 11% and 20% in the prediction of rotation in the industrial tank, which are valid for Metzner and Otto (1957) modified Reynolds in the range of 20 to 4000 and for non-Newtonian pseudoplastic fluids with rheological indexes between 0.45 and 1.00.

nÃo hà / Given the current situation in which it is the global energy sector, biofuels have been gaining more space, earning special attention the ethanol, which has shown growing demands. From this scenario, the objective of this work was to develop a bioprocess technically and economically practicable for ethanol production from cashew apple juice, using yeast Saccharomyces cerevisiae (CCA008) genetically modified containing a flocculent gene (FLO5α). The work was divided in 4 four stages that are linked throughout the study. In the first stage was evaluated the temperature influence (26, 30, 34, 38 and 42ÂC), the inoculum concentration (3, 5, 8 and 10 g.L-1) and the stirring speed (80, 150, 300, 490, 650 and 800 rpm), so it could be determined the best conditions to maximize ethanol production. It was observed that the temperature operating parameter, the initial cellular concentration, substrate concentration and stirring exerted influence on the alcoholic fermentation of the cashew apple juice. The best performance to the fermentative process (98,8 %) happened when the process was conducted at 34 ÂC, under 150 rpm stirring and 5 g.L-1 of initially cell concentration. The second stage was intended to describe the process efficiency in face of the operation parameters evaluated in fermentation. To this end, it was successfully used statistic models to describe the interaction between the initial substrate concentration, temperature, initial cell concentration, stirring and their possible effects on the yield. The model that best fit the experimental data was used to obtain the optimum conditions from the operating variables, indicating the following conditions as great: substrate concentration (S0) of 102 g.L-1, temperature (T) at 34ÂC, inoculum concentration (X0) of 5 g.L-1 and stirring (Agit) of 140 rpm, predicting a 98,80 % of efficiency. In the third stage was studied ethanol production in optimum conditions, being used to implement the scale up process, in which the data obtained in a 1L bioreactor batch were used to predict the fermentation behavior in a 14L bioreactor batch, using the volumetric power consumption as a parameter to scale-up. Using this factor as being of 10,67 kW/m3, it was possible to calculate the fermenter stirring power in a 14 times bigger volume, as well as foresee which stirring would be necessary so the fermentation can occur, similarly as in the lower volume fermenter. Results showed that yield from the 14L bioreactor were satisfactory, having a small difference (96,56 %  0,3 %) between yield from the 1L bioreactor (98,80 %  1,6 %). The fourth and last stage was rated the technical and economic viability of the process. Analyzing results, it is possible to say the industrial process here proponed has shown technical viability, since the value obtained for the process yield (68 L/ton), was close to sugar cane fermentation (61 â 72 L/ton). However, it did not show economic viability since the industrial unity provides negative cash flow (- R$ 93.840.874) in the end of 10 years that was analyzed. So, new studies must be conducted in order to make this process economically viable, this possibility being observed in various scenarios generated in analyzing the sensibility of process, which presents possible economically viable settings. / Diante da conjuntura atual em que se encontra o setor energÃtico mundial, os biocombustÃveis vÃm ganhando cada vez mais espaÃo, merecendo atenÃÃo especial o etanol, o qual apresenta demanda crescente. A partir desse cenÃrio, o objetivo do presente trabalho foi desenvolver um bioprocesso tecnicamente e economicamente viÃvel para produÃÃo de etanol a partir do suco de caju, utilizando levedura Saccharomyces cerevisiae (CCA008) geneticamente modificada contendo gene floculante (FLO5α). O trabalho foi dividido em 4 quatro etapas que se interligam durante todo o estudo. Na primeira etapa foi avaliada a influÃncia da temperatura (26, 30, 34, 38 e 42ÂC), da concentraÃÃo de inÃculo (3, 5, 8 e 10 g.L-1) e da velocidade de agitaÃÃo (80, 150, 300, 490, 650 e 800 rpm) para que as condiÃÃes Ãtimas que maximizam a produÃÃo de etanol, fossem determinadas. Observou-se que os parÃmetros operacionais de temperatura, concentraÃÃo celular inicial, concentraÃÃo de substrato e agitaÃÃo exerceram influÃncia na fermentaÃÃo alcoÃlica do suco de caju. O melhor rendimento para o processo fermentativo (98,8 %) ocorreu quando o processo foi conduzido a 34 ÂC, sob agitaÃÃo de 150 rpm e contendo incialmente 5 g.L-1 de cÃlulas. Na segunda etapa, pretendeu-se descrever o rendimento do processo em funÃÃo dos parÃmetros operacionais avaliados na fermentaÃÃo. Para tanto, utilizaram-se, com sucesso, modelos estatÃsticos para descrever a interaÃÃo entre a concentraÃÃo inicial de substrato, temperatura, concentraÃÃo celular inicial, agitaÃÃo e seus possÃveis efeitos no rendimento. O modelo que melhor se ajustou aos dados experimentais foi utilizado na obtenÃÃo das condiÃÃes Ãtimas das variÃveis operacionais, indicando as seguintes condiÃÃes como Ãtimas: concentraÃÃo de substrato (S0) de 100 g.L-1, temperatura (T) igual a 34 ÂC, concentraÃÃo de inÃculo (X0) igual a 5 g.L-1 e agitaÃÃo (Agit) de 140 rpm, predizendo um rendimento de 98,80 %. Na terceira etapa, realizou-se o estudo da produÃÃo de etanol nas condiÃÃes Ãtimas, sendo as mesmas utilizadas para implementar a ampliaÃÃo de escala do processo, na qual os dados obtidos em biorreator batelada de 1L foram utilizados para predizer o comportamento da fermentaÃÃo em biorreator batelada de 14L, utilizando a potÃncia por unidade de volume como parÃmetro de scale-up. Utilizando tal fator como sendo de 10,67 kW/m3, foi possÃvel calcular a potÃncia de agitaÃÃo do fermentador de volume 14 vezes maior, assim como prever qual agitaÃÃo seria necessÃria para que a fermentaÃÃo ocorresse de forma semelhante à ocorrida no fermentador de menor volume. Os resultados mostraram que o rendimento obtido no biorreator de 14L foi satisfatÃrio, apresentando uma pequena diferenÃa (96,56 %  0,3 %) para o biorreator de 14L em relaÃÃo ao rendimento obtido para o de 1L (98,80 %  1,6 %). Como quarta e ultima etapa, avaliou-se a viabilidade tÃcnica e econÃmica do processo. Analisando os resultados obtidos, à possÃvel afirmar que o processo industrial proposto apresentou viabilidade tÃcnica, uma vez que o valor obtido para o rendimento do processo (68 L/ton), foi prÃximo ao da fermentaÃÃo da cana-de-aÃÃcar (61 â 72 L/ton). Contudo, o mesmo nÃo apresentou viabilidade econÃmica, uma vez que a unidade industrial proporciona um fluxo de caixa negativo (- R$ 93.840.874) ao final dos 10 anos em que foi analisado. Assim, novos estudos devem ser realizados com o intuito de tornar tal processo economicamente viÃvel, sendo esta possibilidade observada nos vÃrios cenÃrios gerados na anÃlise de sensibilidade do processo, o qual apresenta possÃveis configuraÃÃes economicamente viÃveis.

A conversão de biomassa vegetal em produtos químicos e energia é essencial a fim de sustentar o nosso modo de vida atual. O bagaço de cana-de-açúcar, matériaprima disponível em abundância no Brasil, poderá tanto ajudar a suprir a crescente demanda pelo etanol combustível como ser empregado para obtenção de produtos de valor agregado, tais como xilitol, além de trazer vantagens econômicas para o setor sucroalcooleiro. O xilitol, um poliol com poder adoçante semelhante ao da sacarose e com propriedades peculiares, como metabolismo independente de insulina, anticariogenicidade e aplicações na área clínica, no tratamento de osteoporose e de doenças respiratórias, é obtido em escala comercial por catálise química de materiais lignocelulósicos. A produção biotecnológica de xilitol como alternativa ao processo químico vem sendo pesquisada e os resultados revelam que a presença de compostos tóxicos nos hidrolisados hemicelulósicos resultantes do processo de hidrólise ácida contribui para sua baixa fermentabilidade. Isto se deve à inibição do metabolismo microbiano causada principalmente por compostos tais como ácidos orgânicos, fenólicos e íons metálicos. No presente trabalho foi avaliado o efeito de diferentes fontes de carbono (xilose, glicose e mistura de xilose e glicose) empregadas no preparo do inóculo de Candida guilliermondii FTI 20037 sobre a bioconversão de xilose em xilitol a partir de fermentações em frascos Erlenmeyer de hidrolisados hemicelulósicos submetidos a procedimentos de destoxificação. A condição de favorecimento deste bioprocesso foi empregada para a avaliação da ampliação de escala em fermentadores de 2,4L para 16L, utilizando como critério de ampliação o KLa (igual a 15h-1). De acordo com os resultados, os máximos valores dos parâmetros fermentativos como fator de conversão de xilose em xilitol e produtividade em xilitol foram alcançados com a utilização de inóculo obtido em xilose durante fermentação do hidrolisado destoxificado por resinas (YP/S = 0,81 g g-1 e QP = 0,60 g L-1 h-1, respectivamente), embora o emprego de carvão ativado tenha gerado valores de rendimento próximos para as diferentes fontes de carbono (YP/S variando de 0,78 a 0,80 g g-1). Considerando o valor de fator de conversão e que o procedimento de destoxificação com carvão ativado é o de menor custo e de mais fácil manipulação em comparação ao processo com resinas, os experimentos de ampliação de escala da produção de xilitol por C. guilliermondii foram realizados nesta condição de destoxificação e empregando-se xilose como fonte de carbono para o inóculo. Nesta etapa ficou evidente a viabilidade de ampliação de escala de produção de xilitol de fermentador de 2,4L para 16L, já que os valores dos parâmetros fermentativos avaliados foram semelhantes entre os fermentadores (valores médios: YP/S ≈ 0,68 g g-1 e QP ≈ 0,28 g L-1 h-1). No entanto, tais valores foram inferiores aos obtidos em frascos Erlenmeyer, possivelmente devido às condições de disponibilidade de oxigênio diferirem nos fermentadores de bancada, uma vez que o oxigênio é o parâmetro mais crítico neste bioprocesso. / The conversion of vegetable biomass into chemicals and energy is essential to sustain our current style of life. Sugarcane bagasse, a raw material abundantly available in Brazil, greatly contributes to the supply of the evergrowing demand for ethanol. Furthermore, biomass can be employed for obtaining value-added products, such as xylitol, as well as bring economical advantages for the sugar-ethanol sector. Xylitol, a polyol with sweetener power similar to that of saccharose and peculiar properties such as insulin-independent metabolism, anticariogenic power, and applications in the clinical area, in the treatment of osteoporosis and respiratory diseases, is obtained on a commercial scale by chemical catalysis of lignocellulosic materials. The biotechnological production of xylitol as an alternative to the chemical process has been researched and the results reveal that the presence of toxic compounds in hemicelllosics hydrolysates resulting from acid hydrolysis process contributes to its low fermentability. Such toxicity could be due to the inhibition of microbial metabolism promoted mainly by compounds such as organic acids, phenols and metallic ions. In the present work, the effect of different carbon sources (xylose, glucose and a mixture of xylose and glucose) used in the inoculum preparation of Candida guilliermondii FTI 20037 for the xylose-to-xylitol bioconversion by fermentation of hemicellulosics hydrolysates submitted to detoxification procedures in Erlenmeyer flasks was evaluated. The best condition for this bioprocess was employed to evaluate the scale up from the 2.4L to 16L fermentors, using KLa (equal to 15h-1) as scale-up criteria. According to the results the highest values of fermentative parameters such as xylitol yield and productivity were achieved with the use of inoculum cultivated on xylose during the fermentation of hydrolysate detoxified with resins (YP/S = 0.81 g g-1 and QP = 0.60 g L-1 h-1, respectively), although with the use of charcoal the yield value was similar (YP/S ranging for 0.78 to 0.80 g g-1), regardless of the carbon source employed. Considering the value of xylitol yield and that detoxification with activated charcoal is less expensive and more easily manipulated when compared to detoxification procedure with resins, the experiments for scale up xylitol production by C. guilliermondii were performed in such detoxification condition with xylose as the carbon source for the inoculum. At this stage it was evident the scale up xylitol production from a fermenter of 2.4L to 16L was feasible, since the values of fermentative parameters evaluated were similar to those of the fermentors (medium values YP/S ≈ 0.68 g g-1 e QP ≈ 0.28 g L-1 h-1). However, these values were lower than those obtained in Erlenmeyer flasks, maybe due to conditions of oxygen availability for they differ from those in fermentors, since oxygen is the most critical parameter in this bioprocess.

O trabalho visa o desenvolvimento do sistema para medidas de distribuição de corrente e ampliação de escala (50 cm²) buscando aperfeiçoar as condições de preparação do conjunto eletrodo membrana (MEA) quanto às condições de operação da célula e avaliar a melhor geometria. Foram realizados estudos de síntese de catalisadores de Pt-M e avaliação do desempenho desses materias e das rotas de síntese utilizadas com objetivo de aplicar estes materias em sistemas de maior escala. A insuficiência do desempenho e estabilidade dos catalisadores são fatores que ainda inviabilizam o uso em larga escala das células a combustível de eletrólito polimérico sólido, destacando-se as perdas associadas ao desempenho do cátodo. Os catalisadores preparados foram nanopartículas bimetálicas PtM/C (M = Fe, Co e Ni) suportadas em carbono de elevada área superficial, por duas rotas sintéticas. Foram utilizadas as rotas: ácido fórmico e etilenoglicol modificado (EG). Em ambas as rotas se buscou catalisadores com alto grau de incorporação do segundo metal, tamanho de partícula pequeno e bom desempenho catalítico do cátodo. Observou-se que pela rota do ácido fórmico com modificações no processo de síntese é possível obter a incorporação nominal do segundo metal no catalisador, porém há desvantagem de o tamanho de partícula ser elevado. Pela rota do EG obteve-se catalisadores com pequeno tamanho de partícula, porém a incorporação do segundo metal mostrou-se ineficiente. Os estudos de ampliação de escala foram realizados em células de 50 cm2 variando-se as condições de operação; i) diferentes placas de distribuição de gás, e ii) diferentes valores de fluxo dos gases reagentes. Foi observado que a baixos fluxos de gases a quantidade de reagente é insuficiente para ser difundida por todo eletrodo, o que ocasiona reação apenas na região de entrada de gases no sistema, ocasionando uma rápida limitação em obter-se densidades de corrente alta. Pode-se observar que a diferença de desempenho entre as placas é pequena, porém a placa serpentina 6 apresentou melhor desempenho. O desempenho dos cátodos preparados com catalisadores comerciais e os sintetizados no laboratório nas células de 50 cm² mostrou sofrer bastante influência das condições de operação comparada com as células de 4,6 cm². / The work aims at the development of the system for current distribution measurements and scale (50 cm²) seeking to improve the conditions of preparation of the membrane electrode assembly (MEA) as the cell operating conditions and evaluate the best geometry. We were performed catalyst synthesis studies of Pt-M and performance evaluation of these materials and the synthetic routes used in order to apply these materials in larger-scale systems. The failure of the performance and stability of the catalysts are factors that make yet infeasible the scale up use for solid polymer electrolyte fuel cells, highlighting the losses associated with the performance of the cathode. The nanoparticles of bimetallic catalysts Pt-M/C (M = Fe, Co and Ni) supported on high surface area carbon were prepared by two different synthetic routes. The synthesis route utilized were formic acid and modified ethylene glycol (EG). In both route search catalysts with a high degree of incorporation of the second metal, small particle size and good catalytic performance. It was observed that the route of formic acid with modifications in the synthesis process it is possible to obtain the average incorporation of the second metal in the catalyst, but there is a disadvantage of the particle size is high. The route of EG modified was obtained catalysts with small particle size, but incorporation of the second metal was inefficient. The scale-up studies were performed in 50 cm2 cell varying operating conditions: i) different gas distribution plates and ii) different values of flow of reactant gases. It was observed that at low gas flows the amount of reagent is insufficient to be spread throughout the electrode, causing reaction only in the region of entry of gases in the system, causing a fast limitation in obtain high current densities. It can be observed that the performance difference between the plates is small, but the plate serpentine 6 showed the best performance. The performance of the cathodes prepared with commercial catalysts and synthesized in the laboratory in 50 cm² cells showed considerable influence the operating conditions compared to cells 4,6 cm².

L’objectif principal de ce travail est de produire des pièces massives nanostructurées à partir des nanomatériauxd’alliages anisotropes à base des éléments de transition 3d (Co et Ni). Afin d’utiliser ces nanomatériaux àl’échelle industrielle, nous avons extrapolé la méthode de synthèse de l’échelle du laboratoire (procédé polyol) àl’échelle pilote. Tout d’abord, nous avons montré qu’en variant les paramètres de synthèse à l’échelle delaboratoire, nous pouvons contrôler non seulement la morphologie mais aussi la taille et la distribution de tailledes nanoparticules. En effet, des sphères de diamètre 10 nm et des nanofils de longueur 260 nm et de diamètre 7nm ont été obtenus pour la stoechiométrie Co80Ni20. Les paramètres clés de cette étude sont la concentration dela soude, le taux de l'agent nucléant, la vitesse d’agitation et le champ magnétique externe appliqué. Le choix dusystème de mélange approprié pour une géométrie du réacteur donnée a également un rôle important dans lecontrôle et la maîtrise de la taille et la forme des nanofils. Avec une turbine Rushton à six pâles droites, nousavons obtenu des nanofils plus courts avec de plus petites têtes coniques et une forte coercitivité. Par ailleurs, larésolution numérique des équations de Navier-Stocks qui gouvernent le transport de matière et de la quantité demouvement dans un fluide agité a permis d’obtenir une corrélation entre les profils d’énergie turbulente dissipéeet la taille des nanoparticules mesurée expérimentalement. Les études magnétiques montrent que les propriétésmagnétiques des nanofils sont intimement liées à leur forme et à leur taille. La synthèse à grande échelle apermis de produire 25 grammes de nanofils de cobalt-nickel par batch. Grâce au procédé de frittage SPS, nousavons élaboré avec succès des matériaux massifs nanostructurés à partir de la poudre formée des nanofils. Alorsque les nanofils présentent des champs coercitifs élevés et des aimantations relativement faibles, les matériauxdenses consolidés par SPS possèdent les caractéristiques d’un ferromagnétisme doux (faible champ coercitif)mais une aimantation à saturation élevée proche de celle attendue. Des champs coercitifs meilleurs sont obtenusavec le matériau dense nanostructuré élaboré en présence d’un champ magnétique permanent. Ce champmagnétique a permis un meilleur alignement des nanofils au cours du frittage. Le comportement mécanique desmatériaux nanostructurés dépend essentiellement de la taille des grains. La dureté et la résistance mécaniqueaugmentent quand la taille des grains diminue conformément à la relation de Hall-Petch. / The main objective of this PhD work is to produce nanostructured bulk from anisotropic nanomaterials alloysbased on 3d transition elements (Co and Ni). For using these nanomaterials on an industrial scale, we haveextrapolated the synthesis method (polyol process) from laboratory scale to pilot scale. First, we showed that byvarying the parameters synthesis in laboratory scale we can control not only the morphology but also the size andthe size distribution of the nanoparticles. Indeed, spheres with diameter of 10 nm and nanowires with meanlength of 260 nm and a diameter of 7 nm were obtained for a stoichiometry Co80Ni20. The key parameters of thissynthesis are the concentration of the sodium hydroxide, the nucleation rate, the agitation and the appliedexternal magnetic field. The choice of suitable mixing system for a given geometry of the reactor also has animportant role for the control of the size and shape of the nanowires. When a six-bladed Rushton turbine wasused, shorter nanowires with unconventional small conical-shaped heads and a higher coercive field wereobtained, confirming a strong relationship between flow patterns and nanowire growth. Moreover, numericalresolution of Navier-Stocks equations that govern the transport of matter and quantity of movement in anagitated fluid allowed us to obtain a correlation between turbulent energy dissipation profiles and nanoparticlesize measured experimentally. Magnetic studies revealed a narrow relationship between the magnetic propertiesand the shape of nano-objects. The large-scale synthesis has produced 25 grams of cobalt-nickel nanowires perbatch. Thanks to the SPS sintering process, we have successfully elaborated nanostructured bulk materials.Whereas nanofils show high coercive field and low saturation magnetization, dense materials produced at hightemperatures behave as soft ferromagnetic materials (low coercivity) but show high saturation magnetizationvery close to that expected. The best coercivities are obtained with the bulk nanostructured material using SPSassisted by a permanent magnetic field. This magnetic field succeeded to align the nanowires during sintering.The mechanical behavior of the nanostructured materials depends mainly on the grain size. Hardness andmechanical resistance increase when the grain size decreases in agreement with the Hall-Petch relationship.

Submitted in fulfillment of the requirements for the degree of Doctor of Philosophy (PhD) Health Science, Durban University of Technology, Durban, South Africa, 2017. / Background: The HIV pandemic has attracted unprecedented scale-up in resources to curb its escalation and manage those afflicted. Although evidence from developing countries suggests that public health systems have been strengthened as a result of scale-up, only anecdotes exist in other countries. Despite scale-up, the prevalence of HIV/AIDS is still high and the resultant mortality and morbidity demands a refocus. Furthermore, the HIV/AIDS epidemic has severely strained vulnerable health systems in developing countries leading to concerns among policy makers about non-HIV priority services. Although anecdotally, it is clear that HIV scale-up has had profound effects on health systems, available evidence does not allow for an assessment of the impact of such effects on health care access, service delivery or medical outcomes for non- HIV conditions. The aim of this study was to determine the impact of HIV/AIDS scale-up on non-HIV priority services in the former Nyanza Province, Kenya. Additionally we determined the benefits and detriments of HIV programmes, and identified the elements of successful HIV programs and their effect on scale-up and last but not least determined the perceptions, attitudes and experiences of health care staff towards scale-up and integration of health care services. The first part of the main sequential study reviewed practices during scale-up by looking at public health facilities within the Province at Nyanza in Kenya. This looked at health management information systems (HMIS) and routine health facility client records for five years, 2009-2013 with a comparison of trends in 2009 to that in 2013. This data was reviewed in order to show trends in delivery of HIV priority and non-HIV services. The second part of the study utilized a prospective cross sectional survey to determine perceptions, attitudes and experiences xi of facility personnel towards HIV/AIDS scale up. Randomly sampled facilities involved in the delivery of any aspects of HIV diagnosis care and treatment were investigated. Self-administered questionnaires and in-depth interviews were used to obtain information on impact of HIV services on non-HIV priority services on health managerial staff in the facilities and key informants who have shaped scale up. We created a qualitative codebook based on three major themes identified from the data: (1) Meaning and importance of HIV scale-up (2) Perspectives of scale-up on service delivery on non-HIV services and (Ministry of State for Planning) Health facility staff awareness. The findings indicate that the interventions that were utilized in the scale-up of HIV in 2009 resulted in significant increases in uptake of the service in 2013 (p<0.01) and total integration of HIV and non-HIV services at all the health facilities thereby contributing to improved health outcomes beyond those specifically addressed by HIV programs. This study has also shown that utilization of both HIV and non-HIV services increased significantly for both years after integrated HIV care was introduced in the health facilities (p<0.01). Notable increases were found for ANC utilization (p=0.09), family planning (p=0.09), screening for tuberculosis and malaria (p<0.01) and provision of support services (p<0.01) to HIV infected people. The scale up of HIV in the region had several human resource policy implications resulting from staff turnover and workload. Stakeholder engagement and sustainability are critical in the sustenance of these initiatives. Strategic alliances between donors, NGOs and the government underpinned the scale-up process. Policies around scale-up and health service delivery were vital in ensuring sustainability of scale- up and service integration. This study has attempted to provide evidence on the impact of HIV scale-up on non-HIV service delivery in three different settings, in two different time periods and it therefore concludes that the evidence is mixed with most of the impact being positive with some aspects that still needs development. It is critical to pursue the integration of HIV and non- HIV services in a strategic and systematic manner so as to maximize the public health impact of these efforts. The proposed model, best practices and practices requiring improvement will be communicated to the relevant ministries to ensure its integration into policy. / D

L'objectif de cette thèse est de mettre en place des outils permettant l'éco-purification de produits naturels par chromatographie de partage centrifuge (CPC), une technique préparative permettant la séparation de composés grâce à un système solvant constitué de deux liquides non miscibles. Ce manuscrit expose dans un premier temps une brève présentation des différentes techniques préparatives fréquemment utilisées pour la purification de produits naturels, puis détaille la technique de chromatographie de partage centrifuge. Le concept de chimie verte est alors introduit avant d'exposer la manière dont il sera pris en compte par la suite. Ainsi, un développement de méthode CPC à petite échelle, dans le but de limiter la consommation de solvants et la production de déchets, tout en limitant la consommation d'énergie, est illustré par la purification du carnosol issu du romarin. Par la suite, une nouvelle méthodologie de changement d'échelle en CPC est introduite, afin de pouvoir augmenter de manière efficace la productivité d'une méthode de purification, sans avoir à la redévelopper à grande échelle. L'utilisation de cette méthodologie peut notamment permettre à un utilisateur CPC de réduire considérablement sa consommation de solvants et d'énergie, tout comme sa génération de déchets chimiques. Cette méthodologie de changement d'échelle est appliquée dans le cadre de la purification du carnosol développée en amont. Enfin, la dernière partie de ces travaux est consacrée à la substitution de solvants d'origine pétrolière, par des solvants plus respectueux de l'environnement, principalement d'origine agro-sourcée / The main objective of this thesis is to propose some clues for natural products eco-purification by centrifugal partition chromatography (CPC), a preparative separation technique that uses a biphasic solvent system. First, the manuscript describes the differents preparative techniques commonly used for natural products purification. Then, the centrifugal partition chromatography technique is detailed. The green chemistry concept is subsequently introduced and discussed in regard to its application in purification process. A method development is realized on a small scale CPC, illustrating the reduction of solvent consumption and waste production, through the carnosol purification from rosemary. Later, a new scale-up methodology for CPC is introduced to efficiently transfer the method on larger instrument and increase production. This new methodology will allow for a CPC user to reduce solvent and energy consumption and chemical wastes discharges. This scale-up methodology is then applied to carnosol purification from a rosemary solid extract. Finally, the last part of this manuscript is devoted to petroleum solvents substitution by more environmentally friendly solvents like bio-sourced solvents

Le fractionnement supercritique est un procédé prometteur avec un potentiel d’application encore peu exploité à grande échelle. Les travaux expérimentaux et la discussion théorique qui font l’objet de cette thèse ont pour objectif d’apporter des outils fiables permettant d’effectuer la mise en œuvre d’un procédé de fractionnement supercritique à l’échelle industrielle, en abordant le changement d’échelle et la modélisation du procédé. La première partie du travail porte sur le fractionnement de mélanges éthanol-eau en utilisant du dioxyde de carbone supercritique à 333 K et 10 MPa, sur des unités de fractionnement à échelle du laboratoire, pilote et industrielle, avec des diamètres de colonne respectivement de 19, 58 et 126 mm. Les compositions des produits obtenues, ainsi que les prédictions d’un modèle d’étages d’équilibres, montrent une bonne concordance. Le phénomène d’engorgement est discuté suite à son observation. Une corrélation permettant d’estimer la capacité d’engorgement d’une colonne garnie à contre-courant sous pression est proposée, après avoir exprimé l’ensemble des données répertoriées dans la littérature sous forme adimensionnelle. Les possibles sources de déviations observées sont également discutées afin de proposer des perspectives à ce travail. Enfin, le traitement de mélanges complexes est abordé par la mise en œuvre et la modélisation du fractionnement supercritique d’éthyl esters issus d’huiles de poisson, sous des conditions de 14.5 MPa et 333 K, en variant le rapport solvant sur charge entre 21,8 et 143. Un modèle simplifié est développé afin de représenter l’influence du taux d’extraction sur la composition de l’extrait et du raffinat. / Supercritical fractionation is a promising process with a great potential but with little current large-scale applications. The experimental work and theoretical discussion in this dissertation aim providing tools for the implementation of an industrial-scale supercritical fractionation process by covering aspects such as scale-up and process modeling. In order to do so, three principal axes are discussed. Firstly, the fractionation of ethanol-water mixtures by supercritical carbon dioxide at 333 K and 10 MPa was studied using fractionation units at laboratory, pilot and industrial scale with column diameters of 19, 58 and 126 mm, respectively. The extract and raffinate compositions obtained show good agreement between different scales and with the predictions of an equilibrium-stage model. The flooding phenomenon is also discussed after being detected under certain conditions. A correlation to estimate the flooding capacity of a countercurrent column at high pressure conditions is proposed following a dimensionless representation of the available experimental results presented in the literature. The possible sources for deviations found are also discussed in order to propose future works. Then, the treatment of complex mixtures is tackled by modeling and supercritical fractionation of fatty acid ethyl esters derived from fish oil under 14.5 MPa and 333 K, varying the solvent-to-feed ratio between 21.8 and 143. A simplified model derived from the group method is developed to represent the influence of the extract yield on the composition of the extract and raffinate.

La lyophilisation est le procédé de choix dans l'industrie pharmaceutique pour la stabilisation de produits thermosensibles tels que les vaccins. Cependant, en raison du pré-conditionnement du produit dans des flacons individuels, ce processus est difficile à concevoir et aboutit souvent à des lots présentant une hétérogénéité significative dans la qualité du produit final. L'objectif principal de ce doctorat a été le développement d'un modèle mathématique pour la conception du processus de lyophilisation à un niveau de risque donné, c'est à dire un pourcentage de flacons potentiellement non conformes. Le travail a porté sur la compréhension et la quantification des sources possibles responsables de la variabilité des transferts de chaleur et de matière lors du processus. Dans un premier temps, la variabilité du transfert de chaleur entre les flacons a été étudiée en considérant les dimensions du flacon et sa position sur l'étagère de l'équipement. La variabilité des dimensions géométriques observées dans un lot de flacons (i.e., l'aire de contact entre l'étagère et le flacon et la profondeur de concavité du fond) a influencé la distribution du coefficient de transfert de chaleur entre les flacons. De plus, un modèle mathématique original en 3D a été développé dans COMSOL Multiphysics pour expliquer et prédire les transferts de chaleur atypiques observés dans les flacons situés sur les bords de l'étagère lors du processus de lyophilisation. Les phénomènes conductifs à basse pression au sein de la vapeur d'eau ont été reportés comme un mécanisme dominant expliquant ces transferts de chaleur atypiques alors que les phénomènes radiatifs liés à la présence des parois de l'équipement ont toujours été cités dans la littérature. Par ailleurs, ce modèle mathématique en 3D a été utilisé pour étudier l'effet de la configuration de chargement du lyophilisateur et des caractéristiques de l'équipement sur la variabilité du transfert de chaleur. Dans un deuxième temps, la variabilité des transferts de matière a été évaluée sur une solution de saccharose à 5 % en considérant deux paramètres, la résistance de la couche sèche au transfert de matière pendant la sublimation et le temps caractéristique de désorption. La résistance à la couche sèche a été évaluée en combinant deux approches complémentaires, les tests de remontée de pression et la méthode gravimétrique. La variabilité estimée de la résistance à la couche séchée a eu un impact plus important sur la distribution de la température du produit que la variabilité du coefficient de transfert de chaleur. La valeur et la variabilité du temps caractéristique de désorption ont été évaluées pour différentes températures et ont permis de simuler l'hétérogénéité de la teneur en eau finale entre les flacons. Dans la dernière partie du travail, les principales sources quantifiées de variabilité des transferts de chaleur et de matière ont été intégrées dans un modèle mathématique de lyophilisation. Ce modèle dynamique multi-flacons a été utilisé non seulement pour prédire l'évolution de la température et de la teneur en eau du produit pendant la lyophilisation pour un lot de 100 flacons, mais aussi pour estimer le pourcentage de flacons potentiellement non conformes. L'approche de modélisation proposée, étendue à un plus grand nombre de flacons simulés, pourrait être utilisée pour calculer les "design spaces" (espaces de travail) des étapes de dessiccation primaire et secondaire du processus de lyophilisation à un risque connu de pourcentage de flacons non conformes. / Freeze-drying is the process of choice in pharmaceutical industry for the stabilization of heat sensitive products such as vaccines. However, due the product pre-conditioning in individual vials, this process is difficult to design and often results in batches presenting a significant heterogeneity in the quality of the final product. The main goal of this Ph.D. project was the development of a mathematical model making it possible to predict the risk of failure when designing the freeze-drying process, i.e., the percentage of "rejected vials". To this end, the work focused on the understanding and quantification of the sources responsible for heat and mass transfer variability during the process. Firstly, the vial-to-vial heat transfer variability was investigated by taking the vial bottom dimensions and the vial position on the shelf of equipment into account. The variability of geometrical dimensions observed within a batch of vials (i.e., contact area between the shelf and the vial and the mean bottom curvature depth) moderately influenced the heat transfer coefficient distribution among vials (by less than 10 %). Secondly, a original 3D mathematical model was developed in COMSOL Multiphysics to explain and predict atypical heat transfer observed in vials located at the border of the shelf during the freeze-drying process. Conduction through low-pressure water vapour appeared as the dominant mechanism explaining the additional heat transfer to border vials rather than as reported in literature radiation from the walls of the drying chamber. Furthermore, this 3D mathematical model was used to investigate the effect of the vial loading configuration and of the equipment characteristics on heat transfer variability. In a second part, mass transfer variability was quantified on a 5% sucrose solution and by focusing on two parameters, the resistance of the dried layer to mass transfer during sublimation and the characteristic desorption time. The dried layer resistance was assessed by combining complementary approaches, the pressure rise test and gravimetric methods. The estimated variability of the dried layer resistance was found to have a higher impact on the product temperature distribution than the heat transfer coefficient variability. The value and variability of characteristic desorption time was evaluated for different temperatures and made it possible to simulate moisture content heterogeneity between vials in the batch. In the last part of the work, the main quantified sources of heat and mass transfer variability were integrated in a mathematical model of freeze-drying process. This multi-vial, dynamic model was used not only to predict the evolution of product temperature and moisture content during freeze-drying for a batch of 100 vials, but also to estimate the percentage of vials that could potentially be rejected. The proposed approach, extended to a greater number of simulated vials, could be applied to calculate design spaces of the primary and secondary drying steps of freezedrying process at a known risk of failure.