La thèse vise l'application du concept de bioraffinerie (extraction, fractionnement, séparation de composés à partir de biomasse avant transformation ultérieure), via le développement d'étapes de production destinées à être associées en un procédé continu. La complexité du solide nécessite une étape de prétraitement effectuée avec une technologie à faible impact environnemental et l'eau subcritique est déjà utilisée comme solvant d'extraction des produits naturels, en sus de leur hydrolyse. Ces travaux ont porté sur l'hydrolyse de polysaccharides (son de riz) et de triacylglycérols (TAG, huile de tournesol) choisis comme modèles. Les caractéristiques de l'eau subcritique (produit ionique, constante diélectrique) mise en œuvre en réacteurs à circulation construits dans ce but, ont permis l'hydrolyse quasi-totale de l'hémicellulose et des TAG. L'addition de CO2 et donc d'acide carbonique a eu un effet positif sur l'hydrolyse de l'hémicellulose. Les acides gras libres résultant de l'hydrolyse ont été estérifiés en ester éthyliques en présence d'une lipase en réacteur continu en milieu CO2 supercritique, avec un taux de synthèse de 95%. Les cinétiques des réactions ci-dessus d'hydrolyse et d'estérification ont été étudiées. La complexité des interactions entre les nombreux paramètres mis en jeu a conduit à appliquer des méthodes de plans d'expérience. Ces méthodes ont été validées avec succès avec les données expérimentales, montrant ainsi leur utilité dans le développement de procédés. La question importante de la solubilité des extractibles dans l'eau subcritique a été traitée et une méthode de prédiction mise au point et validée avec succès avec les données expérimentales. En conclusion, ce travail montre la possibilité d'appliquer le concept novateur de la Bioraffinerie Intégrée en réacteur continu avec des fluides sub- ou supercritique, contrairement à leur mise en œuvre actuelle en réacteur fermé, pour la production de composés commercialisables. / This work addresses the integrated biorefining concept (extraction, fractionation, separation of compounds from biomass prior to further transformation) by developing discrete units with the ultimate objective of coupling them to enable a continuous flow configuration. Due to the complexity of solid, there is a need for a sustainable and environmentally friendly pre-treatment technology. Sub-critical water has been used as a solvent for extracting natural compounds in addition to hydrolysis. This work investigated the hydrolysis of carbohydrates (rice bran) and triacylglycerols (TAG; sunflower oil) chosen as models. The attribute of subcritical water (ion product and dielectric constant) in continuous flow reactors built for the purpose, allowed almost quantitative hydrolysis of hemicellulose and TAG. The effect of adding CO2 and therefore carbonic acid was positive on the hydrolysis of hemicellulose. Further, free fatty acids were transformed to ethyl esters using lipase within continuous flow super critical CO2 resulting in 95% yield. The hydrolysis and esterification reaction kinetics were studied. To address the complex interplay between multiple processing parameters response surface methodologies (RSM) were developed. Using the empirical data the models were successfully validated, therefore showing the utility of the RSM to assist process development. The important question of solubility of extractible in subcritical water was also addressed, through the development of a prediction method, validated with experimental data. In summary this work shows the possibility of applying the innovative Integrated Biorefining concept under continuous flow conditions -instead of the current application under batch conditions- for producing valuable compounds.

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Technology scaling has been the most obvious choice of designers and chip manufacturing companies to improve the performance of analog and digital circuits. With the ever shrinking technological node, process variations can no longer be ignored and play a significant role in determining the performance of nanoscaled devices. By choosing a worst case design methodology, circuit designers have been very munificent with the design parameters chosen, often manifesting in pessimistic designs with significant area overheads. Significant work has been done in estimating the impact of intra-die process variations on circuit performance, pertinently, noise margin and standby leakage power, for fixed transistor channel dimensions. However, for an optimal, high yield, SRAM cell design, it is absolutely imperative to analyze the impact of process variations at every design point, especially, since the distribution of process variations is a statistically varying parameter and has an inverse correlation with the area of the MOS transistor. Furthermore, the first order analytical models used for optimization of SRAM memories are not as accurate and the impact of voltage and its inclusion as an input, along with other design parameters, is often ignored. In this thesis, the performance parameters of a nano-scaled 6-T SRAM cell are modeled as an accurate, yield aware, empirical polynomial predictor, in the presence of intra-die process variations. The estimated empirical models are used in a constrained non-linear, robust optimization framework to design an SRAM cell, for a 45 nm CMOS technology, having optimal performance, according to bounds specified for the circuit performance parameters, with the objective of minimizing on-chip area. This statistically aware technique provides a more realistic design methodology to study the trade off between performance parameters of the SRAM. Furthermore, a dual optimization approach is followed by considering SRAM power supply and wordline voltages as additional input parameters, to simultaneously tune the design parameters, ensuring a high yield and considerable area reduction. In addition, the cell level optimization framework is extended to the system level optimization of caches, under both cell level and system level performance constraints.

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