Cette thèse vise à la production de poudre de polymère par un procédé continu, en une seule étape et supprimant l'utilisation des solvants organiques en faveur de celle du CO2 supercritique. Avant de développer le procédé, une caractérisation du mélange CO2/polymère a été effectuée. Des mesures de solubilité, de gonflement et de coefficient de diffusion du CO2 ont été réalisées et représentées par différents modèles. De plus, une technique de rhéologie capillaire en ligne a été développée, permettant la mesure de viscosité du polymère, seul ou en mélange, avec le CO2 dans les conditions du procédé. Un montage batch a ensuite permis de tester l'influence des paramètres opératoires sur de faibles quantités. Parallèlement, le procédé continu a été étudié sur une extrudeuse équipée d'outils de mélange du CO2 dans le polymère fondu. L'efficacité et l'homogénéité du mélange ont été étudiées à travers la fabrication de mousses de polymères et la réalisation de distributions de temps de séjour par spectroscopie Raman en ligne. L'ajout d'un dispositif de pulvérisation spécifique a conduit à l'obtention de poudres d'aspect fibreux avec deux populations de tailles. / Polymer powders are widely used in industry and are traditionally manufactured by processes using organic solvent or by grinding low molecular weight polymers with a post-polymerization step. This thesis aimss at the generation of polymer powders with a single-step continuous process, based on the use of supercritical CO2, hence without organic solvent. Before developing this process, the characterization of the mixture CO2/polymer was done. Solubility measurements were carried out and fitted with the Sanchez-Lacombe equation of state. Moreover, a capillary rheometry technique was implemented on-line, allowing the measurement of the viscosity of the polymer alone or in mixture with CO2, under process conditions. The modeling of swelling as a function of time led to the evaluation of the diffusion coefficient of CO2 into the polymer. Afterwards, two experimental devices were designed. A batch process with a pressurized autoclave was used to determine the influence of experimental parameters on powder production, with small amounts of material. Formation of small fibrous particles was obtained. In parallel, the continuous process was studied on an extruder adapted to CO2 introduction and equipped with mixing devices. This study, which led to foam manufacture, was used to evaluate efficiency and homogeneity of the mixing. Residence time distributions were determined by Raman spectroscopy on the die in order to evaluate the flowing in the extruder under different conditions. The equipment was also fitted with a specific nozzle allowing co-injection of hot air. Production of fibrous particles with two different size ranges was obtained.

The impact strength of Nylon 6 was improved by adding Ethylene- n-Butyl acrylate- maleic anhydride (E-nBA-MAH) terpolymer with various concentrations from 0% (w/w) to 15% (w/w). The bare interaction energy between two polymers was investigated by using melting point depression approach utilizing both the Flory-Huggins (FH) theory and the Sanchez-Lacombe Equation of State (SL EOS). The solution of the mixture was electrospun, and the effects of process parameters on the expected radii of nanofibers were investigated. The effects of process parameters such as polymer concentration in solution, electrical field, diameter of syringe needle, feed rate, and collector geometry on nanofibers were studied. The statistical analysis to relate these parameters on the diameter of nanofibers was carried out by using Johnson SB distribution. The ratio of elastic modulus to viscosity coefficient of nanofibers was worked out by using AFM and combined viscoelastic models. The experiments were carried out on single fiber. The ratio came out to be a function of nanofiber diameter and terpolymer concentration. Isothermal crystallization kinetics and WAXS diffraction patterns of blends revealed and also SEM images supported that after 5% addition of elastomeric terpolymer, the interaction between the components of the blend gets weaker. The elastic modulus of the blend with 5% of terpoymer was greater than that of the neat Nylon 6, but the elastic modulus decreased for the blends containing more than 5% terpolymer.

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