The aim of this thesis is the investigation of modeling and optimization particularities of tubular polymerization reactors. The original work is divided in two sections, the first treating a modeling and optimization study of tubular reactors for methyl methacrylate polymerization in solution, and the second, an experimental and theoretical study of L-lactide reactive extrusion. In the first section, reactor simulations in similar operating conditions were performed in order to select a representative kinetic model among the published kinetic models for MMA solution polymerization. Two widely used numerical algorithms, one based on Pontryagin's Minimum Principle and the other a Genetic Algorithm, were compared for an average-complexity optimization problem. The results showed a superior robustness of the Genetic Algorithm for this category of problems. The second part of the thesis deals with the modeling and optimization of L-lactide reactive extrusion. A kinetic model is proposed and its parameters estimated using nonlinear estimation numerical procedures based on experimentally measured data. Reactive extrusion experiments were performed in representative operating conditions. The Llactide/ polylactide flow in the extruder was characterized by simulation using the commercial software LUDOVIC®. The simulated residence time distributions characteristics are used to model the reactive extrusion process of two approaches, an axial dispersion model and a compartment model, based on compartments whose characteristics are deduced from the simulations using LUDOVIC®. The modeling results are in good agreement with the measured data in the same operating conditions.

This research investigates formulation, compounding and thin-wall injection moulding of Polypropylene/clay nanocomposites (PPCNs) prepared using conventional melt-state processes. An independent study on single screw extrusion dynamics using Design of Experiments (DoE) was performed first. Then the optimum formulation of PPCNs and compounding conditions were determined using this strategy. The outcomes from the DoE study were then applied to produce PPCN compounds for the subsequent study of thin-wall injection moulding, for which a novel four-cavity injection moulding system was designed using CAD software and a new moulding tool was constructed based upon this design. Subsequently, the effects of moulding conditions, nanoclay concentration and wall thickness on the injection moulded PPCN parts were investigated. Moreover, simulation of the injection moulding process was carried out to compare the predicted performance with that obtained in practice by measurement of real-time data using an in-cavity pressure sensor. For the selected materials, the optimum formulation is 4 wt% organoclay (DK4), 4 wt% compatibiliser (Polybond 3200, PPgMA) and 1.5 wt% co-intercalant (erucamide), as the maximum interlayer spacing of clay can be achieved in the selected experimental range. Furthermore, DoE investigations determined that a screw speed of 159 rpm and a feed rate of 5.4 kg/h are the optimum compounding conditions for the twin screw extruder used to obtain the highest tensile modulus and yield strength from the PPCN compounds. The optimised formulation of PPCNs and compounding conditions were adopted to manufacture PPCN materials for the study of thin-wall injection moulding. In the selected processing window, tensile modulus and yield strength increase significantly with decreasing injection speed, due to shear-induced orientation effects, exemplified by a significantly increased frozen layer thickness observed by optical microscopy (OM) and Moldflow® simulation. Furthermore, the TEM images indicate a strong orientation of clay particles in the flow direction, so the PPCN test pieces cut parallel to the flow direction have 36.4% higher tensile modulus and 13.6 % higher yield strength than those cut perpendicular to the flow direction, demonstrating the effects of shear induced orientation on the tensile properties of thin-wall injection moulded PPCN parts. In comparison to injection speed, mould temperature has very limited effects in the selected range investigated (25-55 °C), in this study. The changes in moulding conditions show no distinctive effects on PP crystallinity and intercalation behaviour of clay. Impact toughness of thin wall injection moulded PPCN parts is not significantly affected by either the changes in moulding conditions or clay concentration (1-5 %). The SEM images show no clear difference between the fracture surfaces of PPCN samples with different clay concentrations. TEM and XRD results suggest that higher intercalation but lower exfoliation is achieved in PPCN parts with higher clay content. The composites in the thin sections (at the end of flow) have 34 % higher tensile modulus and 11 % higher yield strength than in the thicker sections, although the thin sections show reduced d001 values. This is attributed to the significantly enhanced shear-induced particle/molecular orientation and more highly oriented frozen layer, according to TEM, OM and process simulation results. In terms of the reduced d001 values in the thin sections, it is proposed that the extreme shear conditions in the thin sections stretch the PP chains in the clay galleries to a much higher level, compaction of clay stacks occurs as less interspacing is needed to accommodate the stretched chains, but rapid cooling allows no time for the chains to relax and expand the galleries back. Overall, data obtained from both actual moulding and simulation indicate that injection speed is of utmost importance to the thin-wall injection moulding process, development of microstructure, and thus the resulting properties of the moulded PPCN parts, in the selected experimental ranges of this research.

Submitted by Aelson Maciera (aelsoncm@terra.com.br) on 2017-05-25T19:49:56Z No. of bitstreams: 1 DissBDQ.pdf: 27222907 bytes, checksum: eb17b232bd0096bfa1e0fb1dd7f4bf74 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-05-30T13:44:57Z (GMT) No. of bitstreams: 1 DissBDQ.pdf: 27222907 bytes, checksum: eb17b232bd0096bfa1e0fb1dd7f4bf74 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-05-30T13:45:05Z (GMT) No. of bitstreams: 1 DissBDQ.pdf: 27222907 bytes, checksum: eb17b232bd0096bfa1e0fb1dd7f4bf74 (MD5) / Made available in DSpace on 2017-05-30T13:50:33Z (GMT). No. of bitstreams: 1 DissBDQ.pdf: 27222907 bytes, checksum: eb17b232bd0096bfa1e0fb1dd7f4bf74 (MD5) Previous issue date: 2015-10-06 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / In this study nanocomposites of polyamide-6 (PA-6) reinforced with silica nanoparticles (SiO2) were prepared in order to promote improved mechanical properties for engineering applications. The nanoparticles’ surfaces were chemically modified with the silane agent 3-aminopropyltrimethoxysilane (3- APTMS) to improve the chemical and physical interactions between them and the PA-6 matrix. Nuclear magnetic resonance analysis (NMR) and Fourier transform infrared absorption spectroscopy (FT-IR) showed that 3-APTMS grafting on nanoparticles surface was accomplished. The nanocomposites mixing process was studied in two forms: by torque rheometry, using a torque rheometer internal mixer; and in a co-rotating and intermeshing twin-screw extruder. A preliminary study of the influence of processing variables at the torque rheometer on the degradation of polyamide-6 matrix was performed. The results showed that the greater the filling volume of the mixture in the chamber and the rotational speed of the rheometer’s rotors, the lower the degradation of the polyamide-6. Based on this preliminary study, compositions with 1, 2, and 4 % weight of SiO2 nanoparticles, both unmodified and chemically modified with 3-APTMS were prepared in the torque rheometer. The nanocomposites were compression molded and it was observed that nanocomposites reinforced with 1 wt.% SiO2, both unmodified and surface-modified, presented the best tensile properties. For the nanocomposite samples processed in the twin-screw extruder, the influence of relevant variables – nanoparticle content, chemical surface modification, physical form of the fed PA-6 (granule and powder), rotational speed of screws and extruder feed rate – on mechanical, thermal, and dynamic-mechanical properties were studied. The samples were afterwards injection molded and it was observed that the samples produced using 1 wt.% surface-modified and 100% finely ground PA-6 showed the higher tensile modulus and yield strength values. / Neste estudo foram preparados nanocompósitos de poliamida 6 (PA6) reforçados com nanopartículas de sílica (SiO2), com o objetivo de promover melhoria de propriedades mecânicas para aplicações de engenharia. A superfície das nanopartículas foi modificada quimicamente com o agente silano 3-aminopropiltrimetoxisilano (3-APTMS) para melhorar as interações químicas e físicas entre elas e a matriz de PA6. Análises de ressonância magnética nuclear (RMN) e espectroscopia de absorção no infravermelho por transformada de Fourier (FT-IR) mostraram que houve sucesso na funcionalização das nanopartículas com o agente silano. O processo de mistura dos nanocompósitos foi estudado de duas formas: por meio de reometria de torque em um misturador interno; e em extrusora com rosca dupla co-rotacional e interpenetrante. Um estudo preliminar da influência das variáveis de processamento no reômetro de torque sobre a degradação da poliamida 6, mostrou que quanto maior o volume de preenchimento da câmara de mistura e a velocidade de rotação dos rotores do reômetro, menor foi a degradação da poliamida 6. Com base neste estudo preliminar, foram preparadas no reômetro de torque composições com 1, 2 e 4% em massa de nanopartículas de SiO2 não modificadas e modificadas quimicamente com 3- APTMS. Os nanocompósitos obtidos foram moldados por compressão, tendo sido observado que os nanocompósitos reforçados com 1 %m. de SiO2 não modificada apresentaram as melhores propriedades mecânicas de resistência à tração e deformação na ruptura em ensaio de tração, enquanto os nanocompósitos com 1 %m. de nanosílica modificada apresentaram as melhores propriedades mecânicas de módulo elástico também no ensaio de tração. Para as amostras de nanocompósitos processadas na extrusora de rosca dupla, foram estudadas as influências do teor de nanopartículas, da modificação química superficial, da forma física da PA6 alimentada (grânulo e pó), da velocidade de rotação das roscas e da taxa de alimentação da extrusora sobre as propriedades mecânicas, térmicas e dinâmico-mecânicas. Posteriormente, os corpos de prova foram moldados por injeção e observou-se que a amostra cuja composição polimérica foi de 100% de PA6 fina e reforçada com 1 %m. de nanosílica modificada superficialmente pelo agente silano 3- APTMS apresentou os maiores valores de módulo de elasticidade e de tensão no escoamento no ensaio mecânico sob tração.

Neste trabalho, compósitos de PET sob a forma de flake e pós-condensado foram preparados com teores diferenciados de fibra de vidro (0, 20, 30 e 40%). Dois tipos de fibra foram utilizados: uma fibra com tratamento superficial a base de amino-silano e outra com tratamento a base de epóxi-silano. Os compósitos foram extrusados em extrusora mono-rosca, utilizando uma rosca de filete duplo com barreira, e em extrusora dupla-rosca interpenetrante co-rotacional. Após extrusão, os compósitos foram injetados a 120 ºC que, após várias temperaturas testadas, foi a temperatura que conferiu maior grau de cristalinidade do artefato final (acima de 30%). Os compósitos foram caracterizados quanto às propriedades mecânicas, térmicas e morfológicas. Os resultados mostraram que com a utilização de uma mono-rosca apropriada ao processamento de PET com fibra de vidro foi possível produzir compósitos com boas propriedades, comparáveis aos obtidos em extrusora dupla-rosca. Em relação aos tipos de PET utilizados, verificou-se que a massa molar da matriz polimérica, maior para o PET pós-condensado, teve uma pequena influência no desempenho das propriedades analisadas. Porém foi observado que os resultados foram indiferentes ao tratamento superficial das fibras testadas. Através da determinação do comprimento das fibras por análise óptica, e dos resultados experimentais do módulo de tração dos compósitos, pode-se constatar que nos compósitos injetados as fibras estão orientadas no sentido longitudinal à deformação. Com a microscopia eletrônica de varredura verificou-se que há sempre uma melhor distribuição e dispersão das fibras, com menores vazios à medida que aumenta o teor de fibras, corroborando os resultados mecânicos, sempre crescentes com o teor incorporado. A cristalinidade obtida nos corpos de prova moldados por injeção com o molde a uma temperatura de 120 ºC, aliada à presença da fibra de vidro, leva a um aumento na temperatura de distorção térmica (HDT). As análises de raios-X mostraram que com o aumento da quantidade da fibra, os picos cristalinos característicos do PET perdem definição, o que está associado à característica amorfa da fibra. / Submitted by Marcelo Teixeira (mvteixeira@ucs.br) on 2014-05-15T17:17:43Z No. of bitstreams: 1 Dissertacao Nilcea Mondadori.pdf: 5475607 bytes, checksum: 3b5580025f75099d47502055cd80fde5 (MD5) / Made available in DSpace on 2014-05-15T17:17:43Z (GMT). No. of bitstreams: 1 Dissertacao Nilcea Mondadori.pdf: 5475607 bytes, checksum: 3b5580025f75099d47502055cd80fde5 (MD5) / In this work, flake and post-condensed PET composites of different glass fiber contents (0, 20, 30 and 40%) were prepared. Tow kinds of fibers were employed: one fiber having an amino silane-based surface treatment and another one having an epoxi silane-based surface treatment. The composites were extruded in a single-screw extruder with a barrier double-flight screw, and in a co-rotating interpenetrating twin-screw extruder. After extrusion the composites were injected at 120°C, this temperature being chosen after several tests indicating that it could promote the highest possible degree of crystallinity of the final product (higher than 30%). The composites were characterized as for mechanical, thermal and morphological features. Data indicate that by using a single-screw extruder proper to the processing of PET and fiber glass the properties of the obtained composites are fairly good, being comparable to those obtained from a twin-screw extruder. As for the types of PET utilized, it could be found that the molar mass of the polymeric matrix, larger for the post-condensed PET had some influence on the performance of the tested properties. On the other hand it could be observed that the surface treatment of the fibers does not influence the obtained data. Based on the optical analysis of the fiber length and the elastic modulus data it is possible to determine that the fibers of the injected composites are oriented longitudinally to the strain direction. With the aid of scanning electron microscopy (SEM), improvements in the distribution and dispersion of the fibers were always observed, with smaller voids as the fiber content increases, backing higher mechanical data as the incorporated fiber content is increased. Crystallinity resulting from injection-molded test specimens processed at 120°C, together with the presence of the glass fiber leads to a synergism in the heat distortion temperature (HDT). X-rays analyses indicate that at higher fiber content the composites show lower definition of the crystalline peaks, this being associated to the amorphous feature of the fiber.

As crescentes exigências sobre o desempenho de sistemas de bombeamento multifásico combinadas aos aspectos relacionados com a maior disponibilidade operacional desses sistemas, bem como as futuras condições de funcionamento atingindo pressões perto de 150 bar, destacam a importância de desenvolver modelos matemáticos precisos para prever o comportamento do desempenho nestes equipamentos. Nesta tese foi aperfeiçoado o modelo termo-hidráulico de uma bomba multifásica de tipo duplo parafuso desenvolvido por Nakashima (2005) e foram incluídos os efeitos da abertura gradual da última câmara, recirculação de líquido entre a sucção e descarga, transferência de calor através do liner e expansão térmica. Uma vez fornecidos os dados geométricos da bomba e as suas condições de operação, é possível calcular os parâmetros de desempenho mais importantes, como: eficiência volumétrica, vazão de sucção e refluxo, potência consumida e distribuição de pressão e temperatura. As equações implementadas foram desenvolvidas a partir dos balanços de massa e energia nas câmaras, tendo em conta a geometria da bomba e a variação das fendas durante sua operação. As rotinas e métodos necessários para a sua solução numérica foram implementadas utilizando programação orientada a objetos (C++). Os resultados fornecidos pelo modelo aperfeiçoado foram comparados com dados experimentais da literatura e uma boa concordância foi encontrada na faixa de até 95 % FVG, nos casos estudados, para bombas com e sem tecnologia de recirculação. Devido à complexidade dos fenômenos físicos envolvidos durante a operação da bomba, o impacto de cada um dos efeitos incorporados nos cálculos do modelo foi avaliado e discutido individualmente. Assim, foi demonstrada a grande influencia da recirculação, da abertura gradual da câmara de descarga e da expansão térmica nos cálculos dos parâmetros de operação mais importantes da bomba. Além disso, a transferência de calor pode ser considerada desprezível, já que seu valor é baixo quando comparado com a potência fornecida pela bomba e, portanto, não influencia os balanços de energia que determinam os estados termodinâmicos das câmaras. No entanto, esse efeito é necessário para calcular a distribuição de temperatura da bomba e a expansão térmica nos parafusos e no liner. / The increasing requirements about the performance of multiphase pumping systems combined with those related to a higher operational availability of such systems, as well as future operating conditions with pressure increase at about 150 bar, highlights the importance of developing accurate mathematical models to predict the performance behavior of these equipments. In this thesis it was improved the thermo-hydraulic behavior of a twin screw multiphase pump developed by Nakashima (2005), and were included the effects of the gradual opening of the last chamber, fluid recirculation between suction and discharge of the pump, heat transfer though the liner, thermal expansion and different working fluids (water-air and oil-gas). Giving pump geometry and operational conditions, it is possible to calculate the most important pump parameters performance, such as, volumetric efficiency, suction flow, back-flow, power consumption and pressure and temperature distribution. The model equations were developed based on mass and energy balances in the chambers taking into account the pump geometry and the clearance variation due to operation. Its implementation was made in C++. The results obtained by the new model were compared with experimental data of the bibliography, and a good accuracy was found in it with values till 95% GVF for the studied cases, with and without recirculation technology. Due to the physical phenomenon complexity related with the pump operation, the impact of each effect in the model calculations was evaluated and discussed separately. So, it was demonstrated the importance of the recirculation, the gradual opening of the last chamber and the thermal expansion in the calculation of the most important pump operation parameters. However, the heat transfer can be neglected, because its value is very low when compared with the pump power supply, and therefore, it does not influence the energy balances that determine thermodynamic state in the chambers. However, this effect is necessary to calculate the temperature distribution along the pump and the thermal expansion in the screws and the liner.

Neste trabalho, compósitos de PET sob a forma de flake e pós-condensado foram preparados com teores diferenciados de fibra de vidro (0, 20, 30 e 40%). Dois tipos de fibra foram utilizados: uma fibra com tratamento superficial a base de amino-silano e outra com tratamento a base de epóxi-silano. Os compósitos foram extrusados em extrusora mono-rosca, utilizando uma rosca de filete duplo com barreira, e em extrusora dupla-rosca interpenetrante co-rotacional. Após extrusão, os compósitos foram injetados a 120 ºC que, após várias temperaturas testadas, foi a temperatura que conferiu maior grau de cristalinidade do artefato final (acima de 30%). Os compósitos foram caracterizados quanto às propriedades mecânicas, térmicas e morfológicas. Os resultados mostraram que com a utilização de uma mono-rosca apropriada ao processamento de PET com fibra de vidro foi possível produzir compósitos com boas propriedades, comparáveis aos obtidos em extrusora dupla-rosca. Em relação aos tipos de PET utilizados, verificou-se que a massa molar da matriz polimérica, maior para o PET pós-condensado, teve uma pequena influência no desempenho das propriedades analisadas. Porém foi observado que os resultados foram indiferentes ao tratamento superficial das fibras testadas. Através da determinação do comprimento das fibras por análise óptica, e dos resultados experimentais do módulo de tração dos compósitos, pode-se constatar que nos compósitos injetados as fibras estão orientadas no sentido longitudinal à deformação. Com a microscopia eletrônica de varredura verificou-se que há sempre uma melhor distribuição e dispersão das fibras, com menores vazios à medida que aumenta o teor de fibras, corroborando os resultados mecânicos, sempre crescentes com o teor incorporado. A cristalinidade obtida nos corpos de prova moldados por injeção com o molde a uma temperatura de 120 ºC, aliada à presença da fibra de vidro, leva a um aumento na temperatura de distorção térmica (HDT). As análises de raios-X mostraram que com o aumento da quantidade da fibra, os picos cristalinos característicos do PET perdem definição, o que está associado à característica amorfa da fibra. / In this work, flake and post-condensed PET composites of different glass fiber contents (0, 20, 30 and 40%) were prepared. Tow kinds of fibers were employed: one fiber having an amino silane-based surface treatment and another one having an epoxi silane-based surface treatment. The composites were extruded in a single-screw extruder with a barrier double-flight screw, and in a co-rotating interpenetrating twin-screw extruder. After extrusion the composites were injected at 120°C, this temperature being chosen after several tests indicating that it could promote the highest possible degree of crystallinity of the final product (higher than 30%). The composites were characterized as for mechanical, thermal and morphological features. Data indicate that by using a single-screw extruder proper to the processing of PET and fiber glass the properties of the obtained composites are fairly good, being comparable to those obtained from a twin-screw extruder. As for the types of PET utilized, it could be found that the molar mass of the polymeric matrix, larger for the post-condensed PET had some influence on the performance of the tested properties. On the other hand it could be observed that the surface treatment of the fibers does not influence the obtained data. Based on the optical analysis of the fiber length and the elastic modulus data it is possible to determine that the fibers of the injected composites are oriented longitudinally to the strain direction. With the aid of scanning electron microscopy (SEM), improvements in the distribution and dispersion of the fibers were always observed, with smaller voids as the fiber content increases, backing higher mechanical data as the incorporated fiber content is increased. Crystallinity resulting from injection-molded test specimens processed at 120°C, together with the presence of the glass fiber leads to a synergism in the heat distortion temperature (HDT). X-rays analyses indicate that at higher fiber content the composites show lower definition of the crystalline peaks, this being associated to the amorphous feature of the fiber.

Des produits de consommation de première nécessité aux produits les plus fortuits, l'emballage, en particulier plastique, constitue aujourd'hui un élément indispensable de notre vie quotidienne. Son utilisation intensive dans le domaine agroalimentaire pour un usage unique à courte durée de vie incite aujourd'hui à s'orienter vers de nouveaux matériaux d'origine renouvelable et biodégradables, aux caractéristiques similaires que leurs homologues issus des ressources fossiles. Les mélanges à base de biopolymères et de biopolyesters peuvent être une bonne alternative. Dans ce présent travail de thèse, des mélanges de farine de blé, thermoplastifiée par du glycérol et de l'eau, et des polyesters biosourcés et biodégradables tels que le PLA et/ou le PHB ont été obtenus par extrusion bivis et moulés par injection thermoplastique. Les caractéristiques thermiques, thermomécaniques dynamiques, morphologiques, mécaniques et barrières de ces nouveaux matériaux ont été étudiés. De l'acide citrique a été utilisé comme agent de compatibilisant pour améliorer l'interface amidon/PLA. Les différentes investigations nous ont permis de mettre au point différents types de formulations aux caractéristiques mécaniques et barrières à la vapeur d'eau intéressantes pour la fabrication de corps de barquettes d'emballage alimentaire de denrées périssables comme la viande ou les fromages. L'aptitude au contact alimentaire des matériaux farine thermoplastifiée/polyester et l'impact de l'incorporation des polyesters sur la biodégradabilité de ces matériaux ont également été étudiés. / From basic and essential to unnecessary and optional consumer products, packaging, particularly plastic, is today an indispensable part of our daily life. Its extensive use in the food industry for a single use and for a short shelf-life encourages us today to move towards new renewable and biodegradable materials with similar characteristics than their counterparts from fossil resources. Biopolymers and biopolyesters blends can be a good alternative. Within the framework of this present work, wheat flour, thermoplasticised by glycerol and water, and biobased and biodegradable polyesters such as PLA and/or PHB, were blended using an industrial twin screw extruder and were injection-molded into thermoplastic materials. Thermal, dynamic thermomechanical, morphological, mechanical and barriers properties of these new materials were studied. Citric acid was used as a compatibilizer to improve the interface starch/PLA. The different investigations have allowed us to develop various types of formulations, with mechanical characteristics and barrier properties to water vapor, very attractive for manufacturing plastic food packaging which can be used for meats or cheeses. Food contact suitability and biodegradability of thermoplasticised wheat flour/polyester materials have also studied.

No description available.

L’enrobage à sec par action mécanique permet de formuler des particules composites dont les fonctionnalités et les propriétés physiques, comme l’écoulement, sont améliorées et cela sans l’ajout de solvant ou de liant. Actuellement la plupart des procédés d’enrobage à sec sont conduits en mode discontinu. L’objectif de ce travail est donc de développer et d’étudier une opération d’enrobage à sec par un procédé continu innovant, une extrudeuse bi-vis corotative sans filière, constituant une rupture technologique dans son domaine. Dans le cadre de ce travail, des sphères de cellulose microcristalline, appelées particules hôtes sont enrobées avec soit des talcs de différentes granulométries soit du stéarate de magnésium, nommées particules invitées. Dans un premier temps, le comportement des particules hôtes est étudié dans le procédé. Les particules sorties du procédé sont analysées par microscopie électronique à balayage, par granulométrie laser et par voluménométrie. Pour la configuration de vis présentant que des éléments de transport, la vitesse de rotation des vis (25 à 200 rpm) et le débit d’alimentation (0,5 à 2 kg/h) choisis influencent le taux de remplissage dans le fourreau, et pour un taux supérieur à environ 14 % : la quantité de particules endommagées est négligeable. Un taux de remplissage faible favorise les frictions particules-particules ou particules-métal au niveau de l’entrefer. L’ajout de zones de mélanges dans la configuration des vis accentue ce phénomène de brisure par l’augmentation des contraintes de cisaillement. Par ailleurs, des masses retenues de la poudre dans le fourreau évoluent linéairement en fonction de la masse de poudre transportée en un tour de vis pour différentes configurations de vis. Ces relations laissent penser à l’existence d’un volume mort. Les mesures de distribution de temps de séjour mettent en évidence par l’application d’un modèle d’association de réacteurs idéaux, la présence d’écoulement piston et d’un volume mort. Dans un second temps, la faisabilité d’une opération d’enrobage à sec par le procédé étudié est analysée. Une couche d’enrobage continu de talc modifiant le comportement hydrophile des particules hôtes, est obtenue pour une vitesse de rotation de vis de 50 rpm et une configuration de vis cisaillante. Le type de particules invitées influence la morphologie de la couche d’enrobage : de type film avec le stéarate de magnésium et de type discret avec le talc micronisé. Néanmoins les propriétés de taille, d’écoulement, de compressibilité des particules composites sont semblables à celle des particules hôtes, seule la propriété de mouillabilité est modifiée. La présence de stéarate de magnésium diminue le temps de séjour des particules dans le procédé grâce à son caractère lubrifiant. / Dry particle coating with mechanical action allows the production of composite particles whose functionalities and physical properties, such as flowability, are improved thanks to the absence of solvent or binder. Currently, most of dry particle coating processes are carried out in a discontinous mode. The objective of this work is thus to develop and study a dry particle coating operation with a continuous innovative process, twin screw co-rotating extruder without die, constituting a technological rupture in this application field. For this, spherical particles of microcristalline cellulose, as host particles, are coated with either talc particles of two sizes or magnesium stearate particles (MgSt), as guest particles. Firstly, the host particles behaviour is studied in the process. The exiting particles are analyzed by scanning electronic microscopy, laser granulometry and tapping test. Regarding the transport configuration, the chosen screw speed (between 25 an 200 rpm) and the feed rate (between 0.5 and 2 kg/h) have an important influence on the filling level in the barrel. For a filling level superior to approximatly 14 %, the quantity of broken particles is not significant. A low filling level facilitates the particle-particle or particle-metal friction in the barrel gap. When more mixing zones are added to the screw configuration, the shear stresses increase and, therefore, the breakage particle phenomenon becomes more prominent. Futhermore, the retained powder mass increases linearly when the transported mass in one screw turn increases for all the screw configurations. These evolutions suggest the existence of a dead volume. The residence time distribution mesurements highlight, thanks to the application of flowing model, the presence of plug-flow and a dead volume. Secondly, the feasibility of using the process for dry particle coating is analyzed. A continuous coating layer of talc modifiying the hydrophilic behaviour of the host particles is obtained for a low screw rotation speed (50 rpm) and a screw configuration with one mixing zone. The type of guest particles influence the morphology of the coating layer: film layer with the MgSt particles and discontinous layer with the micronized talc. However, size, flow and compressibility of the coated particles are similar to the ones of the initial host particles, only the wettability properties are modified. The presence of MgSt decreases the particle mean residence time in the process thanks to its lubricant action.

Le but de cette thèse est l’investigation des particularités des problèmes d’optimisation et modélisation des réacteurs tubulaires de polymérisation. La partie originale du travail est divisé en deux sections : la première traitant de l'étude théorique de la modélisation et de l’optimisation des réacteurs tubulaires de polymérisation du méthacrylate de méthyle en solution, et la deuxième, une étude expérimentale et théorique de l'extrusion réactive de L-lactide. Dans la première partie, afin de sélectionner un modèle cinétique représentatif, parmi les modèles publiés pour le processus de polymérisation de MMA, des simulations ont été effectuées en conditions identiques de fonctionnement. Deux algorithmes numériques, l’un basé sur le Principe du Minimum de Pontriaguine et l’autre de type Génétique, ont été comparés pour un problème d'optimisation de complexité moyenne. Les résultats ont montré une robustesse supérieure de l’Algorithme Génétique pour cette catégorie de problèmes. La deuxième partie de la thèse est consacrée à la modélisation et à l’optimisation de l'extrusion réactive du Llactide. Nous avons proposé un modèle cinétique et ses paramètres ont été estimés en utilisant des procédures numériques basées sur les données cinétiques expérimentales. Les expériences d'extrusion réactives ont été exécutées dans les conditions de fonctionnement représentatives. L'écoulement de L-lactide/polylactide dans l'extrudeuse a été caractérisé par la simulation en utilisant un logiciel commercial, LUDOVIC®. Les caractéristiques de la distribution des temps de séjour simulées sont utilisées pour modéliser le processus d'extrusion réactive en utilisant deux approches, un modèle à dispersion axiale et un modèle à base de compartiments, dont les caractéristiques sont déduites des simulations effectuées avec LUDOVIC®. Les résultats de la modélisation du processus sont en bon accord avec des données mesurées en mêmes conditions opératoires. / The aim of this thesis is the investigation of modeling and optimization particularities of tubular polymerization reactors. The original work is divided in two sections, the first treating a modeling and optimization study of tubular reactors for methyl methacrylate polymerization in solution, and the second, an experimental and theoretical study of L-lactide reactive extrusion. In the first section, reactor simulations in similar operating conditions were performed in order to select a representative kinetic model among the published kinetic models for MMA solution polymerization. Two widely used numerical algorithms, one based on Pontryagin’s Minimum Principle and the other a Genetic Algorithm, were compared for an average-complexity optimization problem. The results showed a superior robustness of the Genetic Algorithm for this category of problems. The second part of the thesis deals with the modeling and optimization of L-lactide reactive extrusion. A kinetic model is proposed and its parameters estimated using nonlinear estimation numerical procedures based on experimentally measured data. Reactive extrusion experiments were performed in representative operating conditions. The Llactide/ polylactide flow in the extruder was characterized by simulation using the commercial software LUDOVIC®. The simulated residence time distributions characteristics are used to model the reactive extrusion process of two approaches, an axial dispersion model and a compartment model, based on compartments whose characteristics are deduced from the simulations using LUDOVIC®. The modeling results are in good agreement with the measured data in the same operating conditions.