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No / A novel, green, and continuous method for solid-state polymorphic transformation of artemisinin by high temperature extrusion has recently been demonstrated. This communication describes attempts to understand the mechanisms causing phase transformation during the extrusion process. Polymorphic transformation was investigated using hot stage microscopy and a model shear cell. At high temperature, phase transformation from orthorhombic to the triclinic crystals was observed through a vapor phase. Under mechanical stress, the crystalline structure was disrupted continuously, exposing new surfaces and accelerating the transformation process.

This thesis is concerned with the development of a continuous melt extrusion process utilizing CO₂ for the production of materials that cannot be typically melt processed. The first goal of this study is to determine under what conditions it is possible to use CO₂ to plasticize and, thereby, reduce the viscosity of an acrylonitrile (AN) copolymer in an extrusion process and render it melt processable. In order to assess whether it was possible to absorb adequate amounts of CO₂ in short residence times by injection into a single screw extruder, a slit-die rheometer was attached to the end of the extrusion system for the purpose of directly assessing the viscosity reduction. A chemorheological analysis was performed on 65 and 85% AN copolymers to establish the temperature at which the 85% material would be stable for melt processing. This, coupled with studies correlating the degree of Tg and viscosity reduction with the amount of absorbed CO₂, allowed one to establish conditions for melt extrusion of the 85% AN. It was determined that the 85% AN material should absorb at least 5 weight percent CO₂ for a processing temperature reduction of 26°C in the extrusion process. The second goal of this study is to determine to what extent CO₂ can be used as a processing aid to melt process polyethylenes of higher molecular weight than can be typically melt processed. To assess the ability to melt process high molecular weight polyethylenes with CO₂, the viscosity of a 460,000 g/mol HDPE plasticized with various amounts of absorbed CO₂ as determined with the slit-die rheometer. A relationship was developed to determine the maximum molecular weight polyethylene that could be processed at a given viscosity reduction due to absorbed CO₂. The viscosity of a blend of 40 weight percent UHMWPE with the 460,000 g/mol HDPE with 12 weight percent CO₂ was reduced to that of the pure 460,000 g/mol HDPE as predicted by the relationship. Preliminary studies using a pressurized chamber attached to the exit of the die allowed one to assess the conditions under which suppression of foaming is possible. / Ph. D.

La luzerne est une plante fourragère, de la famille des Fabacées, largement cultivée en France du fait de sa richesse en protéines. Industriellement, cette plante est pressée, puis séchée sur tambour rotatif. L’étape de pressage conduit à l’obtention de grandes quantités de jus, lui aussi riche en protéines. L’objectif de cette thèse a été de développer un procédé de bioraffinerie de la luzerne, applicable aux autres plantes fourragères, permettant la valorisation des toutes les fractions de la plante. La première étape consiste en un fractionnement thermo-mécanique de la luzerne entière par extrusion bi-vis. Deux fractions sont obtenues : un résidu fibreux solide en partie déshydraté, pouvant être utilisé dans la filière agro-matériaux, et un filtrat vert, riche en protéines. L’extrusion bi-vis est une alternative intéressante aux procédés classiques de déshydratation, car l’étude de l’optimisation des paramètres d’extrusion a permis de montrer qu’il est possible de récupérer la grande majorité des protéines de la plante dans le filtrat. Ce filtrat subit par la suite une séparation liquide/solide par centrifugation, permettant la récupération d’un culot vert, dont on peut extraire la chlorophylle. Le jus clarifié est ultrafiltré, puis traité par chromatographie hydrophobe, avec l’huile de tournesol comme solvant extracteur, de manière à séparer différentes protéines. L’étude plus fondamentale de la fixation des protéines sur résine a permis de modéliser le fractionnement des protéines par interactions hydrophobes. / Alfalfa is a common Legume, cultivated as a forage crop, thanks to its high protein content. In the green crop industry, alfalfa is pressed and dried on a rotative cylinder. The pressing step leads to the production of large amounts of green juice, rich in proteins. The aim of this work was to develop a biorefinery process for alfalfa, which could be adapted to other green crops, allowing the valorization of each fraction. The first step is the whole plant thermo-mechanical fractionation in the twin-screw extruder. Two fractions are obtained: a solid fibrous residue, partly dehydrated which could be valorized as an agro-material, and a green filtrate, rich in proteins. Twin-screw extrusion is an interesting alternative to usual industrial dehydration processes. Indeed, the study of the extruder parameters optimization showed that most of the alfalfa proteins can be recovered in the filtrate. This green extract is then centrifuged, in order to separate the solid particles. Chlorophyll can be extracted from the centrifugation pellet. The clarified juice is treated by ultrafiltration, and lastly fractionated thanks to hydrophobic chromatography, with sunflower oil as the solvent, in order to separate the proteins. The more fundamental study of proteins fixation on resins allowed us to modelize proteins fractionation using hydrophobic interactions.

Ce travail de thèse porte sur les liens entre les conditions opératoires du procédé de mise en œuvre par mélange à l'état fondu et la structure de nanocomposites polypropylène/argile, ainsi que sur l'influence de l'état de dispersion de l'argile sur les propriétés mécaniques des matériaux obtenus. L'étude est basée sur des essais expérimentaux. Les analyses structurales sont réalisées en s'appuyant sur la rhéologie, la diffraction de rayons X ainsi que sur des observations en microscopie électronique.Les études en mélangeur interne ont montré, d'une part, que l'augmentation de la concentration en agent compatibilisant (PP-g-MA) favorise la dispersion de l'argile à l'échelle manométrique tout en augmentant la fragilité des nanocomposites, et d'autre part, que le mélange par voie mélange maître permet d'améliorer considérablement l'état de dispersion comparativement à la voie directe. Les essais réalisés en extrusion bivis corotative ont permis de mettre en évidence l'impact de la vitesse de rotation des vis (N), du débit d'alimentation (Q) et de la température de régulation (Trég) sur l'état de dispersion. L'influence de ces trois variables peut être décrite à l'aide d'un paramètre unique : l'énergie mécanique spécifique (EMS). L'accroissement de l'EMS entraîne une augmentation du niveau d'exfoliation jusqu'à une valeur critique au-delà de laquelle les conditions opératoires ne semblent plus influencer l'état de dispersion. Une relation entre le module de Young des nanocomposites et le niveau d'exfoliation a été établie. Le logiciel LUDOVIC© nous a permis de montrer que l'EMS permet également une bonne description de la progression de l'état de dispersion le long du profil d'extrusion. Enfin, l'étude du comportement thixotrope des nanocomposites à l'état fondu a notamment permis de comprendre que le principe de superposition temps-température ne s'applique pas systématiquement aux nanocomposites étant donné leur caractère évolutif. / The present PhD work deals with the relationships between melt processing conditions and the structure of polypropylene-layered silicate nanocomposites, as well as the influence of the dispersion state on the mechanical properties of nanocomposites. This study is based on experimental results. Structural analysis are performed using rheology, X-ray diffraction and electron microscopy.Internal mixer studies revealed that the increase of compatibilizer (PP-g-MA) content simultaneously leads to enhanced nanoscale dispersion and increased brittleness of the nanocomposites. A significantly higher dispersion was stated using a masterbatch method, as opposed to direct blending method. Co-rotating twin screw extrusion experiments allowed to highlight the effect of screw rotation speed (N), feed rate (Q) and barrel temperature (TrÈg) on the degree of dispersion. The influence of these three parameters on the nanocomposites structure can be described using the specific mechanical energy (SME) as a single processing parameter. Exfoliation is clearly promoted by the increase of the SME until it reaches a critical value. Above that threshold, the degree of exfoliation levels off and improvement of the dispersion state cannot be obtained through the optimization of processing conditions anymore. A relationship between the Youngís modulus of the nanocomposites and the exfoliation level has been established. Twin screw extrusion simulation software (LUDOVIC©) was used to calculate the evolution of processing data along the screw profile. From these results, a correlation between the progression of the dispersion state along the extrusion profile and the SME was found. Eventually, rheological investigation on the thixotropic behaviour of nanocomposites enabled to emphasize that time-temperature superposition principle doesn't systematically hold true for nanocomposites because of their structure aging.

Massas de pães são preparadas a partir da mistura de farinha de trigo, água, sal e fermento. Ao entrar em contato com a água e sofrer amassamento mecânico, a farinha de trigo tem a propriedade, quase exclusiva, de produzir uma massa coesa e viscoelástica, por conter proteínas formadoras de glúten. O processo de mistura pela qual passam as massas de pães, seguido de etapas de fermentação é fundamental para o bom desenvolvimento da massa e qualidade final do pão acabado. As análises de textura (back extrusion e extensibilidade) e volume, em massa crua de pão, podem avaliar o desenvolvimento e a qualidade de massas, eficácia de formulações e a eficiência dos ingredientes usados na melhoria do desenvolvimento da massa e do pão acabado. O projeto teve como objetivo elaborar formulações de massas de pães por diferentes processos de fermentação e testá-las através das análises de textura por extensibilidade e back extrusion, e volume sendo esta última sugerida para esse fim. Também foi testada a substituição de parte da farinha de trigo por triticale. As formulações utilizadas incluíram diferentes métodos de preparo de massas, como método direto e indireto, sendo nove formulações propostas. Pelo método direto o fermento seco instantâneo é adicionado diretamente à farinha e em seguida os demais ingredientes da formulação são adicionados, em uma única fase, seguido das etapas de mistura e fermentação. Já para as massas elaboradas de forma indireta, preparou-se uma massa fermentada denominada esponja, que foi feita com parte da farinha e da água e todo fermento seco instantâneo da formulação, deixada fermentar durante uma hora. Em uma segunda fase, a esponja foi adicionada ao restante dos ingredientes, seguido das etapas de mistura e fermentação. Os resultados das análises mostraram as diferenças do comportamento reológico de massas preparadas por diferentes processos fermentativos e a influência dos ingredientes como, o iogurte, adicionado por conter substâncias que são encontradas em pães fermentados naturalmente, resultando no aumento dos parâmetros reológico das massas contendo esse ingrediente. / Dough of bread are prepared from the mixture of flour wheat, water, salt and yeast. By contacting the water and suffer mechanical kneading the flour has property, almost exclusively, to produce a cohesive dough and viscoelasticity, which contain gluten-forming proteins. The mixing process through which runs the dough of bread, followed stages of fermentation is essential for the dough development and final quality of the finished bread. The analysis of texture (back extrusion and extensibility) and the volume dough of raw bread, can measure the development and quality of dough, formulation\'s effectiveness and efficiency of ingredients used in enhancing development of dough and the finished bread. The project had the object to develop formulations of doug for different fermentation processes and test them through the analysis of texture by extensibility and back extrusion, the latter being suggested for this purpose. Also was tested the substitution of part of the flour for triticale. The formulations used included different methods of preparation of dough, as a direct and indirect method, being nine formulations proposed. Through direct method the instant dry yeast is added directly to flour and then other ingredients formulation are added in a single phase, followed by stages of mixing and fermentation. To the dough produced in an indirect way, has been prepared a fermented dough called sponge, which is made with part of the flour and water and all instant dry yeast used in the formulation, and left to ferment for one hour. In a second phase, the sponge was added to the rest of the ingredients, followed the steps of mixing and fermentation. The analysis results showed the differences of rheological behavior of doughs prepared by different fermentation processes and the influence of ingredients as yogurt, added to contain substances that are found in naturally fermented breads, resulting in the increase of rheological parameters of the dough containing this ingredient.