Yes / Polyamide 6 (PA6) is an important engineering thermoplastic, very widely used but prone to thermal degradation during extrusion at temperature not far from its melt temperature (220 oC). Typically, and as measured in this study, PA6 extruded at temperature of 300 oC shows a 40% decrease in tensile modulus compared to non-extruded PA6. To rebuild PA6 molecular weight, the easiest and cheapest method is to use an appropriate chain extender. Many chain extenders have been used in the past but they are essentially suited to nucleophile induced degradation, targeting split PA6 chains carboxyl COOH and amine NH2 end groups. What has been lacking are effective chain extenders for thermally only induced degradation, i.e. for the practical cases where the PA6 is thoroughly dried before extrusion. For such a case, the degradation reaction mechanism dictates that the solution is to develop chain extenders that target the split PA6 chains amide CONH2 groups not the carboxyl COOH and amine NH2 end groups. As amide groups strongly react with anhydride functionalities, we test the effectiveness of a novel chain extender, Joncryl® ADR 3400, a styrene maleic anhydride copolymer with multiple, repeating anhydride functionality. Assessment of chain extension in this study is done as with previous work, using rheology, mechanical and thermal properties of PA6 extruded on its own and with the chain extender. The viscoelastic data conclusively show the efficacy of such chain extender with more than 10 fold changes in the comparative values of the extruded sample storage modulus G' and as much as an 85% increase in the tensile modulus. / Republic of Turkey, Ministry of National Education. University of Bradford

No description available.

Yes / Extrusion-a unit operation in polymer processing has been in extensive use since the great age of plastic technology. It is a simple operation that enables within one equipment the sequential conveying of solid polymer chips or powder, their melting, mixing, pumping and shaping via a die into a variety of high tonnage and/or value products. Pipes, bottles, films are the most common examples but the list of applications is endless from tiny micromoulded parts to large structural profiles. Extrusion is not limited to plastics but is used hot or cold to process soft solids like food, industrial and pharmaceutical pastes, as well as metals and ceramics. Most of the advances in extrusion processing have concentrated in improving the essential functions of extrusion: solid conveying, melting, pumping and mixing. The literature abounds with descriptions of such advances pushing the limits of the extrusion in an incremental way. In this paper, we describe step-changes in enhancing extrusion, which opens up new applications to better old technology-make them safer, cheaper and cleaner. The new designs presented in this paper have also the potential to develop new reactor technology for viscous fluids.

No / Hot melt extrusion is a continuous process with wide industrial applicability. Till current date, there have been no reports on the formulation of extrudates for topical treatment of dermatological diseases. The aim of the present work was to prepare and characterize medicated hot melt extrudates based on Soluplus polymer and nicotinamide, and to explore their applicability in acne treatment. The extrudates were characterized using DSC, FTIR, XRD, and DVS. The extrudates were also tested for their skin adhesion potential, ability to deposit nicotinamide in different skin layers, and their clinical efficacy in acne patients. The 10% nicotinamide extrudates exhibited amorphous nature which was reserved during storage, with no chemical interaction between nicotinamide and Soluplus. Upon contrasting the skin adhesion and drug deposition of extrudates and nicotinamide gel, it was evident that the extrudates displayed significantly higher adhesion and drug deposition reaching 4.8 folds, 5.3 folds, and 4.3 folds more in the stratum corneum, epidermis and dermis, respectively. Furthermore, the extrudates significantly reduced the total number of acne lesions in patients by 61.3% compared to 42.14% with the nicotinamide gel. Soluplus extrudates are promising topical drug delivery means for the treatment of dermatological diseases.

Yes / A continuous, scalable, and solvent‐free method for the synthesis of various naphthalic imides and perylene diimides (PDIs) using twin‐screw extrusion (TSE) is reported. Using TSE, naphthalic imides were obtained quantitatively without the need for excess amine reactant or product purification. With good functional‐group tolerance, alkyl and benzyl amine derived PDIs (incl. commercial dyes) were obtained in 50–99 % yield. Use of K2CO3, enabled synthesis of more difficult aniline‐derived PDIs. Furthermore, an automated continuous TSE process for Pigments Black 31 and 32 is demonstrated, with a throughput rate of about 1500 g day−1, corresponding to a space time yield of about 30×103 kg m−3 day−1, which is 1–2 orders of magnitude greater than for solvent‐based batch methods. These methods provide substantial waste reductions and improved efficiency compared to conventional solvent‐based methods. / Engineering and Physical Sciences Research Council. Grant Numbers: EP/L019655/1, IAA1718-04-1117

Cette thèse a pour objectif le développement et l'implémentation d'un outil de résolution éléments-finis pour les problèmes d'extrusion de matériaux visco-plastiques fondus qui soit adapté à l'industrie du pneumatique. Dans ces travaux nous présenterons une méthodologie complète pour résoudre un modèle couplé comprenant le calcul des écoulements dans l'outillage, la répartition de température dans le domaine et la position d'interfaces entre plusieurs matériaux non miscibles. Pour cela, nous utiliserons les équations de Stokes non linéaires, l'équation de la chaleur, la méthode des interfaces diffuses et l'adaptation de maillage hiérarchique. Après avoir détaillé les différentes méthodes utilisées pour la résolution des différents problèmes, nous présenterons des résultats numériques dans plusieurs géométries d'outillages liés à l'extrusion des polymères. / The objective of this thesis is the development and the implementation of a finite element resolution tool for extrusion problems of molten visco-plastic materials which is suitable for the tire industry. In this works we will present a complete methodology to solve a coupled model including the calculation of the flow field in the equipment, the temperature distribution in the domain and the position of interfaces between several immiscible materials. To achieve this goal, we will solve the nonlinear Stokes equations, the heat equation, the diffuse interface method and we will use hierarchical mesh adaptation. After describing the various methods used for the resolution of the different problems, we present numerical results in several industrial geometries of tools related to the extrusion of polymers.

No / This communication reports a novel solvent free method to generate and stabilise the triclinic form of artemisinin. We show that the stability of the triclinic form obtained by high temperature extrusion is greater than that of material made using a solvent based technique.

In the recent past it has been found that a considerable pressure drop occurred during the extrusion of linear polyethylene in the course of capillary flow. The pressure drop resides within a narrow temperature window of one to two degrees Celsius. In this research the hydrodynamic condition and molecular origin of the extrusion window of linear polymer were investigated further. The advantage of the extrusion window, viz. smooth extrudate with less die swell ratio attained at low extrusion pressure and temperature, has potential in industrial applications. However, the extrusion window, corresponding to linear polyethylene (PE) with relatively low polydispersity (<7), has a narrow window temperature interval, circa 1~2°C, thus it could not be applied to industrial scale processing at the industrial scale. To have a fundamental insight and make the process industrially viable, research in this thesis was devoted to broaden the extrusion window to tolerate the thermal fluctuations in conventional processing. To achieve this goal molecular weight dependence of window temperature and flow criticalities is revealed. The hydrodynamic conditions of the extrusion window observed in a rate-controlled rheometer and stick-slip flow studied in a stress-controlled rheometer could be traced back to the same origin, viz. slip flow arises due to the disentanglement of adsorbed chains on capillary wall from free chains in the bulk. Secondly, a dual window effect was uncovered in the course of capillary flow of a bimodal PE, which is consistent with the window temperature dependence on molecular weight. Moreover, it was found that flow induced orientation within the window effect is even less than that observed in steady state flow at a relatively low shear rate. This implies that in the window region only relaxed free chains are extruded through the capillary die and most of the adsorbed chains, which could be disengaged from the entangled melt, remain sticking to the inner capillary wall. This observation is consistent with the hydrodynamic origin of high-surface-energy-die slip flow. Finally, a unimodal linear PE with extremely broad molecular weight distribution, i.e. polydispersity (PDI) is 27, showed a broad window effect, circa 8°C, at an appropriate apparent shear rate. The molecular origin of such a broad window effect is due to its broad molecular weight distribution. These results have further implications for energy efficient processing.

No description available.

Cette étude s’intéresse aux mélanges Polyamide 6 / Polyéthylène Haute Densité compatibilisés par voie réactive, plus particulièrement aux relations entre (1) la formulation, les paramètres de mise en œuvre en extrusion bivis corotative et (2) la morphologie et la microstructure des mélanges. Des morphologies multi-échelles ont été observées en Microscopie Électronique à Balayage et en Transmission. À l’échelle micrométrique, les morphologies suivantes ont été développées : dispersion nodulaire, nodules étirés et co-continuité. Les paramètres procédés n’influençant pas le type morphologie, les régions correspondant aux types de morphologies ont pu être rassemblées sur des diagrammes ternaires. Dans le cas des mélanges compatibilisés, deux mécanismes de formation de ces morphologies sont proposés : (1) la réaction de compatibilisation très rapide et efficace entraîne la formation de nano-dispersions par instabilités d’interface et (2) le mécanisme classique de rupture/coalescence de domaines moins riches en copolymère permet de former des morphologies jusqu’à l’échelle micrométrique. L’évolution de la taille maximale des domaines en fonction de la composition ainsi que la distribution de tailles ont été modélisés par des mécanismes de percolation. La stabilité des morphologies en statique, sous cisaillement contrôlé et au cours d’une deuxième étape de mise en forme a ensuite été étudiée. Le copolymère formé à l’interface permet de stabiliser la taille des morphologies. Enfin, une cristallisation à plus basse température a été mise en évidence en Calorimétrie Différentielle à Balayage lorsque les polymères sont confinés dans des domaines submicroniques. / This study deals with reactively compatibilized Polyamide 6 / High Density Polyethylene blends. More precisely, it focuses on the relationship between (1) the formulation, the processing parameters in corotating twin screw extrusion and (2) the morphologies and the microstructures of blends. Multi-scale morphologies were observed by Scanning and Transmission Electron Microscopy. At the micron scale, the following morphologies were developed: nodular dispersions, stretched nodules and co-continuous morphology. As the processing conditions did not influence the types of morphology, the different morphological regions were reported in ternary diagrams. In the case of compatibilized blends, two mechanisms for morphology development have been proposed: (1) the compatibilization reaction, being very fast, leads to the formation of nano-dispersions by interfacial instabilities and (2) the standard break-up/coalescence mechanism of domains poor in copolymer could lead to the formation of morphologies up to the micron scale. Both the evolution of the largest size as a function of the composition and the distribution of sizes were modeled using percolation concepts. The stability of the morphologies was then studied either during static annealing or controlled shear or in a second step processing. The copolymer formed at the interface allows stabilizing the size of the morphologies. Finally, crystallization at lower temperature was observed by Differential Scanning Calorimetry when the polymers are confined in submicron domains.