Elaboration et mise en forme de matériaux polymères à base de l’ε-caprolactame (PA6) par le procédé de rotomoulage réactif

A reactive rotational molding (RRM) process was developed to obtain a PA6 by activated anionic ring-opening polymerization of epsilon-caprolactam (APA6). Sodium caprolactamate (C10) and caprolactam magnesium bromide (C1) were employed as catalysts, and difunctional hexamethylene-1,6-dicarbamoylcaprolactam (C20) was used as an activator. The kinetics of the anionic polymerization of ε-caprolactam into polyamide 6 was monitored through dynamic rheology and differential scanning calorimetry measurements. The effect of the processing parameters, such as the polymerization temperature, different catalyst/activator combinations and concentrations, on the kinetics of polymerization is discussed. A temperature of 150°C was demonstrated to be the most appropriate. It was also found that crystallization may occur during PA6 polymerization and that the combination C1/C20 was well suited as it permitted a suitable induction time. Isoviscosity curves were drawn in order to determine the available processing window for RRM. The properties of the obtained APA6 were compared with those of a conventionally rotomolded PA6. Results pointed at lower cycle times and increased tensile properties at weak deformation. Additionally, rotational molding of the bilayer PA6/PE-GMA has been studied, the control of the reactions mechanisms involved in the interface by rheology , during formation of the anionically PA6 polymer layer on a PE- GMA layer was carried out in a rheometer , a good adhesion at the interface was observed. The feasibility of developing nanocomposite PA 6/clay by reactive rotational molding process has been tested; the physico-chemical characterization and morphological observations were studied to assess the state of dispersion and the nature of interactions. During this study, we measured the feasibility of intercalation and swelling the clay in the ε-caprolactam monomer and estimate the possibility of having morphology of exfoliated nanocomposites prepared by reactive rotational molding process.Cette thèse porte sur le rotomoulage réactif de polyamide 6. Ce procédé a la particularité de présenter des cycles thermiques relativement réduit et de fabriquer des polymères sur mesure contrairement à son homologue conventionnelle. La voie envisagée pour la synthèse in situ de PA6 est la polymérisation anionique de l’ε-caprolactame par ouverture de cycle. Le Caprolactamate de sodium et le bromure de caprolactame-magnésium ont été utilisés comme catalyseurs, et l’hexaméthylène dicarbamoyl dicaprolactame a été employé comme activateur. L’étude rhéocinétique de deux systèmes réactifs lactames qui ont été utilisé à différentes compositions et températures a permis de déterminer une formulation appropriée aux exigences du procédé (faible viscosité initiale du système réactif, temps de polymérisation court...). La simultanéité des phénomènes de polymérisation et de cristallisation aux faibles températures à été observé à l’aide des résultats du suivi cinétique par DSC. La mise en forme par la technique de rotomoulage a été réalisée sur une installation pilote de rotomoulage associée à un système d’acquisition de température par télémesure radio. La comparaison des propriétés des articles en PA 6 obtenus par voie réactive par rapport a ceux obtenus par voie fondue, a montré un gain au niveau du temps de cycle et une amélioration des propriétés mécaniques du matériau notamment dans le domaine des faibles déformations. Le rotomoulage de la bicouche PA6/PE-GMA a été ainsi étudié, le contrôle des mécanismes réactionnels mis en jeu à l’interface par rhéologie, durant la formation de la couche de polymère PA6 par voie anionique sur une couche de PE-GMA a été effectué dans un rhéomètre, une bonne adhésion à l’interface a été observé. La faisabilité d’élaboration de nanocomposite PA 6/argile par le procède de rotomoulage réactif a été testé, les caractérisations physico-chimiques et les observations morphologiques ont été étudiés afin d’évaluer l’état de dispersion et la nature des interactions. Durant cette étude, nous avons mesurés la faisabilité de l’intercalation et le gonflement de l’argile dans le monomère ε- caprolactame et estimer la possibilité d’avoir une morphologie exfolié des nanocomposites élaborés par le procédé de rotomoulage réactif

Synthesis and processing of polymeric materials based on the ε-caprolactam (PA6) by reactive rotational molding process

Cette thèse porte sur le rotomoulage réactif de polyamide 6. Ce procédé a la particularité de présenter des cycles thermiques relativement réduit et de fabriquer des polymères sur mesure contrairement à son homologue conventionnelle. La voie envisagée pour la synthèse in situ de PA6 est la polymérisation anionique de l’ε-caprolactame par ouverture de cycle. Le Caprolactamate de sodium et le bromure de caprolactame-magnésium ont été utilisés comme catalyseurs, et l’hexaméthylène dicarbamoyl dicaprolactame a été employé comme activateur. L’étude rhéocinétique de deux systèmes réactifs lactames qui ont été utilisé à différentes compositions et températures a permis de déterminer une formulation appropriée aux exigences du procédé (faible viscosité initiale du système réactif, temps de polymérisation court...). La simultanéité des phénomènes de polymérisation et de cristallisation aux faibles températures à été observé à l’aide des résultats du suivi cinétique par DSC. La mise en forme par la technique de rotomoulage a été réalisée sur une installation pilote de rotomoulage associée à un système d’acquisition de température par télémesure radio. La comparaison des propriétés des articles en PA 6 obtenus par voie réactive par rapport a ceux obtenus par voie fondue, a montré un gain au niveau du temps de cycle et une amélioration des propriétés mécaniques du matériau notamment dans le domaine des faibles déformations. Le rotomoulage de la bicouche PA6/PE-GMA a été ainsi étudié, le contrôle des mécanismes réactionnels mis en jeu à l’interface par rhéologie, durant la formation de la couche de polymère PA6 par voie anionique sur une couche de PE-GMA a été effectué dans un rhéomètre, une bonne adhésion à l’interface a été observé. La faisabilité d’élaboration de nanocomposite PA 6/argile par le procède de rotomoulage réactif a été testé, les caractérisations physico-chimiques et les observations morphologiques ont été étudiés afin d’évaluer l’état de dispersion et la nature des interactions. Durant cette étude, nous avons mesurés la faisabilité de l’intercalation et le gonflement de l’argile dans le monomère ε- caprolactame et estimer la possibilité d’avoir une morphologie exfolié des nanocomposites élaborés par le procédé de rotomoulage réactif.A reactive rotational molding (RRM) process was developed to obtain a PA6 by activated anionic ring-opening polymerization of epsilon-caprolactam (APA6). Sodium caprolactamate (C10) and caprolactam magnesium bromide (C1) were employed as catalysts, and difunctional hexamethylene-1,6-dicarbamoylcaprolactam (C20) was used as an activator. The kinetics of the anionic polymerization of ε-caprolactam into polyamide 6 was monitored through dynamic rheology and differential scanning calorimetry measurements. The effect of the processing parameters, such as the polymerization temperature, different catalyst/activator combinations and concentrations, on the kinetics of polymerization is discussed. A temperature of 150°C was demonstrated to be the most appropriate. It was also found that crystallization may occur during PA6 polymerization and that the combination C1/C20 was well suited as it permitted a suitable induction time. Isoviscosity curves were drawn in order to determine the available processing window for RRM. The properties of the obtained APA6 were compared with those of a conventionally rotomolded PA6. Results pointed at lower cycle times and increased tensile properties at weak deformation. Additionally, rotational molding of the bilayer PA6/PE-GMA has been studied, the control of the reactions mechanisms involved in the interface by rheology , during formation of the anionically PA6 polymer layer on a PE- GMA layer was carried out in a rheometer , a good adhesion at the interface was observed. The feasibility of developing nanocomposite PA 6/clay by reactive rotational molding process has been tested; the physico-chemical characterization and morphological observations were studied to assess the state of dispersion and the nature of interactions. During this study, we measured the feasibility of intercalation and swelling the clay in the ε-caprolactam monomer and estimate the possibility of having morphology of exfoliated nanocomposites prepared by reactive rotational molding process

On the range of the generalized Fourier transform associated with a Cherednick type operator on the real line

In this work, we establish the real Paley–Wiener theorem for the generalized Fourier transform on R. Therefore, we study the connection between the real Paley–Wiener theorem and local spectral theory. Finally, we generalize Roe’s theorem

Reactive rotational molding process of PP/PA6 bilayer systems: experimental investigations

International audienceRotational molding has been regarded as a plastic molding method with great potential. The process offers virtually stress-free products having no weld lines or material wastage, and utilizes relatively inexpensive molds. Yet its widespread growth is hindered due to long production cycle times, which are limited by the time required to heat up and cool down the mold and the product. This presentation is about the study of making multilayer PP/PA6 parts with the reactive rotational molding process. Different studies have already been made in the past about rotational molding or about reactive process of monolayer part. The aim of this work is to reduce cycle time by making a layer via anionic polymerization of caprolactam, and them to compare each process. This presentation is divided into two parts: the first part deals with rheological, dieclectric aland thermal analysis to investigate the effect of mixtures and the crystallization/polymerization effect; the second part deals with the processing of bilayer parts. Firstly, different mixtures of catalysts and activators were investigated by Rheology and thermal analysis in order to determine which mixture would be the most appropriate for the rotational molding process: 2-2 (2% of activator and 2% of catalyst), 3-3, 4-4 and 6-6. In the second step, different processing investigations have been done in order to study the influences of the parameters like oven time or cooling time. An experimental analysis of heat transfer in reactive rotational molding process was also lead. By using an instrumented mold associated with a radio transmission data acquisition system, we demonstrate that the rotational parts of the bilyar PP/PA6 (reactive way) can be obtained with optimised conditions in correlation with the results of rheology and dielectric measurements. Moreover, the results allows us that it is possible to make bilayer reactive part with the rotational molding process by using less energy in a shorter time

Fluorinated Ethylene Propylene Coatings Deposited by a Spray Process: Mechanical Properties, Scratch and Wear Behavior

International audienceTo increase the lifetime of metallic molds and protect their surface from wear, a fluorinated ethylene propylene (FEP) polymer was coated onto a stainless-steel (SS304) substrate, using an air spray process followed by a heat treatment. The microstructural properties of the coating were studied using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) as well as X-ray diffraction. The mechanical properties and adhesion behavior were analyzed via a nanoindentation test and progressive scratching. According to the results, the FEP coating had a smooth and dense microstructure. The mechanical properties of the coatings, i.e., the hardness and Young’s modulus, were 57 ± 2.35 and 1.56 ± 0.07 GPa, respectively. During scratching, successive delamination stages (initiation, expansion, and propagation) were noticed, and the measured critical loads LC1 (3.36 N), LC2 (6.2 N), and LC3 (7.6 N) indicated a high adhesion of the FEP coating to SS304. The detailed wear behavior and related damage mechanisms of the FEP coating were investigated employing a multi-pass scratch test and SEM in various sliding conditions. It was found that the wear volume increased with an increase in applied load and sliding velocity. Moreover, the FEP coating revealed a low friction coefficient (around 0.13) and a low wear coefficient (3.1 × 10−4 mm3 N m−1). The investigation of the damage mechanisms of the FEP coating showed a viscoelastic plastic deformation related to FEP ductility. Finally, the coating’s resistance to corrosion was examined using electrochemical measurements in a 3.5 wt% NaCl solution. The coating was found to provide satisfactory corrosion protection to the SS304 substrate, as no corrosion was observed after 60 days of immersion

Blending PP with PA6 industrial wastes: Effect of the composition and the compatibilization

International audienceBlending polypropylene to recycled PA6 industrial wastes at different compositions, with and without compatibilizer PPgMA was produced in a corotating twin screw extruder where, polypropylene acts as the polymer matrix and polyamide as the dispersed phase. Several techniques were used to investigate the morphology, thermal, viscoelastic and tensile properties of these blend. Binary PP/PA6 blends showed the presence of PA6 particles dispersed in the PP continuous phase and exhibited a coarse morphology. Increasing PA6 contents in the blend increased their crystallinity and their size and improved the tensile properties at weak deformation. In addition to compatibilizer PPgMA, the morphology shows lower diameters and a decrease in size of the dispersed PA6 particles. The interfacial adhesion was also improved, as a result of the creation of an interphase that was formed by the interaction between the formed PPgPA6 copolymer in situ and both phases. This interphase induced an improvement in tensile properties. The PPgPA6 copolymer generated by the interphase was identified with DMA analysis thanks to an additional transition in loss modulus curves

Valorization of poly(butylene terephthalate) wastes by blending with virgin polypropylene: Effect of the composition and the compatibilization

International audienceBlends of recycled poly(butylene terephthalate) (PBT) parts obtained from scrapped cars, and virgin polypropylene (PP), were prepared in a twin-screw extruder at different compositions. Selected compositions were also prepared with the presence of ethylene-co-glycidyl methacrylate copolymer (E-GMA) and ethylene/methyl acrylate/glycidyl methacrylate terpolymer (E-MA-GMA) compatibilizers. The effect of the composition and the type of compatibilizer, as well as the mixing conditions, on the morphology phase, thermal, viscoelastic behavior, and mechanical properties of the blends has been investigated. Blends PP/PBT of various composition exhibit a coarse morphology and a poor adherence between both phases, resulting in the decrease of ductility, whereas at weak deformation, PBT reinforced the tensile properties of PP. Addition of E-GMA and E-MA-GMA to the PP/PBT blend exhibited a significant change in morphology and improved ductility because of interfacial reactions between PBT end chains and epoxy groups of GMA that generate EG-g-PBT copolymer. Moreover, thermal and viscoelastic study indicated that the miscibility of PP and PBT has been improved further and the reactions were identified. The E-MA-GMA results in the best improvement of ductility

Mechanical behavior of 3D-printed PEEK and its application for personalized orbital implants with various infill patterns and densities

International audienceThis study proposed a 3D-printed PEEK with a specific design to restore the damaged orbit shape. Such printedpersonalized implants are greatly affected by the process parameters, wherefore the effects of the nozzle temperatures,printing speed and layer thickness on the tensile properties were investigated based on the Taguchiapproach. The optimal mechanical properties, i.e., the tensile strength and Young’s modulus, were found to be54.97 MPa and 2.67 GPa, respectively. These properties were obtained by adjusting the nozzle temperature to itshigh level (450 ◦C), while the layer thickness (0.1 mm) and printing speed (20 mm/s) were set to their low levels.Secondly, the mechanical behavior of a personalized orbital implant with these optimized properties wasevaluated via finite elements analysis with various infill patterns and densities, at three thicknesses: 0.3, 0.5 and0.7 mm. It was found that all thicknesses were acceptable for the 100% filling. For the honeycomb pattern, thethicknesses 0.5 and 0.7 mm were satisfactory with a fill rate of 70% and 55% whereas only the thickness of 0.7mm was suitable for the 40% filling. The honeycomb pattern with 40% filling and a maximum stress (7.186 MPa)and strain (0.00627 mm) should be beneficial for light-weight orbital implants