Parmi les différentes technologies de stockage de l'hydrogène, le stockage gazeux sous haute pression apparaît comme la plus mature. Les développements effectués récemment visent à réduire les coûts et améliorer les performances et la sécurité des réservoirs. A l'heure actuelle, le dimensionnement de ces structures est effectué en considérant les propriétés initiales des matériaux et en se basant sur des coefficients de sécurité empiriques ou arbitraires. Les aspects durabilité et résistances à l'endommagement sont rarement pris en compte dans le dimensionnement. Cette étude vise non seulement à développer les connaissances sur les mécanismes d'endommagement des structures composites fibres de carbone / polyamide (6 et 12) pour leur prise en compte dans le dimensionnement des réservoirs mais aussi à identifier les paramètres matériaux et procédés susceptibles d'avoir une influence sur la structure et les propriétés. Dans un premier temps, le comportement mécanique vierge des matériaux est analysé. Ensuite, une étude expérimentale corrélée à des calculs par éléments finis est menée pour déterminer les cinétiques de trois modes d'endommagement et évaluer leur conséquence sur le comportement du stratifié. Dans un troisième temps, un procédé d'enroulement filamentaire est développé et l'influence des paramètres clefs sur la structure et les propriétés des matériaux est mise en évidence. Enfin, des dimensionnements de réservoirs sont réalisés en tenant compte des mécanismes d'endommagement et évaluer leur influence sur le comportement.

Les thermoplastiques renforcés en fibres de verre courtes (TPRFV) sont de plus en plus couramment employés dans l'industrie automobile, en raison de leurs propriétés mécaniques spécifiques intéressantes, de leur mise en forme aisée grâce au moulage par injection et de leur coût modéré. Cette thèse vise à développer une démarche de dimensionnement à la fatigue des composants automobiles en TPRFV, à partir d'un polyamide 66 chargé à 35 % en masse. La première étape est la proposition d'une loi de comportement cyclique, qui modélise les composantes non linéaires de la déformation (viscoélasticité, viscoplasticité, adoucissement) dans différents environnements hygrothermiques. Le modèle anisotrope s'appuie sur la distribution d'orientation des fibres, induite par le procédé d'injection, puis est validé sur structures. La connaissance des chargements mécaniques locaux et des mécanismes non linéaires permet de proposer un critère de fatigue fondé sur la densité d'énergie dissipée par cycle.

Nous nous sommes intéressés à l'optimisation de la dispersion des nanotubes de carbone (CNTs) dans une matrice semi-cristalline : le polyamide 6 (PA-6), et une matrice vitreuse : le poly(méthacrylate de méthyle) (PMMA). Nous avons réalisé des dispersions dans le PA-6 et le PMMA par voie fondu. Nous avons montré que la conductivité et le seuil de conductivité étaient nettement améliorés après un post traitement thermique, quelle que soit la matrice (PMMA ou PA-6). Dans le cas du PMMA, l'étude cinétique de la conductivité en fonction de la température nous a permis de préciser le mécanisme de formation de contacts entre CNTs observé dans le fondu. Une étude structurale et morphologique des composites de PA-6 a été réalisée. Nous montrons la disparition des sphérolites de PA et avons mis en évidence la croissance de lamelles trans-cristallines de PA-6 perpendiculairement à la surface des CNTs. Les CNTs ont aussi été dispersés à partir d'un pré-composite copolymère à blocs/nanotube. Le copolymère à blocs utilisé est un polystyrène-b-polybutadiène-b-polyméthacrylate de méthyle (SBM), les différences de compatibilité de chaque bloc avec les CNTs, la matrice ou le solvant sont utilisées pour stabiliser et disperser les CNTs. L'utilisation du SBM a permis d'améliorer l'état de dispersion dans les deux matrices pour deux méthodes de dispersion : par voie solvant et par voie fondu. Dans le PA-6, l'utilisation du SBM a également permis d'abaisser le seuil de conductivité, grâce à une localisation spécifique des CNTs. Ils sont localisés à l'interface PA-6/SBM pour les pré-composites réalisés par voie fondu et dans la matrice PA-6 pour les pré-composites réalisés par voie solvant.

The extraction and quantitative analysis of low molar mass compounds in polymers is an analytical challenge. It is also important from a practical point of view because the low molar mass compounds in time will migrate from the polymers into the surrounding environment. It is especially important to gain knowledge about the migrating compounds in applications such as medical implants, packaging materials and car interiors. The main aim of this thesis was to develop headspace solid phase microextraction (HS-SPME) methods to meet this challenge. In addition, the work aimed to show the applicability of the methods developed in quality control of polymers, degradation studies and assessment of polymer durability. Factors influencing the extraction of low molar mass compounds from polyamide 6.6 were studied. Particular attention was paid to the matrix effects and to the establishment of headspace equilibrium of 2-cyclopentyl-cyclopentanone in solid polyamide. Hydrogen bonding and adsorption of analyte to the polar matrix was observed and found to cause exceedingly slow establishment of equilibrium. The adsorption could be eliminated by the addition of water, which replaced 2-cyclopentyl-cyclopentanone at the adsorption sites of the polyamide and made it possible to measure the 2-cyclopentyl-cyclopentanone content in polyamide 6.6 using multiple headspace solid-phase microextraction (MHS-SPME). A correlation between the emitted amount of 2-cyclopentyl-cyclopentanone and the amount 2-cyclopentyl-cyclopentanone in the material was found. The correlation was valid also under non-equilibrium conditions, which allows rapid assessment of the 2-cyclopentyl-cyclopentanone content in polyamide 6.6 using headspace sampling. 20 different low molar mass compounds were identified in virgin and recycled polyamide 6.6. The compounds could be classified into four groups: cyclic imides, pyridines, chain fragments and cyclopentanones. The structures of the degradation products imply that the thermo-oxidative degradation starts at the N-vicinal methyl group. Larger amounts of degradation products at lower degree of degradation were formed in recycled than in virgin polyamide 6.6. Thus, processing increases the susceptibility of polyamide 6.6 to thermal oxidation. The total amount of cyclopentanones was reduced upon processing and oxidation. Cyclopentanones are thus not thermo-oxidation products of polyamide 6.6. N-pentyl-succinimide showed the most significant increase due to oxidation and processing. The formation of N-pentyl-succinimide was in correlation with the simultaneous changes in tensile strength. The largest increase in N-pentyl-succinimide coincided with the largest drop in tensile strength.

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.

A fracture mechanics protocol appropriate for small fibers (35 micron diameter) is presented, which allows for the determination of the strength limitations of high performance nylon 6,6 fibers. Specifically, linear elastic fracture mechanics (LEFM) techniques are employed in addition to elastic-plastic fracture mechanics (EPFM) theories to achieve this. We assume that a minute semi-elliptical flaw of an unknown size exists in the specimen, as a result of the detrimental effects of the manufacturing process (melt spinning). Next, we seek to propagate this flaw in a stable manner through an ancillary process such as high cycle or low cycle fatigue (load-unload). After propagation, uniaxial tensile experiments are performed on the fatigued samples, by which the crack growth eventually becomes catastrophic during the process. After performing scanning electron microscopy (SEM) techniques and reviewing fractography, we are able to determine the critical flaw size and ligament length that leads to unstable crack propagation. These results are substituted into the appropriate LEFM equations and are in close agreement with material properties for nylon 6,6. A discussion is provided that draws parallel to the topics discussed in the literature investigation and the experimental results of this study.

The objective of this study is to process and characterize the compatibilized blends of acrylonitrile-butadiene-styrene (ABS) and polyamide-6 (PA6) using olefin based reactive copolymers and subsequently to utilize this blend as a matrix material in short glass fiber (SGF) reinforced composites and organoclay based nanocomposites by applying melt processing technique. In this context, commercially available epoxydized and maleated olefinic copolymers, ethylene-methyl acrylate-glycidyl methacrylate (EMA-GMA) and ethylene-n butyl acrylate-carbon monoxide-maleic anhydride (EnBACO-MAH) were used as compatibilizers at different ratios. Compatibilizing performance of these two olefinic polymers was investigated through blend morphologies, thermal and mechanical properties as a function of blend composition and compatibilizer loading level. Incorporation of compatibilizer resulted in a fine morphology with reduced dispersed particle size. At 5 % EnBACO-MAH, the toughness was observed to be the highest among the blends produced. SGF reinforced ABS and ABS/PA6 blends were prepared with twin screw extrusion. The effects of SGF concentration and extrusion process conditions on the fiber length distribution, mechanical properties and morphologies of the composites were examined. The most compatible organosilane type was designated from interfacial tension and short beam flexural tests, to promote adhesion of SGF to both ABS and PA6. Increasing amount of PA6 in the polymer matrix improved the strength, stiffness and also toughness of the composites. Effects of compatibilizer content and ABS/PA6 ratio on the morphology and mechanical properties of 30% SGF reinforced ABS/PA6 blends were investigated. The most striking result of the study was the improvement in the impact strength of the SGF/ABS/PA6 composite with the additions of compatibilizer. Melt intercalation method was applied to produce ABS/PA6 blends based organoclay nanocomposites. The effects of process conditions and material parameters on the morphology of blends, dispersibility of nanoparticles and mechanical properties were investigated. To improve mixing, the screws of the extruder were modified. Processing with co-rotation yielded finer blend morphology than processing with counter-rotation. Clays were selectively exfoliated in PA6 phase and agglomerated at the interface of ABS/PA6. High level of exfoliation was obtained with increasing PA6 content and with screw speed in co-rotation mode. Screw modification improved the dispersion of clay platelets in the matrix.

The effects of melt state compounding and addition order of ethylene-butyl acrylate-maleic anhydride (E-BA-MAH), ethylene-glycidyl methacrylate (E-GMA), ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA) terpolymer and/or three types of organoclays (Cloisite&reg / 15A, 25A and 30B) on morphology, thermal, mechanical and dynamic mechanical properties of polyamide-6 are investigated. XRD patterns show that the interlayer spacing for Cloisite&reg / 15A remained unchanged / however it increased for the organoclays Cloisite&reg / 25A and Cloisite&reg / 30B in both polyamide-6/organoclay binary nanocomposites and in polyamide-6/organoclay/impact modifier ternary systems. TEM analyses indicate that exfoliated-intercalated nanocomposites are formed. Sizes of elastomeric domains in nanocomposites are larger than the domains in their corresponding blends. The MFI results show that incorporation of elastomer reduces the MFI, due to the formation of graft copolymer. Both storage and loss moduli and complex viscosity of polyamide-6 increase with organoclay addition. In DMA measurements, in rubbery region, all nanocomposites show higher storage modulus than the unfilled counterparts. In general, the organoclays increase tensile and flexural strength, Young&amp / #8217 / s and flexural modulus and elongation at break, but decrease the impact strength, on the contrary, the addition of elastomer has the opposite effect. Generally, Cloisite&reg / 15A containing ternary nanocomposites have higher tensile, flexural and impact strength and Young&amp / #8217 / s and flexural modulus than the ternary nanocomposites prepared with Cloisite&reg / 25A and Cloisite&reg / 30B. In general, nanocomposites processed by adding all the ingredients simultaneously give higher tensile and flexural strength and modulus than the nanocomposites produced by other mixing sequences.

In this study, effect of injection molding process parameters on fiber length and on mechanical properties of Polyamide-6 / glass fiber composite were investigated to produce higher performance composites. Polyamide-6 was first compounded with an E-grade glass fiber in a co-rotating intermeshing twin screw extruder. Then, by using this composite, twenty-five types of experiments were performed by injection molding by changing the barrel temperature, injection pressure, hold pressure, mold temperature, cooling time and screw speed. Izod notched impact, tensile, viscosity, heat deflection temperature, differential scanning calorimetry tests were performed on injection molded samples. By performing these tests, the effects of process parameters on mechanical properties and on fiber length were observed. In order to understand the variation in mechanical properties, thermal tests were also conducted. Also, fiber length distributions of the samples were measured.Experimental data show that fiber breakage decreases with increasing screw speed, injection pressure, however, fiber length increases with increasing barrel temperature, mold temperature and cooling time. Fiber length is almost not affected with the hold pressure. It is assumed in this study that crystallinity is not affected with injection pressure, hold pressure and screw speed. As barrel temperature and cooling time increase, crystallinity increases, however, as mold temperature increases, crystallinity decreases. Impact strength, tensile modulus and tensile strength increase, whereas elongation at break decreases with the average fiber length. Crystallinity affects the tensile strength and modulus positively. The tensile strength and modulus increase with increasing crystallinity.

In the first part of this dissertation, glass fiber reinforced/unreinforced polyamide 6 (PA6) and polyamide 66 (PA66) were compounded with three different flame retardants, which were melamine cyanurate, red phosphorus and brominated epoxy with antimony trioxide, by using an industrial scale twin screw extruder. Then, to investigate flame retardancy of these specimens, UL-94, Limiting Oxygen Index (LOI) and Mass Loss Cone Calorimeter (MLC) tests were carried out. In addition to flammability tests, thermogravimetric analysis (TGA) and tensile testing were performed. Results of the tensile tests were evaluated by relating them with fiber length distributions and fracture surface morphologies under scanning electron microscope (SEM). Incorporation of melamine cyanurate (MCA) to PA6 led to some increase in LOI value and minor reductions in Peak Heat Release Rate (PHRR) value. However, it failed to improve UL-94 rating. Moreover, poor compatibility of MCA with PA6 matrix caused significant reductions in tensile strength. Brominated epoxy in combination with antimony trioxide (Br/Sb) was compounded with both glass fiber reinforced PA6 and PA66. Br/Sb synergism was found to impart excellent flammability reductions in LOI value and UL-94 as V-0 rating. Effectiveness of Br/Sb flame retardant was also proven by the MLC measurements, which showed excessive reductions in PHRR and Total Heat Evolved (THE) values. On the other hand, Br/Sb shifted the degradation temperature 100&deg / C lower and decreased the tensile strength value, due to poor fiber-matrix adhesion and decreased fiber lengths. Red phosphorus (RP), when introduced to glass fiber reinforced PA66 induced V-0 rating in UL-94 together with significant increase in LOI value, and major decrease in PHRR. Degradation temperature was 20&deg / C lower while mechanical properties were kept at acceptable values compared to neat glass fiber reinforced PA66. In the second part of this dissertation, to investigate synergistic flame retardancy of nanoclays / glass fiber reinforced PA6 was compounded by certain nanoclay and an organo-phosphorus flame retardant (OP), which contains aluminum phosphinate, melamine polyphosphate and zinc borate, in a laboratory scale twin screw extruder. Exfoliated clay structure of the nanocomposites was assessed by X-Ray Diffraction (XRD) and Transmission Electron Microscopy (TEM), while thermal stability and combustion behaviors were evaluated by TGA, LOI, UL-94 and MLC. Replacement of a certain fraction of the flame retardant with nanoclay was found to significantly reduce PHRR and THE values, and delay the ignition. Moreover, remarkable improvements were obtained in LOI values along with maintained UL-94 ratings. Residue characterization by ATR-FTIR and SEM ascribed the enhanced flame retardancy of nanocomposite specimens to the formation of a glassy boron-aluminum phosphate barrier reinforced by clay layers at the nanoscale.