Consumption of plastics has increased exponentially, in line with the world's population. Not surprisingly this is reflected in enormous growth of the plastic industry especially during the last five decades. Commensurate with this, waste produced from plastics consumption has created a major environmental problem. Many types of waste disposal methods have been used all over the world so far, but all of them have disadvantages. Furthermore, some methods are responsible for the generation of green house gases and further contribution to global warming. Recently, reduction of green house gas emission has become a target of most industries. Plastic recycling and reuse breaks the cycle of endless production of virgin polymer and thus contributes to a net reduction of green house gas emission. Recycling of plastics should produce materials with improved properties to replace virgin plastics for a variety of applications. Improvement in the properties of recycled plastics can be achieved by blending with other plastics, by filler addition and by modification using free radical initiators. Introduction of the free radical initiator (organic peroxide) during reprocessing of the recycled plastics has been found to offer significant property improvements to the recycled materials. Extremely small amounts of a free radical initiator (typically ranging between 0.01 wt% to 0.2 wt%) is capable of enhancing the properties of the recycled plastics to a great extent. This project investigates the use of free radical initiators in the recycling of post consumer recycled high density polyethylene using reactive extrusion. Both molecular and rheological characterisation of recycled and reprocessed materials was carried out and this was followed by tensile testing of the modified materials to satisfy end use applications such as packaging and drainage piping. Post consumer recycled high density polyethylene (R-HDPE) resin and virgin high density polyethylene (V-HDPE) were reactively extruded with low concentrations of dicumyl peroxide (DCP) and 1, 3 1, 4 Bis (tert- butylperoxyisopropyl) Benzene (OP2) respectively in a twin screw extruder in order to produce modified materials with varying composition (0.0 wt%, 0.02 wt%, 0.05 wt%, 0.07 wt%, 0.10 wt% and 0.15 wt%) of both organic peroxides. Morphological characterisation using modulated differential scanning calorimetry (MDSC) demonstrated that there is a decrease in the crystallinity level for all the modified samples. Shear rheological tests were carried out to study the structure of the modified materials within the linear viscoelastic region. Viscoelastic parameters, such as storage modulus (G'), loss modulus (G

Alternative methods to control the molecular weight and short chain branching distribution of polyethylene were investigated. The ability to produce polyolefins with multimodal microstructural distributions using single catalyst/single reactor set-up is very attractive and could, in principle, be used to produce polyolefin resins with advanced molecular architecture. In this thesis, resins with controlled microstructures were produced, characterized and properties tested in order to develop a better understanding of polymerization structure-property relationships. Copolymerizations of ethylene and 1-hexene were carried out with an in-situ supported metallocene catalyst. Copolymers were produced with different alkylaluminum activators and the effect on molecular weight and short chain branching distributions was examined. It was found that different activator types produce polymer with unimodal and narrow molecular weight distributions but with very different short chain branching distributions. Each activator exhibits unique comonomer incorporation characteristics to produce bimodal short chain branching distributions with the use of a single activator. By using individual and mixed activator systems, it is possible to control the short chain branching distributions of the resulting copolymers while maintaining narrow molecular weight distributions. To further investigate the capabilities of this in-situ supported catalyst system, an experimental design was carried out to study the effect of polymerization conditions on the catalyst activity and microstructure of poly(ethylene-co-1-octene). The parameters investigated were: polymerization temperature, monomer pressure, chain transfer to hydrogen, comonomer/ethylene feed ratio and concentration of alkylaluminum. The effect of each parameter on the catalyst activity, comonomer incorporation and molecular weight distribution was investigated. The results obtained were not typical of a conventional single-site catalyst. The copolymerization system was sensitive to all of the parameters and many interactions were evident. The most prominent effect was the catalyst response to temperature. As the temperature was decreased, the short chain branching distributions of the copolymers became broad and bimodal. Overall, it was found that a wide range of microstructures could be produced, ranging from copolymers with low and high 1-octene content with unimodal to broad short chain branching distributions, and from low to high molecular weight with narrow to broad molecular weight distributions. To examine the effect of these broad short chain branching distributions on the polymer properties, a series of poly(ethylene-co-1-hexene) resins with very distinct, and in some cases bimodal crystalline distributions, were synthesized. The attractive feature of the resins in this study is that their molecular weight distributions are similar but each possesses a different short chain branching distribution, thus effectively minimizing the effect of molecular weight on the properties investigated. It was found that the tensile properties of a copolymer could be controlled by the ratio of the crystalline species present in the sample. In this study, a balance of stiffness and toughness was exhibited by a copolymer containing a large proportion of crystalline material and a small fraction of material of lower crystallinity. A series of poly(ethylene-co-1-octene) resins with tailored molecular weight and short chain branching distributions were synthesized with a heterogeneous metallocene catalyst in a two-stage polymerization process. Blends of high molecular weight copolymer and low molecular weight homopolymer and reverse blends of low molecular weight copolymer and high molecular weight homopolymer were produced. The physical properties of these resins were tested for their dynamic mechanical (tensile) and rheological properties. Increasing the copolymer content in the blend resulted in a decrease in stiffness. However, the energy dampening properties of these blends benefit from the presence of the copolymer. It was also confirmed that the melt flow properties of polymers mostly depend on their molecular weight distribution. Regardless of the comonomer content, the melt viscosities decreased with the addition of low molecular weight polymer.

Alternative methods to control the molecular weight and short chain branching distribution of polyethylene were investigated. The ability to produce polyolefins with multimodal microstructural distributions using single catalyst/single reactor set-up is very attractive and could, in principle, be used to produce polyolefin resins with advanced molecular architecture. In this thesis, resins with controlled microstructures were produced, characterized and properties tested in order to develop a better understanding of polymerization structure-property relationships. Copolymerizations of ethylene and 1-hexene were carried out with an in-situ supported metallocene catalyst. Copolymers were produced with different alkylaluminum activators and the effect on molecular weight and short chain branching distributions was examined. It was found that different activator types produce polymer with unimodal and narrow molecular weight distributions but with very different short chain branching distributions. Each activator exhibits unique comonomer incorporation characteristics to produce bimodal short chain branching distributions with the use of a single activator. By using individual and mixed activator systems, it is possible to control the short chain branching distributions of the resulting copolymers while maintaining narrow molecular weight distributions. To further investigate the capabilities of this in-situ supported catalyst system, an experimental design was carried out to study the effect of polymerization conditions on the catalyst activity and microstructure of poly(ethylene-co-1-octene). The parameters investigated were: polymerization temperature, monomer pressure, chain transfer to hydrogen, comonomer/ethylene feed ratio and concentration of alkylaluminum. The effect of each parameter on the catalyst activity, comonomer incorporation and molecular weight distribution was investigated. The results obtained were not typical of a conventional single-site catalyst. The copolymerization system was sensitive to all of the parameters and many interactions were evident. The most prominent effect was the catalyst response to temperature. As the temperature was decreased, the short chain branching distributions of the copolymers became broad and bimodal. Overall, it was found that a wide range of microstructures could be produced, ranging from copolymers with low and high 1-octene content with unimodal to broad short chain branching distributions, and from low to high molecular weight with narrow to broad molecular weight distributions. To examine the effect of these broad short chain branching distributions on the polymer properties, a series of poly(ethylene-co-1-hexene) resins with very distinct, and in some cases bimodal crystalline distributions, were synthesized. The attractive feature of the resins in this study is that their molecular weight distributions are similar but each possesses a different short chain branching distribution, thus effectively minimizing the effect of molecular weight on the properties investigated. It was found that the tensile properties of a copolymer could be controlled by the ratio of the crystalline species present in the sample. In this study, a balance of stiffness and toughness was exhibited by a copolymer containing a large proportion of crystalline material and a small fraction of material of lower crystallinity. A series of poly(ethylene-co-1-octene) resins with tailored molecular weight and short chain branching distributions were synthesized with a heterogeneous metallocene catalyst in a two-stage polymerization process. Blends of high molecular weight copolymer and low molecular weight homopolymer and reverse blends of low molecular weight copolymer and high molecular weight homopolymer were produced. The physical properties of these resins were tested for their dynamic mechanical (tensile) and rheological properties. Increasing the copolymer content in the blend resulted in a decrease in stiffness. However, the energy dampening properties of these blends benefit from the presence of the copolymer. It was also confirmed that the melt flow properties of polymers mostly depend on their molecular weight distribution. Regardless of the comonomer content, the melt viscosities decreased with the addition of low molecular weight polymer.

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Yes / Highly-oriented poly (lactic acid) (PLA) with bionic fibrillar structure and micro-grooves was fabricated through solid hot drawing technology for further improving the mechanical properties and blood biocompatibility of PLA as blood-contacting medical devices. In order to enhance the melt strength and thus obtain high orientation degree, PLA was first chain branched with pentaerythritol polyglycidyl ether (PGE). The branching degree as high as 12.69 mol% can be obtained at 0.5 wt% PGE content. The complex viscosity, elastic and viscous modulus for chain branched PLA were improved resulting from the enhancement of molecular entanglement, and consequently higher draw ratio can be achieved during the subsequent hot stretching. The stress-induced crystallization of PLA occurred during stretching, and the crystal structure of the oriented PLA can be attributed to the α′ crystalline form. The tensile strength and modulus of PLA were improved dramatically by drawing. Chain branching and orientation could significantly enhance the blood compatibility of PLA by prolonging clotting time and decreasing hemolysis ratio, protein adsorption and platelet activation. Fibrous structure as well as micro-grooves can be observed for the oriented PLA which were similar to intimal layer of blood vessel, and this bionic structure was considered to be beneficial to decrease the activation and/or adhesion of platelets.

Yes / Highly-oriented poly (lactic acid) (PLA) with bionic micro-grooves was fabricated through solid hot drawing technology for further improving the mechanical properties and blood biocompatibility of PLA. In order to enhance the melt strength and thus obtain high orientation degree, long chain branched PLA (LCB-PLA) was prepared at first through a two-step ring-opening reaction during processing. Linear viscoelasticity combined with branch-on-branch (BOB) model was used to predict probable compositions and chain topologies of the products, and it was found that the molecular weight of PLA increased and topological structures with star like chain with three arms and tree-like chain with two generations formed during reactive processing, and consequently draw ratio as high as1200% can be achieved during the subsequent hot stretching. With the increase of draw ratio, the tensile strength and orientation degree of PLA increased dramatically. Long chain branching and orientation could significantly enhance the blood compatibility of PLA by prolonging clotting time and decreasing platelet activation. Micro-grooves can be observed on the surface of the oriented PLA which were similar to the intimal layer of blood vessel, and such bionic structure resulted from the formation of the oriented shish kebab-like crystals along the draw direction.

SOLUTION AND MELT BEHAVIOUR OF HIGH-DENSITY POLYETHYLENE - Successive Solution Fractionation mechanism - Influence of the molecular structure on the flow In the field of polyethylene characterization, one of the most challenging research topic is certainly an accurate molecular structure determination of industrial products, in terms of molar mass distribution (MMD), corresponding average-molar masses and molecular architecture (branching nature, content and heterogeneity). Solution to this long-term problem necessarily calls for a multi-disciplinary approach. Therefore, respective advantages of molecular structure characterization in solution and in the melt are exploited. In solution, chromatographic and spectroscopic methods allow determination of MMD, average branching content and intermolecular heterogeneity within their detection limits. Rheological testing in the melt could be a very powerful molecular structure investigation tool, due to its extreme sensitivity to high molar mass (MM) tailing or long chain branching (LCB) traces. But when the rheological tests results are in hand, we often still wonder what kind of molecular structure gives rise to such results. Indeed, melt signal depends on MM, MMD and LCB presence. MMD determination and LCB quantification by melt approach is impossible as long as respective effects of these molecular parameters are not clearly quantified. The general purpose of the present work is to contribute to a better molecular structure characterization of high-density polyethylene by developing, in a first time, a preparative fractionation method able to provide narrow-disperse linear and long chain branched samples, essential to separate concomitant effects of MM, MMD and LCB on rheological behaviour. Once such model fractions isolated, influence of MM and LCB on both shear and elongational flow behaviours in the melt is studied. /Dans le domaine du polyéthylène, un des sujets de recherche les plus investigués à l'heure actuelle est la détermination précise de la structure moléculaire de résines industrielles, en termes de distribution des masses molaires (MMD), de masses molaires moyennes correspondantes et d'architecture moléculaire (nature, teneur et hétérogénéité). La résolution de cette problématique nécessite une approche multi-disciplinaire, afin d' exploiter simultanément les avantages d'une caractérisation en solution et à l'état fondu. En solution, certaines méthodes chromatographiques et spectroscopiques permettent de déterminer une MMD, une teneur moyenne en branchement et leur distribution, dans leurs limites de détection. La mesure du comportement rhéologique à l'état fondu pourrait s'avérer un formidable outil de caractérisation de la structure moléculaire en raison de son extrême sensibilité à certains détails moléculaires, tels que la présence de traces de LCB ou de très hautes masses molaires (MM). Malheureusement, le signal rhéologique dépend de manière conjointe de la MM, MMD et de la présence ou non de LCB, de telle sorte que la détermination d'une MMD ou d'une teneur en LCB par cette voie est impossible aussi longtemps que les effets respectifs de ces paramètres moléculaires sur le comportement rhéologique n'ont pas été clairement et distinctement établis. L'objectif global de cette thèse est de contribuer à une meilleure caractérisation de la structure moléculaire du polyéthylène haute densité en développant, dans un premier temps, une méthode préparative de fractionnement capable de produire des échantillons, linéaires ou branchés, à MMD la plus étroite possible, indispensables en vue de séparer les effets concomitants de la MM, MMD et LCB sur le comportement rhéologique à l'état fondu. Une fois de tels objets modèles isolés, l'influence de la MM et du LCB sur le comportement rhéologique, en cisaillement et en élongation, sera étudié.

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