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Our research focuses on re-using a waste a material, cross-linked polyethylene abbreviated XLPE, which is a widely used coating for wires. XLPE is strong and has excellent thermal properties due to its chemical structure - what leads to the significance of recycling this valuable polymer. Properties of XLPE include good resistance to heat, resistance to chemical corrosion, and high impact strength. A wire is usually composed of a metal core conductor and polymeric coating layers. One creates a new coating, including little pieces of recycled XLPE in the lower layer adjacent to the wire, and virgin XLPE only in the upper layer. Industries are often wasting materials which might be useful. Mostly, some returned or excess products could be recycled to create a new type of product or enable the original use. This method helps cleaning the waste, lowers the costs, and enhances the income of the manufacturing company. With the changing of the thickness of the outer layer, the roughness changes significantly. Moreover, different processing methods result in surfaces that look differently.

Les travaux entrepris dans le cadre de cette thèse portent sur l’étude de la représentativité du vieillissement thermique accéléré par rapport au vieillissement en conditions d’usage de mélanges de polyéthylènes utilisés comme isolant de câbles qualifiés K1 de dernière génération dans les bâtiments réacteurs des centrales nucléaires. L’influence de l’état physique des constituants du mélange pendant le vieillissement sur les cinétiques et les mécanismes de vieillissement est également étudiée. Le matériau est un mélange de deux polyéthylènes : un polyéthylène linéaire (PE) et un polyéthylène ramifié (PEcB) réticulé au peroxyde. Une approche basée sur l’analyse multi-échelle (moléculaire, microstructurale, macromoléculaire et macroscopique) a été mise en place. Plusieurs températures de vieillissement ont été choisies afin de faire varier l’état physique de l’un ou des deux polyéthylènes du mélange au cours du vieillissement. Les résultats à l’échelle moléculaire montrent les mêmes produits d’oxydation et les mêmes cinétiques pour le PE et le PEcB. En revanche, on observe une oxydation plus rapide du mélange 5050. Les cinétiques d’oxydation obéissent à une loi d’Arrhenius pour des vieillissements compris entre 80°C et 110°C, mais l’extrapolation à la température d’utilisation (60°C) n’est pas représentative du résultat expérimental. L’état physique (solide ou fondu) des échantillons au moment du vieillissement n’explique pas la non-représentativité des vieillissements accélérés. Les variations des propriétés mécaniques peuvent être reliées à l’évolution de la microstructure de chaque polymère et de leur architecture macromoléculaire au cours du vieillissement thermo-oxydant. Néanmoins, il apparaît difficile de corréler l’évolution de la structure chimique au cours du vieillissement avec l’évolution des propriétés mécaniques. Cette étude souligne l’importance de l’approche multi-échelle pour avoir une compréhension globale des phénomènes de vieillissement. / This work is devoted to the study of the representativeness of accelerated thermal ageing compared to ageing in use conditions of polyethylene blends used as insulant in the lastest-generation K1 qualified cables in nuclear power plants’ reactor buildings. The influence of the physical state of the components in the blends during ageing on the kinetics and ageing mechanisms is also studied. The material is a blend of two polyethylenes: a linear polyethylene (PE) and a branched polyethylene (PEcB) crosslinked with peroxides. An approach based on the multi-scale analysis (molecular, microstructural, macromolecular and macroscopic) was set up. Several ageing temperatures were chosen in order to vary the physical state of one or both polyethylenes in the blend during ageing. The results at molecular scale show the same oxidation products and kinetics for PE and PEcB. However, one can observe a faster degradation for the 5050 blend. The oxidation kinetics obey the Arrhenius law for thermal ageing between 80°C and 110°C, but extrapolation to the operating temperature (60°C) is not representative of the experimental data. The physical state (solid or molten) of the samples during thermal ageing does not explain the non-representativeness of accelerated ageing. The variations of mechanical properties can be linked to the evolution of the microstructure of each polymer and of their macromolecular architecture during thermo-oxidative ageing. Nevertheless, it is difficult to correlate the evolution of the chemical structure during ageing with the evolution of the mechanical properties. This study emphasizes the importance of the multi-scale analysis in order to have a comprehensive understanding of the ageing phenomena.

Vinyltrialkoxysilanes are grafted onto polyolefins via a radical mechanism; in a subsequent step, the pendant alkoxysilanes hydrolyze and condense upon exposure to water, resulting formation of crosslinks. Straight chain hydrocarbons were used as model compounds to investigate the regioselectivity of vinyltrimethoxysilane grafting. To stabilize the water-sensitive grafted products, the methoxy groups were substituted using phenyllithium. It was found that this reaction must be carried out for a minimum of three days to ensure full substitution. The grafted products were then separated on a weight basis using semi-preparative HPLC. Analysis of the di-grafted fraction using edited HSQC and HSQC-TOCSY NMR showed that radical propagation occurs via 1,4- and 1,5-intramolecular hydrogen shifts along the hydrocarbon backbone, resulting in multiple grafts per backbone. Post-combustion carbon capture targets CO₂ emissions from large point sources for capture and sequestration. A new class of potential carbon capture agents known as reversible ionic liquids (RevILs) has been synthesized and evaluated in terms of potential performance parameters (e.g. CO₂ capacity, viscosity, enthalpy of regeneration). These RevILs are silylated amines, which react with CO₂ to form a salt comprising an ammonium cation and a carbamate anion that is liquid at room temperature. Structural modifications of the basic silylamine skeleton result in drastic differences in the performance of the resulting RevIL. Systematic variation of the silylated amines allowed determination of a structure-property relationship, and continued iterations will allow development of an ideal candidate for scale-up. The properties and potential applications of gold nanoparticles (AuNP) are highly dependent on their size and shape. These properties are commonly controlled during liquid-phase synthesis through the use of capping agents, which must be removed following synthesis. Reverse micelles can also be used to control the morphology of AuNP during their synthesis. When RevILs are used in the formation of these reverse micelles, either as the disperse phase or as the surfactant, the built-in switch can be used to release the nanoparticles following their synthesis. This release on command could decrease the post-synthetic steps required to clean and purify AuNP prior to use. We have successfully synthesized AuNP using a number of different RevILs.