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Significant advances have been made in the understanding of living/controlled radical polymerization processes since their discovery in the early 1990’s. These processes enable an unprecedented degree of control over polymer architecture that was previously not possible using conventional radical polymerization processes, and this has made possible the synthesis of many new and interesting materials. However, there has been only limited success in commercializing these new methods. Recently there has been increased focus on the development of more industrially viable processes. Dispersed aqueous phase reactions have received much attention because these water-based processes have several technical, economic, and environmental benefits over the more common solution and bulk reactions that were originally developed. Likewise, there has been some investigation of using continuous reactors that have potential technical and economic benefits over the more commonly employed batch reactors. This thesis presents an in-depth study that combines the three aforementioned technologies: living/controlled radical polymerization, dispersed phase aqueous reactions, and continuous reactors. Specifically, the system of interest is a nitroxide-mediated miniemulsion polymerization reaction in a continuous tubular reactor to produce polymer latex. Design of the continuous tubular reactor is discussed in some detail with a focus on specific technical challenges that were faced in building a functional apparatus for this system. Scoping experiments are described which identified a significant effect of temperature ramping rate that is critical to understand when moving to larger scale reactors for this system. The unexpected phenomenon of room temperature polymerization initiated by ascorbic acid is also described. There is demonstration for the first time that bulk and miniemulsion polymers can be produced in a tubular reactor under controlled nitroxide-mediated polymerization conditions, and copolymers can be produced. A detailed residence time distribution study for the tubular reactor is also shown, and several interesting phenomena are discussed that have implications on the practical operating conditions of the tubular reactor. This particular study makes it clear that one should experimentally verify the residence time distribution within a continuous system with the reactants of interest, and that model systems may not give an accurate picture of the real system. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2010-12-20 12:00:37.974

L’industrie automobile est confrontée à la problématique de dimensionnement en fatigue de pièces structurelles en polymères thermoplastiques. En effet, de nombreux facteurs liés à l’environnement ou aux conditions de service influencent la tenue en fatigue. Les campagnes d’essais en fatigue classiquement menées sont longues (1 mois pour une condition donnée). L’objectif de cette thèse est d’accélérer la caractérisation en fatigue de ce type de matériau en utilisant des essais d’auto-échauffement. Une première analyse empirique est démontrée possible et permet d’estimer l’endurance limitée à 106 cycles. L’analyse des indicateurs mécaniques et de l’évolution de la microstructure (MEB et Micro-tomographie rayon X) durant les paliers de chargements confirme l’existence d’un seuil correspondant à cette endurance limitée. Dans un second temps, une méthode est proposée en associant un critère énergétique à la courbe d’auto-échauffement complète afin de prédire en moins de 2 jours une courbe de Wöhler déterministe. Ce critère est confronté à l’étude de facteur influent telle la géométrie de l’échantillon ou la reprise en eau du matériau. Une courbe unifiée reliant l’énergie dissipée par cycle au nombre de cycles à la rupture est proposée. Enfin, la méthode est appliquée avec succès à l’étude de structures. / Designing short fibers reinforced thermoplastics (SFRP) components is now a major concern for the automotive industry. This task is difficult because of the numerous factors affecting the fatigue lifetime coupled to long fatigue campaigns (usually a month for a given experimental condition).The objective of this thesis is to apply a heat built-up protocol on a SFRP used for structural automotive applications (PA66GF50, a polyamide filled with 50% of glass fiber in mass) to predict quickly the fatigue properties from temperature measurements. A heat build-up protocol developed for metallic materials has been used to speed up the fatigue characterization of PA66GF50. The life time estimation given by a first rough analysis is compared successfully to the fatigue curve obtained from a classical campaign. To understand what is caught from the thermal measurements, the evolution of the microstructure throughout the heat build-up test was investigated by X-ray micro-tomography and SEM and compared to the evolution of the mechanical features. In order to provide a relation between the full heat build-up curve and the Wohler curve, the dissipated energy is then evaluated from the thermal measurements and the parameters of an energetic fatigue criterion are identified from the results obtained from one single sample. The fatigue curve predicted from the heat build-up curve and obtained in 2 days, is compared to the one obtained from a classical fatigue campaign and the agreement is very good. The energy based criterion as well as the identification of the dissipation sources from the temperature measurements are finally challenged by an experimental campaign achieved on a sample with a different geometry and different water content. Dissipated energy curve seems unified results. Finally, the method is applied to the study of the lifetime of structures.