Thesis (M.S.)--West Virginia University, 2006. / Title from document title page. Document formatted into pages; contains viii, 31 p. : ill. (some col.). Includes four zip file programs. Includes abstract. Includes bibliographical references (p. 26-27).

Thesis (M. Env. St.)--University of Adelaide, 1984. / Includes bibliographical references (leaves 273-308).

Thesis (Ph. D.)--Institute of Paper Chemistry, 1959. / Includes bibliographical references (p. 142-143).

Cette thèse en partenariat industriel s’intéresse aux peintures polyuréthane et époxy utilisées à des fins protectrices pour des applications ferroviaires. L’objectif de ce projet est de développer de nouveaux additifs spécifiques à ces peintures afin d’améliorer les propriétés mécaniques et adhésives des films sur acier, tout en gardant une bonne dispersion des charges minérales présentes dans la formulation. Des additifs polymères ont été développés. Ces polymères miscibles avec la résine ont été synthétisés par polymérisation cationique (technique du monomère activé) ou anionique coordinée, et présentent différents degrés de polymérisation. Ces polymères sont fonctionnalisés d’une part par un groupement réactif vis-à-vis des charges minérales afin d’assurer leur dispersion, et d’autre part par un groupement réactif vis-à-vis de la résine (polyuréthane ou époxy) afin d’optimiser les propriétés mécaniques des films finaux par ancrage des charges au réseau. Des études par analyses thermogravimétrique et granulométrie laser ont permis de sélectionner les additifs les plus pertinents et de mettre en évidence leur efficacité sur la désagglomération des charges, notamment par rapport aux dispersants commerciaux actuellement utilisés. Des essais mécaniques sur des films de peintures libres ont montré l’impact positif des additifs sur les propriétés mécaniques et adhésives des films sur acier, tant pour les peintures polyuréthane que pour les peintures époxy. Ces nouveaux additifs jouent donc le rôle d’agent dispersant et de promoteur d’adhésion. / Polyurethane and epoxy paints are used in rail applications for protective purposes. The aim of this Ph.D thesis was to develop new additives to improve mechanical and adhesive properties of polyurethane and epoxy paints on steel, keeping good dispersion of pigments and fillers present in paint formulation. Additives were designed as dispersing agents. A polymer which is miscible with the resin paint is synthesized by ring-opening polymerization with different polymerization degrees. Post-modifications were realized to introduce reactive functions ensuring the dispersion of fillers and pigments, and to optimize mechanical properties of paint films (anchoring fillers and pigment to the resin). Thermogravimetry analysis and dynamic light scattering were used to select the best additives and to underline their efficiency on the deagglomeration of pigments and fillers, especially compared to commercial dispersing agents currently used. Mechanical tests highlight that new additives enhanced mechanical and adhesives properties of paint films on steel, both for polyurethane and epoxy paints. Additives, designed as coupling agents, are used at as dispersing agents and adhesion promoters.

Dans l’industrie du pneumatique, l’incorporation de nanoparticules de silice dans les élastomères permet d’obtenir des pneumatiques avec des propriétés mécaniques améliorées. D’un point de vue fondamental, deux contributions sont communément invoquées pour expliquer ces changements : (i) une contribution du réseau de charges, fortement dépendante de leur état de dispersion, (ii) une contribution des chaines dont la conformation est potentiellement modifiée en présence du réseau de charges. Cependant, les mécanismes permettant de relier cette structure nanométrique aux propriétés macroscopiques du matériau sont encore mal compris. Dans ce contexte, nous avons synthétisé des systèmes SBR/Silice modèles constituant une première approche de systèmes industriels plus complexes. En modifiant les conditions de dispersion au moyen d’agent de greffage, nous avons obtenu des nanocomposites avec des dispersions variées et reproductibles, avec des organisations multi-échelle. Celles-ci ont été caractérisées finement par l’utilisation combinée de la Diffusion de Rayons X aux Petits Angles (DXPA) et de la Microscopie Electronique en Transmission (MET). La conformation des chaines, déterminée expérimentalement par Diffusion de Neutrons aux Petits Angles (DNPA), n’est pas affectée par un effet à longue distance des charges. La caractérisation quantitative de la dispersion a permis de mettre en évidence le rôle prépondérant de la compacité des agrégats de silice et de la densité de leur réseau sur le renforcement dans le régime élastique. / In tire industry, the incorporation of nano-sized silica in rubber leads to elastomeric materials with enhanced mechanical properties. In a fundamental approach, two main contributions are commonly accepted to explain these changes: (i) a first from the filler network highly depending on their dispersion, (ii) a second from the chains whose the conformation is potentially modified by the filler network. However, the mechanisms which permit to correlate these nanometric structural properties to the macroscopic mechanical properties are still poorly understood. In such a context, we have synthesized model nanocomposites SBR/silica systems constituting a first approach of more complex industrial systems. By varying dispersions conditions by using grafting agents, we have obtained various and reproducible dispersions, with multi-scale organizations. They have been finely characterized by combining Small Angle X-Ray Scattering (SAXS) and Transmission Electron Microscopy (TEM). Chain conformation experimentally determined by Small Angle Neutron Scattering (SANS) is not affected by any long range effect of fillers. The quantitative characterization of filler dispersions has shown the major role of silica aggregates compactness and the density of their network on the reinforcement in the elastic regime.

The development of analytical methods for emerging contaminants creates many unique challenges for analytical chemists. By their nature, emerging contaminants have inherent data gaps related to their environmental occurrence, fate, and impact. This dissertation is a compilation of three studies related to method development for the structural identification of emerging contaminants, the detection and quantification of chemicals used in unprecedented quantities and applications, and the extraction of compounds from complex matrices where the solvent-solute-matrix interactions are not completely understood. The three studies present analytical methods developed for emerging contaminants in complex matrices, including: fluorochemical surfactants in aqueous film-forming foams, oil dispersant surfactants in seawater, and fullerene nanomaterials in carbonaceous solids. Aqueous film-forming foams, used in military and commercial firefighting, represent environmentally-relevant commercial mixtures that contain a variety of fluorochemical surfactants. Combining the surfactant-selective ionization of fast atom bombardment mass spectrometry with high resolution mass spectrometry, chemical formulas for 11 different fluorochemical classes were identified. Then AFFF-related patents were used to determine the structures. Of the eleven classes of fluorochemicals, ten have little, if any, data on their environmental occurrence, fate, and potential impacts in the peer-reviewed literature. In addition, nine of the identified classes had either cationic or zwitterionic functionalities and are likely to have different transport properties compared to the well-studied anionic fluorochemicals, such as perfluorooctanoate. After the Deepwater Horizon oil spill in the summer of 2010, one of the emergency response methods for the mitigation of the oil's environmental impact was the use of unprecedented amounts of oil dispersant to break down the oil slick and encourage biodegradation. This event illustrated the need for rapid analytical method development in order to respond to the potential environmental disaster in a timely manner. Using large volume injection liquid chromatography with tandem mass spectrometry, an analytical method was developed for the trace analysis of the multiple dispersant surfactant classes and the potential degradation products of the primary surfactant. Limits of detection ranged from 49 ��� 3,000 ng/L. The method provided excellent recovery (86 ��� 119%) and precision (10 ��� 23% RSD), while also accommodating for the high salinity of seawater samples and analyte contamination. Despite the fact that fullerene nanomaterials have been studied for almost three decades, research is still being conducted to fully understand the environmental properties of these materials. Previous studies to extract fullerenes from environmental matrices have resulted in low efficiency, high variability, or the extraction efficiencies have gone unreported. Extraction by ultrasonication with toluene and 1-methylnaphthalene increased the recovery 5-fold of a spiked, isotopically-labeled C������ surrogate from carbon lampblack as compared to that of the conventional approach of extracting with 100% toluene. The study revealed the importance of evaluating experimental variables such as extraction solvent composition and volume, and sample mass, as they have a significant impact on the quantitative extraction of fullerenes from environmental matrices. / Graduation date: 2013 / Access restricted to the OSU Community at author's request from Aug. 15, 2012 - Aug. 15, 2013