Thesis (Ph. D.)--Virginia Polytechnic Institute and State University, 1992. / Vita. Abstract. Includes bibliographical references (leaves 296-301). Also available via the Internet.

The interphase region at modified polymer surfaces or at polymer\ metal interfaces may be critical in determining the strength and durability in adhesive applications. Methods to investigate these regions are limited however and this research has focused on the use of infrared reflection absorption spectroscopy (IRRAS) and x-ray photoelectron spectroscopy (XPS) to investigate the molecular structure of both modified and unmodified thin films. The optical constants of polyphenylene sulfide (PPS) were determined and exact optical theory was utilized to simulate spectra for a variety of reflectance techniques. This method was also utilized to confirm the ordered state of thin spin coated PPS films. The surface modification of polystyrene, polyphenylene sulfide, and poly(arylene ether) phosphine oxides was also examined by these techniques and optical theory used to optimize experimental conditions. Results after plasma treatment indicated a very thin modified surface layer (< 10 nm) where the thickness and specific surface chemistry depended on the polymer and plasma gas used. The interaction of an epoxy resin with a surface modified PPS film showed that while most of the modified surface layer is removed after this treatment, a remaining amount can serve to cross-link a thin adsorbed epoxy film. Results for the oxygen plasma treatment of poly(arylene ether) phosphine oxides showed the formation of a surface phosphate layer that inhibited further plasma etching. The kinetics of formation and the particular chemistry involved were examined in detail. A new technique, variable temperature reflection absorption spectroscopy (VTRAS) was developed as a method to investigate the reorganization of thin PPS films on a variety of substrates. Both the crystallization and melting temperatures could be determined for quenched coatings on a variety of substrates. While degradation under vacuum was not observed on chromium and aluminum surfaces, PPS films on copper surfaces showed a loss in crystallizability, and did not return to the original ordered state after exposure to temperatures near 300°C. Loss of cuprous oxide was also observed, and chain scission mechanisms were postulated. Additional measurements on thin sputtered cuprous oxide films showed less degradation for the same temperature treatments, emphasizing the role of the underlying metal in the degradation process. Spin coated films of polyetherimide were shown to be oriented after spin coating, and the relaxation to a more random state could also be observed by the VTRAS technique. Degradation of PPS films in air was examined and the diffusion of copper species into the bulk of the film with the formation of copper carboxylates was observed. The use of the VTRAS technique in air also was useful in determining the temperature needed for the onset of degradation. Bonded PPS/copper laminates were investigated and results showed that the particular surface chemistry was crucial in determining the peel strength observed. After a simple thermal! oxidation pretreatment for copper foil, an increase in the peel strength of almost one order of magnitude was observed over non-oxidized foils. Chemical oxidation with alkaline persulfate solutions resulted in a needle-like surface oxide morphology, and bond strengths were also increased by this pretreatment method. Failure surface analysis and model interaction studies with PPS tetramer showed that the formation of excess cuprous sulfide at the interface was the most probable cause of poor adhesion in these systems. Foil pretreatment by thermal oxidation gave the highest peel strength, and also exhibited the lowest amount of interfacial cuprous sulfide. / Ph. D.

In the effort to improve oil production riser performance, new materials are being studied. In the present case, a Polymer Matrix Composite (PMC) is being considered as a replacement for carbon steel in flexible risers manufactured by Wellstream Inc., Panama City, Florida. The Materials Response Group (MRG) at Virginia Tech had the primary responsibility to develop the models for long-term behavior, especially remaining strength and life. The MRG is also responsible for the characterization of the material system with a focus on the effects of time, temperature, and environmental exposure. The present work is part of this effort. The motivation to use a composite material in a non-bonded flexible riser for use in the offshore oil industry is put forth. The requirements for such a material are detailed. Strength analysis and modeling methods are presented with experimental data. The effect of matrix crystallinity on composite mechanical properties is shown. A new method for investigating matrix behavior at elevated temperatures developed. A remaining strength life prediction methodology is recalled and applied to the case of combined fatigue and rupture loading. / Master of Science

Dans ce travail, l’effet du vieillissement thermique sur le comportement en fatigue ducomposite de poly (sulfure de phénylène) renforcé par fibres de verre (PPS/FV) a été étudié. Ce matériau est d’abord étudié par différentes méthodes d’analyse afin de déterminer ses caractéristiques physicochimiqueset mécaniques. Ensuite, le matériau subit un vieillissement thermo-oxydatif accéléré à différentes températures comprises entre 100 °C et 200 °C. Certaines caractéristiques du matériau sont d’ailleurs suivies au cours du vieillissement. A partir des résultats obtenus, un mécanisme d’oxydation estproposé et un modèle cinétique est développé. La validité de ce modèle est vérifiée par les résultats expérimentaux, essentiellement obtenus par la spectrométrie infrarouge. L’effet du vieillissement sur lecomportement mécanique est étudié par les deux axes suivants : D’abord d’une manière indirecte en étudiant l’évolution de la morphologie de la phase cristalline au cours du temps et ensuite par la méthode directe. Dans cette méthode directe, premièrement, le comportement en fatigue et en traction-traction duPPS/FV a été étudié en faisant varier la fréquence et l’amplitude de la sollicitation. La courbe de Wöhler est tracée en fonction du nombre de cycles à la rupture. Il a été constaté que le vieillissement modifie lepositionnement et l’allure de la courbe de Wöhler. Ensuite les éprouvettes vieillies à différentes températures sont testées en fatigue (traction-traction) avec une amplitude maximale (σmax=40 MPa) et un rapport de chargement (R=0,1) afin de suivre l’influence de la dégradation thermo-oxydative au cours du vieillissement. Il a été constaté que l’oxydation a un effet néfaste sur le comportement en fatigue du PPS/FV. Ce matériau perd significativement de ses performances même au début du vieillissement etsurtout à haute température de vieillissement. La perte de la performance en fatigue du matériau s’accentue au fur et à mesure que le processus d’oxydation se poursuit. / In this work, the effect of thermal aging on the fatigue behavior of a glass fiber reinforced poly (phenylene sulfide) composite (PPS/GF) was studied. This material is first characterized by differentmethods of analysis to determine its physicochemical and mechanical characteristics. Subsequently, thematerial undergoes accelerated thermo-oxidative aging at different temperatures between 100 °C and 200 °C. Some characteristics of this material are followed during thermal aging. From the results obtained, an oxidation mechanism is proposed and a kinetic model is developed. The validity of this model is verifiedby the experimental results, essentially obtained by infrared spectrometry. The effect of thermal aging on mechanical behavior is studied in two ways: Firstly, indirect manner by studying the evolution of the morphology of the crystalline phase over time and subsequently by the direct method. In this directmethod, firstly the tension-tension fatigue behavior of PPS/GF was studied by varying the frequency and amplitude of stress. The Wöhler curve is plotted on the basis of the number of cycles at break. Thermalaging has been found to alter the position and shape of the Wöhler curve. Then the samples aged at different temperatures were tested by tension-tension fatigue with a maximum amplitude (σmax = 40 MPa)and a loading ratio (R = 0.1) to follow the influence of thermo-oxidative degradation during aging. It has been found that thermal aging has a detrimental effect on the fatigue behavior of PPS/GF. This material loses its performance significantly even at the beginning of aging, especially in high aging temperature.The loss of fatigue performance grows in the oven as the oxidation process continues.