In this work the relationship between physical properties, such as physical aging and relaxation time distributions, and chemical structure for a variety of polymeric systems were investigated. Although there is a vast amount of physical aging data for polymers, most of these studies do not attempt to correlate structure with physical aging. Therefore, a set of engineering thermoplastics was examined with the goal of relating certain of their characteristic molecular dimensions to their mechanical and volumetric physical aging attributes.Another series of polymeric materials, based on a poly(ether sulfone) backbone, and having various endgroups differing in size, was also studied to determine physical aging rates and relaxation time distributions. Furthermore, it was concluded that the density of the poly(ether sulfones) increased while the glass transition temperature decreased as the endgroup became smaller.Thermoplastic toughened epoxies were also examined to clarify the importance of covalent bonds between toughener and epoxy on physical aging, relaxation time distributions and fracture toughness. In these studies the covalently bonded tougheners differed from their non-reactive counterparts in the rates of volumetric physical aging at high temperatures for the difunctional epoxy. The solvent resistance of the reactive thermoplastic toughened tetrafunctional epoxy was higher than the non-reactive thermoplastic toughened system. The tetrafunctional epoxies with the reactive toughener also had higher toughener glass transition temperatures. / Ph. D.

In this work the relationships between penetrant structure, its transport properties, and its effects on the mechanical properties of a polymer matrix were investigated. Although there is a vast amount of data on the diffusion of low molecular weight molecules into polymeric materials and on the mechanical properties of various polymer-penetrant systems, no attempts have been made to inter-relate the two properties with respect to the chemical structure of the diffusant. Therefore, two series of penetrants - n-alkanes and esters - were examined in this context, with the goal of correlating molecular size, shape, and chemical nature of the penetrant to its final transport and matrix mechanical properties. These correlations have been demonstrated to allow quantitative prediction of one property, given a reasonable set of data on the other parameters. A series of n-alkanes (C6-C17) and esters (C5-C17) have been used to separate the effects of penetrant size and shape, from those due to polymer-penetrant interactions, in the diffusion through a polyamide polymeric adhesive. These effects have been taken into account in order to yield a qualitative relationship that allows for prediction of diffusivity based upon penetrant structural information. Transport properties have been analyzed using mass uptake experiments as well as an in-situ FTIR-ATR technique to provide detailed kinetic as well as thermodynamic information on this process. The phenomenon of diffusion and its effects on the resulting dynamic mechanical response of a matrix polymeric adhesive have been studied in great detail using the method of reduced variables. The concept of a diffusion-time shift factor (log aDt) has been introduced to create doubly-reduced master curves, taking into account the effects of temperature and the variations in the polymer mechanical response due to the existence of a low molecular weight penetrant. / Ph. D.