ABSTRACT:The moisture diffusion process of an epoxy system is studied as a function of epoxy-amine stoichiometry and the resulting microstructure. Differences in diffusion behavior are related to the relative importance of diffusion through the low-density and high-density microstructural phases for different stoichiometries. Also, changes in saturation level with stoichiometry are explained by competing effects of free volume versus the content of the low-density phase. Increasing the humidity level causes a corresponding increase in saturation level, while increasing the temperature causes more pronounced non-Fickian behavior. The effects of absorbed moisture on the thermomechanical properties of the epoxies are also investigated. Reductions in the glass transition temperature, T g , and moisture-induced swelling strains are measured after exposure of samples to the three conditioning environments. Moisture-induced swelling strains increase with increasing moisture content. The reductions in T g range from 5 to 20°C and are generally larger for amine-rich samples than for epoxy-rich and stoichiometric samples.

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Changes in microstructure and mechanical properties are investigated as a function of epoxy-amine stoichiometry. The epoxy-amine system studied exhibits a two-phase structure consisting of a hard microgel phase and a dispersed phase of soft, unreacted and/or partially reacted material. The size distribution of the microgel regions tends to increase with increasing amine content. Concurrently, the connectivity of the softer phase increases dramatically. This two-phase structure is inherently fractal, exhibiting a single glass transition temperature, T g . The T g and elevatedtemperature properties of the epoxy are directly correlated with crosslink density and the percentage of microgel phase observed in microstructure studies. The fracture toughness at room temperature increases with increasing amine content, most likely due to the increased presence of the soft phase, which absorbs more energy during crack growth. Changes in modulus values at 30°C with stoichiometry are explained by considering the effective aspect ratio of the polymer structure in the determination of sample rigidity. Relationships between microgel sizes and the sizes of interphase regions that form in composite and adhesive systems are also discussed in terms of interphase properties.

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