Results are presented for two unrelated studies. The primary topic involved the crystallization behavior and morphological features of two polyimides, namely LARCCPI (Langley Research .Center Crystalline folyimide) and LARC-TPI (Thermoplastic folyimide). The LARC-CPI study first considered feature~ affecting crystallization behavior including inherent viscosity, crystallization temperature, and melt temperature and time. Data were analyzed using the A vrami analysis. Morphological features were investigated using techniques including scanning electron microscopy (SEM), transmission electron microscopy (TEM), and small angle x-ray scattering (SAXS). Permanganic etching combined with SEM successfully revealed morphological detail, further supported by TEM data. These data support the Avrami analysis results. SAXS data reflected the influence of several crystalliz.ation variables on the long spacing. SAXS results also revealed the presence of a broad second scattering peak for semicrystalline samples appearing in the same position regardless of crystalliz.ation temperature or inherent viscosity. Molecular modelling predicted a low-energy helical conformation with a near-periodic repeat distance corresponding to the second SAXS peak. This conformation is offered as a tentative explanation for that peak. Finally, the effe.ct of nucleating agent on the recrystalliz.ability of a higher inherent viscosity LARC-CPI was considered. One of several nucleators appeared effective in enhancing recrystallization. The LARC-TPI study involved the development of a thermal cycle based upon crystalliz.ation kinetics results, allowing the successful recrystallization of LARC-TPI following exposure to elevated temperatures. This cycle was then used to modify an existing composite fabrication process to produce semicrystalline composites. Two carbon fiber types were utilized to make composites via both fabrication cycles. These composites were evaluated using several techniques. The second unrelated project examined very localized orientation behavior in two types of semi crystalline superstructure using FTIR microspectroscopy. Results were obtained utilizing linear dichroism for orientation within spherulitic and transcrystalline superstructure in poly(glycolide co-lactide) and isotactic polypropylene. An increase in orientation on an absolute basis as a function of position was successfully measured. Orientation function values were higher on an absolute basis for the transcrystalline superstructure. However, the sign of the isotactic polypropylene spherulite orientation function values was the opposite of what was anticipated. These results were considered in light of spherulite W AXS data also obtained. / Ph. D.