The isothermal crystallization and melting temperatures of poly(ε-caprolactone) were correlated using fast differential scanning calorimetry. The melting kinetics was found to be independent of isothermal crystallization temperature and time. The conventional Hoffman-Weeks method could not be used to determine the equilibrium melting temperature because the observed melting temperatures were greater than the crystallization temperatures by a constant, so the Gibbs-Thomson method was used instead, yielding an equilibrium melting temperature of 103.4 ± 2.3°C. A modification was proposed to the non-linear Hoffman-Weeks equation that included a non-linear undercooling dependence for the kinetic fold surface free energy upon crystallization and permitted accurate modeling of the observed melting behavior. The isothermal crystallization rates of four narrow molecular weight poly(ethylene oxide) fractions were characterized using fast differential scanning calorimetry for crystallization temperatures spanning 100°C range with the lower limit approaching the glass transition. A transition from homogeneous to heterogeneous primary nucleation was observed at −5°C. The kinetic analysis suggested that the crystal growth geometry depends strongly on temperature, where rod-like structures begin to appear near the glass transition temperature, highly branched solid sheaves grow throughout the homogeneous primary nucleation temperature range, and spherulites grow in the heterogenous primary nucleation range. Poly(δ-valerolactone) was synthesized using microwave-assisted techniques. Narrow molecular weight fractions were obtained using successive precipitation fractionation. Preliminary isothermal crystallization studies suggest that conventional thermal analysis methods are not adequate to measure the melting temperatures accurately due to reorganization during heating.Doctor of PhilosophyPlastics may be classified into two general categories: those which form ordered domains upon solidification, i.e. undergo crystallization, and those which remain disordered upon solidification, i.e. form glasses. This work is focused on studying the crystallization and melting processes in two linear polymers, poly(ε-caprolactone) and poly(ethylene oxide), using new experimental technology. In the case of poly(ε-caprolactone), the experimental data could not be rationalized by existing theories, and we have proposed modifications to these theories that explained the results. In the case of poly(ethylene oxide), the application of new experimental technology resulted in previously unreported data that indicated novel behavior at very low crystallization temperatures. In the last portion of this work, poly(δ-valerolactone) was made using a novel approach. Conventional experimental approaches to measuring the crystallization and melting behavior were shown to be inadequate.