Kinetics of Polymer Crystallization with Aggregating Small Crystallites.

The isothermal crystallization near the glass transition temperature from the melt state of poly(trimethylene terephthalate) has been studied by wide-angle x-ray diffraction (WAXD), small-angle x-ray scattering (SAXS), and optical microscopy. The SAXS and WAXD results show the crystallization mechanism in which the crystalline nodules cover the entire sample with the formation of aggregation regions. The analysis of the SAXS results using Kolmogorov-Johnson-Mehl-Avrami theory indicates that the formation kinetics of the aggregation regions is of three-dimensional homogeneous nucleation type. The analysis of the SAXS profiles using Sekimoto's theory provides the growth velocity and the nucleation rate of the aggregation region. The temperature dependence of the growth velocity of the aggregation region is a natural extrapolation of that of spherulite to the high supercooling region. The temperature dependence of the nucleation rate of the aggregation region is also represented by the parameters of the spherulitic growth rate. The result of the growth velocities of the aggregation region and the spherulite suggests the existence of precursors at the front of the crystal growth.