INFLUENCE OF SAMPLE THICKNESS ON ISOTHERMAL CRYSTALLIZATION KINETICS OF POLYMERS IN A CONFINED VOLUME

Isothermal crystallization process of polymers in a confined volume was simulated in the case of instantaneous nucleation by use of the Monte Carlo method. The influence of sample thickness on some kinetic parameters of crystallization was quantitatively evaluated. It was found that there was a critical thickness value. Influence of thickness on the crystallization behavior was only found for samples of thickness near and less than the critical value. For thick samples the Avrami plot showed straight lines with a turning point at the late stage of crystallization due to the secondary crystallization. When the thickness was near or less than the critical value a primary turning point appeared in the Avrami plot at the very beginning of the crystallization process. A model was proposed to explain the mechanism of this phenomenon. According to this model the critical thickness value is related to the nucleation density or the average distance between adjacent nuclei, and the primary turning point is an indication of a transformation of crystal growth geometry from a three-dimensional mode to a two-dimensional one. Analysis of experimental results of PEO isothermally crystallized at 53.5℃ was consistent with the proposed model.