Effect of molecular weight on the crystallization and morphology of poly (ethylene oxide) fractions

Abstract

Abstract The temperature dependence of the isothermal growth rate of spherulites and overall crystallization kinetics of different fractions of poly (ethylene oxide) over the range of molecular weight from 300 to 20,000 were studied by calorimetry, dilatometry, and polarized light microscopy, in order to establish the dependence of the kinetic parameters upon molecular weight. The morphology of crystallites was studied by small‐angle x‐ray scattering. In the course of this study it has been established that the growth rates of spherulites and the overall crystallization rates at any fixed supercooling essentially depend upon molecular weight. The minimum in the crystallization rate which occurs at molecular weight 4000 is a consequence of transition from extended‐chain crystallization to folded‐chain crystallization. Small‐angle x‐ray scattering study of the morphological features confirmed this conclusion. This minimum depends very strongly on the degree of supercooling, increasing rather sharply at small supercooling. The temperature and molecular weight dependence of the growth rates of spherulites and the overall crystallization rates has been analyzed by means of the theoretical expression given by Hoffman and Lauritzen. The product of the lateral and basal surface free energies of the crystallites σσe increases with molecular weight and reaches a limiting value at molecular weight 6000. Such behavior is in agreement with morphological transformations.