Growth kinetics of polymer crystals in bulk

Temperature-dependent measurements of spherulite growth rates carried out for i-polystyrene, poly(epsilon -caprolactone) and linear polyethylene show that the controlling activation barrier diverges at a temperature which is 14K, 22K and 12K, respectively, below the equilibrium melting points. We discuss the existence of such a "zero growth temperature" T (zg) in the framework of a recently introduced thermodynamic multiphase scheme and identify T (zg) with the temperature of a (hidden) transition between the melt and a mesomorphic phase which mediates the crystal growth. The rate-determining step in our model of crystal growth is the attachment of chain sequences from the melt onto the lateral face of a mesomorphic layer at the growth front. The necessary straightening of the sequence prior to an attachment is the cause of the activation barrier. A theory based on this view describes correctly the observations. With a knowledge of T (zg) it is possible to fully establish the nanophase diagram describing the stability ranges of crystalline and mesomorphic layers in a melt. An evaluation of data from small-angle X-ray scattering, calorimetry and optical growth rate measurements yields heats of transition and surface free energies of crystals and mesophase layers, as well as the activation barrier per monomer associated with the chain stretching. According to the theory, the temperature dependence of the crystallization rate is determined by both the activation energy per monomer and the surface free energy of the preceding mesomorphic layer. Data indicate that the easiness of crystallization in polyethylene is first of all due to a particularly low surface free energy of the mesomorphic layer.