Crystallization kinetics of dilute polyethylene solutions

The crystallization kinetics of a high molecular weight fraction of linear polyethylene was studied in dilute solutions of p ‐xylene, n ‐hexadecane, and decalin by dilatometric methods. For all solvents and temperatures, the experimental isotherms could be quantitatively described by the Avrami formulation for the complete transformation. This result is unique in the realm of polymer crystallization, since marked deviations from this theory are usually observed in more concentrated systems. The Avrami exponent is found to be n = 4 in all cases. The temperature coefficients of the rate constants are indicative of a nucleation controlled process. The data fit either a two‐dimensional or three‐dimensional nucleation mode, and a discrimination can not be made between these two cases. The interfacial free energies are found to be independent of the solvent medium. It is also shown that, irrespective of the type of nucleation control governing the kinetics, the same type governs the crystallite thickness of the lamella‐like crystals that are formed.