Rough‐surface crystallization: Some applications to poly(ethylene oxide)

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Abstract
A model incorporating a rough (disordered) crystal growth surface is capable of treating many of the observations and measurements on the crystal growth of short chains of poly(ethylene oxide) from the melt. A simple preliminary treatment if presented which aims primarily to analyze the growth rate data within one growth “branch,” i.e., for a regime in which crystal thickness is approximately constant. Under these conditions the growth rate is approximately linear with crystallization temperature, as expected for rough growth surfaces, but not for smooth (faceted) ones. Simulation results are included which are in agreement with a simple equation and with experiment. The analysis enables the growth rates for different branches to be compared in a systematic way. A very steep decrease in growth rate with increasing crystal thickness is clearly illustrated, together with some influence of molecular weight. The general trend for chain folding can be seen as a consequence of this steep decrease. Parallel work on systems in which crystal thicknesses vary continuously with crystallization temperature led to the realization that “rounding off” will occur at the crystal perimeter and that this will give rise to an entropic barrier for the crystal advance. This argument is presented in the context of extended‐chain and once‐folded crystallization, from which it is clear that growth rates should be much lower as crystal thicknesses increase, and for folded‐chain as compared with extended‐chain crystals. Different morphologies are interpreted in terms of changes in surface structure which are probably due to kinetic as well as equilibrium effects.