Crystallization kinetics of linear polyethylene: The maximum in crystal growth rate–temperature dependence

This rapid communication reports a summary of the key findings of crystallization kinetics studies of unfractionated high density (linear) polyethylene at extremely large supercoolings. We report, for the first time, the maximum in crystal growth rate–crystallization temperature data for linear polyethylene, which has been sought by many researchers since the 1950s. The maximum growth rate was found to occur in the range of 70–75 °C with two separate methods. The kinetics studies were performed using a newly developed quench-crystallization technique based on depolarized reflection light microscopy that is capable of achieving enormously higher quench rates than existing methods. Typical onset crystallization temperatures accessed with this technique range from 40 to 90 °C. Bulk growth rates of crystals were obtained as the reciprocal of crystallization half times measured from the change in the depolarized light intensity upon direct crystallization from the melt. Separately, radial growth rates of spherulites were measured over a wide range of supercoolings. Secondary nucleation analysis of the crystal growth rates resulted in single linear fits extending into deep regime III, suggesting no change in mechanism of formation of the crystals at the largest supercoolings. The deeply quenched films, crystallized at temperatures below the maximum, contain non-impinged spherulites, capable of further crystallization.