Polymer Melting Kinetics Appears to be Driven by Heterogeneous Nucleation

Abstract

A recently proposed method is used to parameterize the nucleation‐driven kinetics of poly( ε ‐caprolactone) melting. The method is based on fitting a theoretically derived temperature dependence of the effective activation energy to the experimental dependence obtained from the Kissinger plot. Although the theoretical dependence fits the experimental one accurately, the fit gives rise to a surface free energy that is significantly smaller than the one obtained from crystallization data. A similar result is reported in other publications that make use of a homogeneous nucleation model for poly­mer melting. It is argued that a heterogeneous nucleation model is a more appropriate representation of the melting process and that its use resolves the problem of estimating the unusually small surface free energies. image