Polymer Melting Kinetics Appears to be Driven by Heterogeneous Nucleation

摘要

A recently proposed method is used to parameterize the nucleation-driven kinetics of poly(ε -caprolactone) melting. The method is based on fi tting a theoretically derived temperature dependence of the effective activation energy to the experimental dependence obtained from the Kissinger plot. Although the theoretical dependence fi ts the experimental one accurately, the fi t gives rise to a surface free energy that is signifi cantly 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 poly mer 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.