Details of Structure Formation During the Induction Period of Spinodal-Type Polymer Crystallization

An unexpected type of primary crystal nucleation is described, involving spinodal decomposition (SD) type microphase separation due to the orientation fluctuations of rigid segments prior to crystal nucleation. This type of mechanism was found by the present authors about 10 years ago, and recently, it was theoretically revealed by Olmsted et al. to be one of three types of primary crystal nucleation: the well-known homogeneous crystal nucleation directly from the liquid–crystal coexistence domain, which occurs at higher temperatures above the binodal temperature T b , crystal nucleation after binodal microphase separation between T b and spinodal temperature T s , and that after SD below T s . The detailed experimental results for the spinodal-type crystal nucleation, especially the temperature dependence of characteristic wavelength in SD, are explained as well.