Spinodal patterns indicating unstable regime of polymer crystallization

It has been considered that crystallization of polymer from melt proceeds via the coexistence of molten matrix and growing crystals that have once overcome a nucleation barrier to a critical size. The nucleation process has often been explained analogously with so-called nucleation and growth (NG) behavior of the phase separation of a binary mixture in metastable conditions, although the crystallization in one-component polymer is not a real component separation but a phase transition. Among the mechanisms of polymer crystallization, the topic is whether a liquid–liquid transition between states of different densities within one-component polymers takes place before the aforementioned nucleation process. The liquid–liquid transition between states, which is probably driven by chain orientation, is also categorized into NG and the controversial spinodal decomposition (SD) type processes depending on the quenching depth. This article provides the optical microscopic observations that favor the occurrence of the SD-like process when a one-component polymer melt is very rapidly quenched below a stability limit, including a drastic morphological change from a spherulitic to a spinodal pattern at the critical (or spinodal) temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1817–1822, 2004