Reversible cross-linking facilitates the formation of critical nucleus in binary polymer blends

Using self-consistent field theory, we study the effect of reversible cross-linking on the nucleation behavior of a binary polymer blend where only one of the components is able to form cross-links. To control the total number of cross-links and their distribution, we introduce a position-dependent cross-linking probability function that is characterized mainly by two parameters, the magnitude and the width. In the weakly cross-linked region, where the product of the magnitude and width, I, is small, the nucleation behavior is classical-like and the profile of the free energy excess is unimodal. In contrast, in the strongly cross-linked region, the profile of the free energy excess becomes bimodal, and the free energy minimum specifies a metastable nucleus. In a certain I, the free energy barrier for the metastable nucleus turns to be negative, which means it becomes more stable. In both cases, the free energy barrier of the critical nucleus is lower than that without cross-linking, indicating that cross-linking always facilitates nucleation although the dynamic behavior may be different when a metastable nucleus is involved during the nucleation process. The free energy analysis demonstrates that the interaction energy rather than the entropy is responsible for the properties of the critical nucleus. Our study provides an easy alternative way for the control of the nucleation behavior and may attract practical interest.