Epitaxial orientation and localized microphase separation prior to formation of nanohybrid shish-kebabs induced by one-dimensional nanofiller in miscible diblock copolymers with selective interaction

The incorporation of nanofillers can result in the changes of crystallization behaviors of block copolymers. We performed dynamic Monte Carlo simulations to investigate the crystallization behaviors induced by one-dimensional nanofiller in miscible diblock copolymers with selective interaction. The addition of nanofiller significantly improves the crystallizability of block copolymers by inducing heterogeneous nucleation on its surface. In addition, the presence of nanofiller leads to the formation of a novel nanohybrid epitaxial brush structure, which consists of a central nanofiller and surrounding “bristles” formed by lamellar crystals of crystallizable blocks with random coils of non-crystallizable blocks. During the formation of this hierarchical structure, the orientation of local crystallizable segments along the long axis of the nanofiller, as well as the local microphase separation between crystallizable and non-crystallizable blocks, both occur prior to crystallization.