Tuning Diblock Copolymer Morphology by Adding Associative Homopolymers

Abstract

The ability to tune the microstructures formed by block copolymers using accessible physical approaches provides control for practical material applications. A common strategy involves the addition of homopolymers, which can induce morphological changes through their preferential partitioning into specific microdomains. More recently, supramolecular interactions - being chemistry-specific and stimuli-responsive - have emerged as powerful tools for enabling switchable morphologies. To gain microscopic insight into this process, we present a simulation study of diblock copolymers blended with homopolymers that selectively associate with one of the blocks via reversible associations. By varying the mode of association, we examine the structural changes induced by supramolecular complexation and compare them with those arising from Van der Waals (VDW) interactions. Our results reveal that, despite exhibiting similar levels of homopolymer partitioning, the lamellar structures differ significantly between the association-driven system and the VDW driven system. Cluster analysis indicates that only small clusters form at weak association strength, whereas a continuous network emerges under strong association conditions. Dynamic analysis further indicates that both morphology and supramolecular binding kinetics significantly influence the diffusion of homopolymers across microdomains, highlighting the material's potential responsiveness to external stimuli.