Structure and Energetics of Grain Boundaries in Self-Assembled Double-Gyroid Block Copolymer Networks

Abstract

Grain boundaries (GBs) are ubiquitous defects in crystalline materials but remain less explored in block copolymer ordered phases. Here, we develop a self-consistent field theory framework to investigate GB structure and energetics in double-gyroid (DG) diblock copolymer networks. Two energy landscapes are obtained for tilt and twist GBs as functions of GB orientations, revealing multiple local minima. The lowest-energy GB among the sampled GBs is an asymmetric-tilt network-switching GB ([1̄1̄1] ATNS) rather than the experimentally observed (422) twin boundary (TB) among the sampled GBs. Comparative analyses of tilt ([1̄1̄1], [100] ATNS) and twist ((422) TB, [01̄1̄] TNS) GBs reveal that, unlike enthalpy-dominated hard matter, GB stability in DG networks is entropy-driven. Twist-type GBs generate new nodes and disrupt nodal coplanarity, causing chain-packing frustration and entropy penalties. Although the [100] ATNS does not generate new nodes, its disruption of nodal coplanarity still incurs large entropy penalties. Conversely, the [1̄1̄1] ATNS preserves favorable network connectivity and minimizes conformational constraints, making it the energetically preferred GB.