Medial packing and elastic asymmetry stabilize the double-gyroid in block copolymers

TL;DR

This paper introduces a geometric framework based on medial packing and elastic asymmetry to explain the thermodynamic stability of the double-gyroid phase in block copolymer melts, resolving previous contradictions and expanding understanding of complex self-assembled structures.

Contribution

It develops a geometric formulation of strong stretching theory incorporating medial maps, revealing new stability conditions for the double-gyroid phase in block copolymers.

Findings

Medial packing is crucial for double-gyroid stability.

Elastic asymmetry non-monotonically affects phase stability.

The stability window of double-gyroid widens with elastic asymmetry.

Abstract

Triply-periodic networks are among the most complex and functionally valuable self-assembled morphologies, yet they form in nearly every class of biological and synthetic soft matter building blocks. In contrast to simpler assembly motifs -- spheres, cylinders, layers -- TPN assemblies require molecules to occupy variable local domain shapes, confounding attempts to understand their formation. Here, we examine the double-gyroid (DG) network phase of block copolymer (BCP) melts, a prototypical soft self-assembly system, by using a geometric formulation of the strong stretching theory (SST) of BCP melts. The theory establishes the direct link between molecular BCP packing, thermodynamics of melt assembly and the {\it medial map}, a generic geometric measure of the center of complex shapes. We show that "medial packing" is essential for thermodynamic stability of DG in strongly-segregated melts, reconciling a long-standing contradiction between infinite- and finite-segregation theories, corroborating our SST predictions at finite-segregation via self-consistent field calculations. Additionally, we find a previously unrecognized non-monotonic dependence of DG stability on the elastic asymmetry, the comparative entropic stiffness of matrix-forming to tubular-network forming blocks. The composition window of stable DG -- intermediate to competitor lamellar and columnar phases -- widens both for large and small elastic asymmetry, seemingly overturning the heuristic view that packing frustration is localized to the tubular domains. This study demonstrates utility of geometric optimization of {\it medial tesselations} for understanding in soft-molecular assembly. As such, the particular medial-based approach deployed here is readily generalizable to study packing frustration far beyond the case of DG morphologies in neat BCP assemblies.