Emergence of Hexagonally Close-Packed Spheres in Linear Block Copolymer Melts

The hexagonally close-packed (HCP) sphere phase is predicted to be stable across a narrow region of linear block copolymer phase space, but the small free energy difference separating it from face-centered cubic spheres usually results in phase coexistence. Here, we report the discovery of pure HCP spheres in linear block copolymer melts with A = poly(2,2,2-trifluoroethyl acrylate) (F) and B = poly(2-dodecyl acrylate) (2D) or poly(4-dodecyl acrylate) (4D). In 4DF diblocks and F4DF triblocks, the HCP phase emerges across a substantial range of A-block volume fractions (circa f(A) = 0.25-0.30), and in F4DF, it forms reversibly when subjected to various processing conditions which suggests an equilibrium state. The time scale associated with forming pure HCP upon quenching from a disordered liquid is intermediate to the ordering kinetics of the Frank-Kasper sigma and A15 phases. However, unlike sigma and A15, HCP nucleates directly from a supercooled liquid or soft solid without proceeding through an intermediate quasicrystal. Self-consistent field theory calculations indicate the stability of HCP is intimately tied to small amounts of molar mass dispersity (D); for example, an HCP-forming F4DF sample with f(A) = 0.27 has an experimentally measured D = 1.04. These insights challenge the conventional wisdom that pure HCP is difficult to access in linear block copolymer melts without the use of blending or other complex processing techniques.

Automated summary

The study reveals the presence of pure HCP sphere phase in specific linear block copolymer melts, challenging the conventional belief that pure HCP is difficult to access without complex processing techniques.