Stability of the A15 phase in diblock copolymer melts.

Bates, Morgan W; Lequieu, Joshua; Barbon, Stephanie M; Lewis, Ronald M; Delaney, Kris T; Anastasaki, Athina; Hawker, Craig J; Fredrickson, Glenn H et al. · Proc Natl Acad Sci U S A · 2019

basic_science · Level V

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Abstract

The self-assembly of block polymers into well-ordered nanostructures underpins their utility across fundamental and applied polymer science, yet only a handful of equilibrium morphologies are known with the simplest AB-type materials. Here, we report the discovery of the A15 sphere phase in single-component diblock copolymer melts comprising poly(dodecyl acrylate)-<i>block</i>-poly(lactide). A systematic exploration of phase space revealed that A15 forms across a substantial range of minority lactide block volume fractions (<i>f</i><sub>L</sub> = 0.25 - 0.33) situated between the σ-sphere phase and hexagonally close-packed cylinders. Self-consistent field theory rationalizes the thermodynamic stability of A15 as a consequence of extreme conformational asymmetry. The experimentally observed A15-disorder phase transition is not captured using mean-field approximations but instead arises due to composition fluctuations as evidenced by fully fluctuating field-theoretic simulations. This combination of experiments and field-theoretic simulations provides rational design rules that can be used to generate unique, polymer-based mesophases through self-assembly.