Stability of the A15 phase in diblock copolymer melts

Bates, Morgan W.; Lequieu, Joshua; Barbon, Stephanie M.; Lewis, III, Ronald M.; Delaney, Kris T.; Anastasaki, Athina; Hawker, Craig J.; Fredrickson, Glenn H.; Bates, Christopher M.

doi:10.1073/pnas.1900121116

Title: Stability of the A15 phase in diblock copolymer melts

Journal Article · 16 June 2019 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.1900121116 · OSTI ID:1526766

Bates, Morgan W.; Lequieu, Joshua; Barbon, Stephanie M.; Lewis, III, Ronald M.; Delaney, Kris T.; Anastasaki, Athina; Hawker, Craig J.; Fredrickson, Glenn H.;

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)− block −poly(lactide). A systematic exploration of phase space revealed that A15 forms across a substantial range of minority lactide block volume fractions ( f _L = 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.

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Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division; National Science Foundation

Grant/Contract Number:: SC0019001; SC0019272; AC02-06CH11357

OSTI ID:: 1526766

Alternate ID(s):: OSTI ID: 1545879; OSTI ID: 1594106

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 27 Vol. 116; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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