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Stability of the A15 phase in diblock copolymer melts.


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)-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 ?-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.

SUBMITTER: Bates MW 

PROVIDER: S-EPMC6613078 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature

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Stability of the A15 phase in diblock copolymer melts.

Bates Morgan W MW   Lequieu Joshua J   Barbon Stephanie M SM   Lewis Ronald M RM   Delaney Kris T KT   Anastasaki Athina A   Hawker Craig J CJ   Fredrickson Glenn H GH   Bates Christopher M CM  

Proceedings of the National Academy of Sciences of the United States of America 20190617 27


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 la  ...[more]

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