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Title: 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 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.

Authors:
; ; ; ; ; ; ; ; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1526766
Grant/Contract Number:  
SC0019001; SC0019272
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 116 Journal Issue: 27; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Bates, Morgan W., Lequieu, Joshua, Barbon, Stephanie M., Lewis, III, Ronald M., Delaney, Kris T., Anastasaki, Athina, Hawker, Craig J., Fredrickson, Glenn H., and Bates, Christopher M. Stability of the A15 phase in diblock copolymer melts. United States: N. p., 2019. Web. doi:10.1073/pnas.1900121116.
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. Stability of the A15 phase in diblock copolymer melts. United States. doi:10.1073/pnas.1900121116.
Bates, Morgan W., Lequieu, Joshua, Barbon, Stephanie M., Lewis, III, Ronald M., Delaney, Kris T., Anastasaki, Athina, Hawker, Craig J., Fredrickson, Glenn H., and Bates, Christopher M. Mon . "Stability of the A15 phase in diblock copolymer melts". United States. doi:10.1073/pnas.1900121116.
@article{osti_1526766,
title = {Stability of the A15 phase in diblock copolymer melts},
author = {Bates, Morgan W. and Lequieu, Joshua and Barbon, Stephanie M. and Lewis, III, Ronald M. and Delaney, Kris T. and Anastasaki, Athina and Hawker, Craig J. and Fredrickson, Glenn H. and Bates, Christopher M.},
abstractNote = {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.},
doi = {10.1073/pnas.1900121116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 27,
volume = 116,
place = {United States},
year = {2019},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1900121116

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Works referenced in this record:

Block Copolymer Lithography
journal, November 2013

  • Bates, Christopher M.; Maher, Michael J.; Janes, Dustin W.
  • Macromolecules, Vol. 47, Issue 1, p. 2-12
  • DOI: 10.1021/ma401762n

Conformationally asymmetric block copolymers
journal, April 1997


Polymer-Polymer Phase Behavior
journal, February 1991