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.
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Materials for Water and Energy Systems (M-WET); Univ. of California, Santa Barbara, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Science Foundation (NSF)
- OSTI Identifier:
- 1526766
- Alternate Identifier(s):
- OSTI ID: 1594106
- Grant/Contract Number:
- SC0019001; SC0019272; AC02-06CH11357; DMR 1720256; CNS-1725797
- 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:
- National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; block copolymer; topological close packing; tetrahedral close packing; A15 phase
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. https://doi.org/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. https://doi.org/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 = {Mon Jun 17 00:00:00 EDT 2019},
month = {Mon Jun 17 00:00:00 EDT 2019}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1073/pnas.1900121116
https://doi.org/10.1073/pnas.1900121116
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 109 works
Citation information provided by
Web of Science
Web of Science
Figures / Tables:
Fig. 1: Left: SCFT simulations ($χN$ = 40) predict the A15 phase will be favored in AB diblock copolymers with sizeable conformational asymmetry, ε ≳2.1. Right: Illustration of the difference in pervaded block volumes that leads to large ε; poly(dodecyl acrylate)-block-poly(lactide) accentuates this effect.
All figures and tables
(4 total)
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
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
Renormalized one-loop theory of correlations in disordered diblock copolymers
journal, August 2011
- Qin, Jian; Grzywacz, Piotr; Morse, David C.
- The Journal of Chemical Physics, Vol. 135, Issue 8
Effect of Architecture on the Phase Behavior of AB-Type Block Copolymer Melts
journal, February 2012
- Matsen, M. W.
- Macromolecules, Vol. 45, Issue 4
Geometric Theory of Diblock Copolymer Phases
journal, July 2003
- Grason, Gregory M.; DiDonna, B. A.; Kamien, Randall D.
- Physical Review Letters, Vol. 91, Issue 5
50th Anniversary Perspective : Block Polymers—Pure Potential
journal, December 2016
- Bates, Christopher M.; Bates, Frank S.
- Macromolecules, Vol. 50, Issue 1
Sphericity and symmetry breaking in the formation of Frank–Kasper phases from one component materials
journal, November 2014
- Lee, Sangwoo; Leighton, Chris; Bates, Frank S.
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 50
Conformational Asymmetry and Quasicrystal Approximants in Linear Diblock Copolymers
journal, May 2017
- Schulze, Morgan W.; Lewis, Ronald M.; Lettow, James H.
- Physical Review Letters, Vol. 118, Issue 20
Fluctuation effects in the theory of microphase separation in block copolymers
journal, July 1987
- Fredrickson, Glenn H.; Helfand, Eugene
- The Journal of Chemical Physics, Vol. 87, Issue 1
Universality of Block Copolymer Melts
journal, August 2014
- Glaser, Jens; Medapuram, Pavani; Beardsley, Thomas M.
- Physical Review Letters, Vol. 113, Issue 6
Geometry induced sequence of nanoscale Frank–Kasper and quasicrystal mesophases in giant surfactants
journal, November 2016
- Yue, Kan; Huang, Mingjun; Marson, Ryan L.
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 50
Monte Carlo Field-Theoretic Simulations for Melts of Symmetric Diblock Copolymer
journal, September 2013
- Stasiak, P.; Matsen, M. W.
- Macromolecules, Vol. 46, Issue 19
Conformationally asymmetric block copolymers
journal, April 1997
- Matsen, M. W.; Bates, F. S.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 35, Issue 6, p. 945-952
Polyisoprene-Polystyrene Diblock Copolymer Phase Diagram near the Order-Disorder Transition
journal, December 1995
- Khandpur, Ashish K.; Foerster, Stephan; Bates, Frank S.
- Macromolecules, Vol. 28, Issue 26
An experimental realization of the Weaire–Phelan structure in monodisperse liquid foam
journal, January 2012
- Gabbrielli, Ruggero; Meagher, Aaron J.; Weaire, Denis
- Philosophical Magazine Letters, Vol. 92, Issue 1
Complex alloy structures regarded as sphere packings. II. Analysis and classification of representative structures
journal, July 1959
- Frank, F. C.; Kasper, J. S.
- Acta Crystallographica, Vol. 12, Issue 7
Mesophase Structure-Mechanical and Ionic Transport Correlations in Extended Amphiphilic Dendrons
journal, September 2004
- Cho, B. -K.
- Science, Vol. 305, Issue 5690
Rational Design of the First Spherical Supramolecular Dendrimers Self-Organized in a Novel Thermotropic Cubic Liquid-Crystalline Phase and the Determination of Their Shape by X-ray Analysis
journal, February 1997
- Balagurusamy, V. S. K.; Ungar, G.; Percec, V.
- Journal of the American Chemical Society, Vol. 119, Issue 7
A counter-example to Kelvin's conjecture on minimal surfaces
journal, February 1994
- Weaire, D.; Phelan, R.
- Philosophical Magazine Letters, Vol. 69, Issue 2
Stable Frank–Kasper phases of self-assembled, soft matter spheres
journal, September 2018
- Reddy, Abhiram; Buckley, Michael B.; Arora, Akash
- Proceedings of the National Academy of Sciences, Vol. 115, Issue 41
Thermal processing of diblock copolymer melts mimics metallurgy
journal, May 2017
- Kim, Kyungtae; Schulze, Morgan W.; Arora, Akash
- Science, Vol. 356, Issue 6337
Cornucopia of Nanoscale Ordered Phases in Sphere-Forming Tetrablock Terpolymers
journal, April 2016
- Chanpuriya, Siddharth; Kim, Kyungtae; Zhang, Jingwen
- ACS Nano, Vol. 10, Issue 5
Selective assemblies of giant tetrahedra via precisely controlled positional interactions
journal, April 2015
- Huang, M.; Hsu, C. -H.; Wang, J.
- Science, Vol. 348, Issue 6233
Elektrolysen in Phosphatschmelzen. I. Die elektrolytische Gewinnung von ?- und ?-Wolfram
journal, May 1931
- Hartmann, Hellmuth; Ebert, Fritz; Bretschneider, Otto
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 198, Issue 1
Existence of fcc-Packed Spherical Micelles in Diblock Copolymer Melt
journal, February 2007
- Huang, Yen-Yu; Hsu, Jen-Yung; Chen, Hsin-Lung
- Macromolecules, Vol. 40, Issue 3
Thermodynamics and phase behavior of acid-tethered block copolymers with ionic liquids
journal, January 2017
- Jung, Ha Young; Park, Moon Jeong
- Soft Matter, Vol. 13, Issue 1
Inverse Pm3̄n cubic micellar lyotropic phases from zwitterionic triazolium gemini surfactants
journal, January 2013
- Perroni, Dominic V.; Mahanthappa, Mahesh K.
- Soft Matter, Vol. 9, Issue 33
Polymer Electrolytes
journal, July 2013
- Hallinan, Daniel T.; Balsara, Nitash P.
- Annual Review of Materials Research, Vol. 43, Issue 1
Melt Chain Dimensions of Polylactide
journal, March 2004
- Anderson, Kelly S.; Hillmyer, Marc A.
- Macromolecules, Vol. 37, Issue 5
Orthorhombic Fddd Network in Diblock Copolymer Melts
journal, June 2007
- Takenaka, Mikihito; Wakada, Tsutomu; Akasaka, Satoshi
- Macromolecules, Vol. 40, Issue 13
Conformational Asymmetry and Polymer-Polymer Thermodynamics
journal, July 1994
- Bates, Frank S.; Fredrickson, Glenn H.
- Macromolecules, Vol. 27, Issue 4
Role of Chain Length in the Formation of Frank-Kasper Phases in Diblock Copolymers
journal, November 2018
- Lewis, Ronald M.; Arora, Akash; Beech, Haley K.
- Physical Review Letters, Vol. 121, Issue 20
Polymer-Polymer Phase Behavior
journal, February 1991
- Bates, Frank S.
- Science, Vol. 251, Issue 4996, p. 898-905
From structure to function via complex supramolecular dendrimer systems
journal, January 2015
- Sun, Hao-Jan; Zhang, Shaodong; Percec, Virgil
- Chemical Society Reviews, Vol. 44, Issue 12
Discovery of a Frank-Kasper Phase in Sphere-Forming Block Copolymer Melts
journal, October 2010
- Lee, S.; Bluemle, M. J.; Bates, F. S.
- Science, Vol. 330, Issue 6002
Ion Transport in Nanostructured Phosphonated Block Copolymers Containing Ionic Liquids
journal, April 2016
- Jung, Ha Young; Kim, Onnuri; Park, Moon Jeong
- Macromolecular Rapid Communications, Vol. 37, Issue 14
Chain Architecture and Asymmetry in Copolymer Microphases
journal, April 1994
- Milner, Scott T.
- Macromolecules, Vol. 27, Issue 8
Recent Developments in Fully Fluctuating Field-Theoretic Simulations of Polymer Melts and Solutions
journal, July 2016
- Delaney, Kris T.; Fredrickson, Glenn H.
- The Journal of Physical Chemistry B, Vol. 120, Issue 31
Complex alloy structures regarded as sphere packings. I. Definitions and basic principles
journal, March 1958
- Frank, F. C.; Kasper, J. S.
- Acta Crystallographica, Vol. 11, Issue 3
A15-type superconductors
journal, May 1980
- Muller, J.
- Reports on Progress in Physics, Vol. 43, Issue 5
σ Phase Formed in Conformationally Asymmetric AB-Type Block Copolymers
journal, August 2014
- Xie, Nan; Li, Weihua; Qiu, Feng
- ACS Macro Letters, Vol. 3, Issue 9
Interfaces in Diblocks: A Study of Miktoarm Star Copolymers
journal, September 2004
- Grason, Gregory M.; Kamien, Randall D.
- Macromolecules, Vol. 37, Issue 19
Stability of the Gyroid Phase in Diblock Copolymers at Strong Segregation
journal, April 2006
- Cochran, Eric W.; Garcia-Cervera, Carlos J.; Fredrickson, Glenn H.
- Macromolecules, Vol. 39, Issue 7
PCHE-based pentablock copolymers: Evolution of a new plastic
journal, April 2001
- Bates, Frank S.; Fredrickson, Glenn H.; Hucul, Dennis
- AIChE Journal, Vol. 47, Issue 4
Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.